CN103714874A - Method and device for processing radioactive strontium-contained waste water - Google Patents
Method and device for processing radioactive strontium-contained waste water Download PDFInfo
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- CN103714874A CN103714874A CN201410009260.5A CN201410009260A CN103714874A CN 103714874 A CN103714874 A CN 103714874A CN 201410009260 A CN201410009260 A CN 201410009260A CN 103714874 A CN103714874 A CN 103714874A
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Abstract
The invention relates to a method and device for processing radioactive strontium-contained waste water. Chemical reactions are achieved between the radioactive strontium-contained waste water in a hydrocyclone and calcium carbonate seed crystals through hydrocycolone stirring and between the radioactive strontium-contained waste water in the hydrocyclone and sodium carbonate through hydrocycolone stirring, and therefore strontium carbonate is deposited on the surfaces of the calcium carbonate seed crystals and forms large-grain-size tight crystal particulate matter, and the large-grain-size tight crystal particulate matter rapidly sedimentates at the bottom of the hydrocyclone so that a part of radioactive strontium ions can be removed; small-grain-size strontium carbonate and small-grain-size seed crystals enter a membrane separator along with the supernatant to react with ferric chloride, the radioactive strontium ions are further removed after the particulate matter is separated through a hollow fibrous membrane, and therefore the radioactivity of discharged water is greatly lowered. The particulate matter formed through the method is large in grain size, compact in structure and good in sedimentation performance, the defects that the chemical precipitation method is low in decontamination factor and large in mud production amount are effectively overcome, the disadvantage that the membrane is seriously contaminated in the membrane separation process is also eliminated, and the method for processing the radioactive strontium-contained waste water is economical and practical.
Description
Technical field
The present invention relates to a kind of Spent Radioactive water technology, is exactly from waste water, to remove radiostrontium ion.
Background technology
Radiostrontium (
90sr and
89sr) be by
235u and
239pu nuclear fission produces, and is extensively present in radioactive wastewater.In March, 2011, Fukushima, Japan nuclear power station leaked because earthquake causes radiomaterial, contained a large amount of radiostrontiums in the waste water of discharge.
90the Sr half life period reaches 28.9, and bio-toxicity is strong, is gathered in skeleton and is difficult to discharge, and therefore it need to be removed from radioactive wastewater, with protection of the environment and health.
Chemical precipitation method technological process is simple, easy to operate, and operating cost is low, and being applicable to strontium concentration is the Spent Radioactive water treatment of constant or trace; Yet, mud particle diameter that chemical precipitation method forms is little, settling property is poor, thereby the mud volume production of the method is large, the cycles of concentration ratio of remaining radioactivity sludge volume (the radioactive wastewater cumulative volume of processing with) is only 10-20, and decontamination factor (ratio of former water-borne radioactivity strontium activity concentration and water outlet radiostrontium activity concentration) is only 10-100, the strontium ion clearance in radioactive wastewater is lower.Chemical precipitation-micro-filtration (or ultrafiltration) group technology, although solved the shortcoming of Separation of Solid and Liquid difficulty in chemical precipitation method, is enhanced cycles of concentration, and its cost is to cause serious film to pollute, and the amplitude that decontamination factor increases is limited.
While adopting chemical precipitation method or chemical precipitation-micro-filtration (or ultrafiltration) group technology to process the lower waste water of radiostrontium ion concentration, according to solubility product principle, for reaching identical radiostrontium ion remaval effect, need to enlarge markedly the dosage of precipitation agent.For this problem, conventionally in radiotropism waste water, add inactive strontium ion, utilize radiostrontium ion and on-radiation strontium ion to there is the feature of identical chemical property, make radiostrontium ion and on-radiation strontium ion precipitate removal simultaneously, thereby reduce the dosage of precipitation agent.
Compare with the conventional chemical precipitation method, although mechanical raking coprecipitation has improved cycles of concentration and decontamination factor, the amplitude improving is not remarkable, and the plant equipment increasing improves radiation proof requirement, and operation, maintenance, operational management are difficult.It is higher that reverse osmosis technology removes strontium operating cost; Ion-exchange and continuous electric desalination have strict restriction to waste water salt content, and the former can produce a large amount of radioactive spent resins, cause follow-up Solid Waste Treatment difficulty, expense higher, and the latter's power consumption are higher.
