CN103714874B - A kind of radioactivity processing method containing strontium waste water and device - Google Patents
A kind of radioactivity processing method containing strontium waste water and device Download PDFInfo
- Publication number
- CN103714874B CN103714874B CN201410009260.5A CN201410009260A CN103714874B CN 103714874 B CN103714874 B CN 103714874B CN 201410009260 A CN201410009260 A CN 201410009260A CN 103714874 B CN103714874 B CN 103714874B
- Authority
- CN
- China
- Prior art keywords
- strontium
- hydraulic cyclone
- membrane
- radioactivity
- cyclone reactor
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium Chemical compound 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[Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 36
- 239000002351 wastewater Substances 0.000 title claims abstract description 33
- 238000003672 processing method Methods 0.000 title claims abstract description 5
- 239000011901 water Substances 0.000 claims abstract description 33
- 239000011649 sodium carbonate Substances 0.000 claims abstract description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 18
- 238000000034 methods Methods 0.000 claims abstract description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound 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[Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229960003563 Calcium Carbonate Drugs 0.000 claims abstract description 13
- NMCUIPGRVMDVDB-UHFFFAOYSA-L Iron(II) chloride Chemical compound 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Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound 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[Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000008105 calcium carbonate Substances 0.000 claims abstract description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 13
- 239000000835 fibers Substances 0.000 claims abstract description 11
- 239000002245 particles Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000006243 chemical reactions Methods 0.000 claims abstract description 5
- 239000006228 supernatants Substances 0.000 claims abstract description 5
- 239000002354 radioactive wastewater Substances 0.000 claims description 12
- 239000003570 air Substances 0.000 claims description 8