Summary of the invention
For problems of the prior art, the method that the present invention proposes hydraulic cyclone stirring and Middle hollow fiber membrane coupling removes the radiostrontium ion in waste water.Adopt hydraulic cyclone to stir and micro-filtration (or ultrafiltration) coupling, expense is low, simple to operation, automaticity is high, both can make to form large particle diameter, structure is closely knit, settling property is good particle containing strontium mud, having reduced the pollution of follow-up microfiltration membranes (or ultra filtration membrane), improved again decontamination factor and the cycles of concentration of strontium, is that a kind of economical and practical radioactive wastewater is except strontium method.
The method makes the radioactivity in hydraulic cyclone reactor be stirred and be carried out chemical reaction by hydraulic cyclone containing strontium waste water and calcium carbonate crystal seed, sodium carbonate, strontium carbonate is deposited at calcium carbonate seed surface, form the closely knit crystal grain thing rapid precipitation of large particle diameter to hydraulic cyclone bottom, to remove part radiostrontium ion; Short grained strontium carbonate and crystal seed enter membrane separator with supernatant, and react with iron chloride, and particle is further removed radiostrontium ion after Middle hollow fiber membrane, and the radioactivity of water outlet is significantly reduced.
Technical scheme of the present invention is as follows:
Radioactivity is containing a disposal route for strontium waste water, and step is as follows:
1) add crystal seed: the calcium carbonate crystal seed of preparing in advance to the disposable 300-800mg/L of adding of hydraulic cyclone reactor, before hydraulic cyclone reactor is emptying, no longer adds crystal seed;
2) hydraulic mixing pre-service: the sodium carbonate that adds 1000mg/L to hydraulic cyclone reactor, make strontium ion and calcium carbonate crystal seed, sodium carbonate in radioactive wastewater stir and generate large particle diameter compact grain thing by hydraulic cyclone, deposit to hydraulic cyclone reactor bottom;
3) radioactive wastewater of processing enters membrane separator, adds with Fe simultaneously
3+the molysite 3.0mg/L of meter continues reaction and generates particle, water outlet after Middle hollow fiber membrane under aeration agitation effect.
In described radioactive wastewater, the mass concentration of strontium ion is 5-10mg/L.
Described radioactivity is 45-60 minute containing the residence time of strontium waste water in hydraulic cyclone reactor.
Described radioactivity is 45-60 minute containing the residence time of strontium waste water in membrane separator.
Radioactivity of the present invention is containing the treating apparatus of strontium waste water, and wastewater storage tank 1 is connected to the import of hydraulic cyclone reactor 3 cone bases, 3 supernatant pipeline junctional membrane separation vessel 6 imports of hydraulic cyclone reactor through lift pump 2 and flow of inlet water meter 14; Hollow-fibre membrane 7 rising pipes in membrane separator 6 are connected with solenoid valve 13 with water flow meter 16 through going out water pump 11; Sodium carbonate medicine storing drum 5 is connected to the feeding opening of hydraulic cyclone reactor 3 cone bases through SODIUM PERCARBONATE dosing pump 4, iron chloride medicine storing drum 10 is connected to the feeding opening of membrane separator 6 through iron chloride dosing pump 9, fan blower 8 is connected to the air intake opening of membrane separator bottom through air flowmeter 15.Liquid level gauge 12 is arranged on the top of membrane separator 6.
Described hydraulic cyclone reactor is comprised of cone and right cylinder, and cone angle is 38 ° ± 2 °, and cone and cylindrical volume ratio are 1:3.
Described hollow-fibre membrane is microfiltration membranes or ultra filtration membrane conventional in water treatment.
Beneficial effect of the present invention is: by enforcement of the present invention, can significantly improve decontamination factor and the cycles of concentration of radiostrontium, when improving strontium removal effect, reduce the output of radioactive waste, reduce the potential hazard of radioactive contamination to environment and the public.Reactor based on the method can be designed to fixed or wheeled apparatus as required, design scale also can be chosen flexibly, while being applicable to nuclear facilities containing strontium wastewater treatment and burst nuclear pollution, the emergency processing of waste water, has a extensive future, obvious environment benefit.
Accompanying drawing explanation
Fig. 1: be the present invention: Experimental equipment.
In figure: 1-wastewater storage tank; 2-lift pump; 3-hydraulic cyclone reactor; 4-sodium carbonate dosing pump; 5-sodium carbonate medicine storing drum; 6-membrane separator; 7-hollow fiber mocromembrane; 8-fan blower; 9-iron chloride dosing pump; 10-iron chloride medicine storing drum; 11-goes out water pump; 12-liquid level gauge; 13-solenoid valve; 14-flow of inlet water meter; 15-air flowmeter; 16-water flow meter.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the present invention are described.It should be noted that the present embodiment is narrative, rather than determinate, with this embodiment, do not limit protection scope of the present invention.
The device of example of the present invention is shown in accompanying drawing.Wastewater storage tank size Φ * H=1100 * 2150mm; Hydraulic cyclone reactor bottom is cone, 38 ° of cone angles, height 260mm; Top is right cylinder Φ * H=200 * 300mm; Membrane separator Φ * H=120 * 150mm, is equipped with 1 hollow fiber microfiltration membrane assembly, and nominal pore size is 0.22 μ m, and useful area is 0.5m
2, intake pump is peristaltic pump with going out water pump, water inlet, water outlet, air flowmeter are spinner-type flowmeter.Device employing PLC(Programmable Logic Controller) control, fully automatic operation, PLC adopts current techique programming.Device for every day 24h move continuously, wherein hydraulic cyclone reactor be continuously water inlet, membrane separator is water outlet at intermittence, in the circulation of every 10 minutes, water outlet 9 minutes, empty aeration 1 minute.
Specific operation process is: before when device starts, in simulated emission wastewater storage tank 1, add strontium chloride, preparation is set the simulated emission of concentration containing strontium waste water.When device starts, to the disposable calcium carbonate crystal seed of preparation in advance that adds of hydraulic cyclone reactor 3.Then under PLC controls, lift pump 2 contains strontium waste water from wastewater storage tank 1 suction, current tangentially enter the bottom of hydraulic cyclone reactor 3, sodium carbonate dosing pump 4 adds hydraulic cyclone reactor 3 bottoms by the sodium carbonate in sodium carbonate medicine storing drum 5 simultaneously, containing strontium waste water, crystal seed and sodium carbonate, under hydraulic cyclone beating action, mutually collide, react, form large particle diameter, the particle that closely knit, settling property is good, be deposited to gradually the bottom of hydraulic cyclone reactor 3, supernatant gravity flow enters membrane separator 6.For slowing down the pollution of hollow fiber mocromembrane 7, fan blower 8 to membrane separator 6 aerations so that air stirring to be provided, iron chloride dosing pump 9 adds membrane separator 6 by the iron chloride in iron chloride medicine storing drum 10 simultaneously, small particle in mixed liquor is further reacted and forms bulky grain floc unit, through 7 separation of hollow fiber mocromembrane, go out water pump 11 suctions after water outlet.Liquid level gauge 12 is for controlling out the start and stop of water pump 11 and the keying of solenoid valve 13.Flow of inlet water meter 14 is for controlling the flow of inlet water of hydraulic cyclone reactor, and air flowmeter 14 is for the aeration rate of controlling diaphragm separation vessel 6, and water flow meter 15 is for controlling the water flow of hollow-fibre membrane 7.
Embodiment 1: the flow of device is 16.6L/h, and total residence time is 90 minutes, and wherein the residence time of hydraulic cyclone reactor is 45 minutes, and the hydraulic detention time of membrane separator is 45 minutes.Utilize the simulated emission that this device place strontium concentration is 5mg/L to contain strontium waste water.Experiment adds the calcium carbonate crystal seed that 300mg/L is prepared in advance while starting in hydraulic cyclone reactor; In experiment, sodium carbonate dosage is that 1000mg/L, iron chloride dosage are that 3.0mg/L(is with Fe
3+meter), time, water outlet strontium mass concentration is stabilized in 5 μ g/L.The cycles of concentration of this technique is 3150, and decontamination factor is 1000.
Embodiment 2: the flow of device is 12.5L/h, and total residence time is 120 minutes, and wherein the residence time of hydraulic cyclone reactor is 60 minutes, and the hydraulic detention time of membrane separator is 60 minutes.Utilize this device to process the simulated emission that strontium concentration is 10mg/L and contain strontium waste water.Experiment adds the calcium carbonate crystal seed that 800mg/L is prepared in advance while starting in hydraulic cyclone reactor; In experiment, sodium carbonate dosage is that 1000mg/L, iron chloride dosage are that 3.0mg/L(is with Fe
3+meter), time, water outlet strontium mass concentration is stabilized in 7 μ g/L.The cycles of concentration of this technique is 3400, and decontamination factor is 1400.
Embodiment 3: the flow of device is 15L/h, and total residence time is 100 minutes, and wherein the residence time of hydraulic cyclone reactor is 50 minutes, and the hydraulic detention time of membrane separator is 50 minutes.Utilize this device to process the simulated emission that strontium concentration is 8mg/L and contain strontium waste water.Experiment adds the calcium carbonate crystal seed that 500mg/L is prepared in advance while starting in hydraulic cyclone reactor; In experiment, sodium carbonate dosage is that 1000mg/L, iron chloride dosage are that 3.0mg/L(is with Fe
3+meter), time, water outlet strontium mass concentration is stabilized in 6 μ g/L.The cycles of concentration of this technique is 3200, and decontamination factor is 1300.
Embodiment 4: the flow of device is 16.6L/h, and total residence time is 90 minutes, and wherein the residence time of hydraulic cyclone reactor is 45 minutes, and the hydraulic detention time of membrane separator is 45 minutes.Utilize the simulated emission that this device place strontium concentration is 5mg/L to contain strontium waste water.Experiment adds the calcium carbonate crystal seed that 300mg/L is prepared in advance while starting in hydraulic cyclone reactor; In experiment sodium carbonate dosage be 1000mg/L, while not adding iron chloride, water outlet strontium mass concentration is stabilized in 7 μ g/L.The cycles of concentration of this technique is 2800, and decontamination factor is 710.
Claims (7)
1. radioactivity, containing a disposal route for strontium waste water, is characterized in that step is as follows:
1) add crystal seed: the calcium carbonate crystal seed of preparing in advance to the disposable 300-800mg/L of adding of hydraulic cyclone reactor, before hydraulic cyclone reactor is emptying, no longer adds crystal seed;
2) hydraulic mixing pre-service: the sodium carbonate that adds 1000g/L to hydraulic cyclone reactor, make strontium ion and calcium carbonate crystal seed, sodium carbonate in radioactive wastewater stir and generate large particle diameter compact grain thing by hydraulic cyclone, deposit to hydraulic cyclone reactor bottom;
3) radioactive wastewater of processing enters membrane separator, adds with Fe simultaneously
3+the molysite 3.0mg/L of meter continues reaction and generates particle, water outlet after Middle hollow fiber membrane under aeration agitation effect.
2. the method for claim 1, the mass concentration that it is characterized in that strontium ion in radioactive wastewater is 5-10mg/L.
3. the method for claim 1, is characterized in that described radioactivity is 45-60 minute containing the residence time of strontium waste water in hydraulic cyclone reactor.
4. the method for claim 1, is characterized in that described radioactivity is 45-60 minute containing the residence time of strontium waste water in membrane separator.
5. realize the radioactivity of claim 1 containing the treating apparatus of strontium waste water, it is characterized in that wastewater storage tank (1) is connected to the import of hydraulic cyclone reactor (3) cone base, hydraulic cyclone reactor (3) supernatant pipeline junctional membrane separation vessel (6) import through lift pump (2) and flow of inlet water meter (14); Hollow-fibre membrane (7) rising pipe in membrane separator (6) is connected with solenoid valve (13) with water flow meter (16) through going out water pump (11); Sodium carbonate medicine storing drum (5) is connected to the feeding opening of hydraulic cyclone reactor (3) cone base through SODIUM PERCARBONATE dosing pump (4), iron chloride medicine storing drum (10) is connected to the feeding opening of membrane separator (6) through iron chloride dosing pump (9), fan blower (8) is connected to the air intake opening of membrane separator bottom through air flowmeter (15); Liquid level gauge (12) is arranged on the top of membrane separator (6).
6. device as claimed in claim 5, is characterized in that described hydraulic cyclone reactor is comprised of cone and right cylinder, and cone angle is 38 ° ± 2 °, and cone and cylindrical volume ratio are 1:3.
7. device as claimed in claim 5, is characterized in that described hollow-fibre membrane is microfiltration membranes or ultra filtration membrane conventional in water treatment.
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| CN201410009260.5A CN103714874B (en) | 2014-01-08 | 2014-01-08 | A kind of radioactivity processing method containing strontium waste water and device |
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| CN201410009260.5A CN103714874B (en) | 2014-01-08 | 2014-01-08 | A kind of radioactivity processing method containing strontium waste water and device |
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| CN103714874B CN103714874B (en) | 2016-06-15 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104332209A (en) * | 2014-09-05 | 2015-02-04 | 上海华畅环保设备发展有限公司 | Waste liquid processing system radiating waste liquid whirl separating purifying method and device |
| CN105399274A (en) * | 2015-11-26 | 2016-03-16 | 常州大学 | Strontium-containing radioactive wastewater treatment device |
| CN106057262A (en) * | 2016-06-14 | 2016-10-26 | 东莞市联洲知识产权运营管理有限公司 | Treatment method of radioactive strontium-containing waste water |
| CN107658036A (en) * | 2017-08-22 | 2018-02-02 | 天津大学 | The method of secondary carrier band co-precipitation membrane separation radiostrontium contaminant water |
| CN108231233A (en) * | 2018-02-01 | 2018-06-29 | 上海场域环保科技有限公司 | A kind of nuclear power plant's Spent Radioactive liquid processing method |
| CN109205829A (en) * | 2018-09-08 | 2019-01-15 | 天津大学 | The method of film assisting crystallisation technique MAC selective removal and the copper in recycle-water |
| CN111320245A (en) * | 2018-12-14 | 2020-06-23 | 天津科技大学 | Sr in radioactive wastewater treated by composite pre-coating technology2+Method (2) |
| CN112635091A (en) * | 2019-10-08 | 2021-04-09 | 天津科技大学 | Processing apparatus of radioactive strontium-containing wastewater |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104332209A (en) * | 2014-09-05 | 2015-02-04 | 上海华畅环保设备发展有限公司 | Waste liquid processing system radiating waste liquid whirl separating purifying method and device |
| CN104332209B (en) * | 2014-09-05 | 2017-02-01 | 上海华畅环保设备发展有限公司 | Waste liquid processing system radiating waste liquid whirl separating purifying method and device |
| CN105399274A (en) * | 2015-11-26 | 2016-03-16 | 常州大学 | Strontium-containing radioactive wastewater treatment device |
| CN106057262A (en) * | 2016-06-14 | 2016-10-26 | 东莞市联洲知识产权运营管理有限公司 | Treatment method of radioactive strontium-containing waste water |
| CN107658036A (en) * | 2017-08-22 | 2018-02-02 | 天津大学 | The method of secondary carrier band co-precipitation membrane separation radiostrontium contaminant water |
| CN107658036B (en) * | 2017-08-22 | 2019-10-01 | 天津大学 | Secondary carrier band co-precipitation-membrane separation radiostrontium contaminant water method |
| CN108231233A (en) * | 2018-02-01 | 2018-06-29 | 上海场域环保科技有限公司 | A kind of nuclear power plant's Spent Radioactive liquid processing method |
| CN109205829A (en) * | 2018-09-08 | 2019-01-15 | 天津大学 | The method of film assisting crystallisation technique MAC selective removal and the copper in recycle-water |
| CN111320245A (en) * | 2018-12-14 | 2020-06-23 | 天津科技大学 | Sr in radioactive wastewater treated by composite pre-coating technology2+Method (2) |
| CN112635091A (en) * | 2019-10-08 | 2021-04-09 | 天津科技大学 | Processing apparatus of radioactive strontium-containing wastewater |
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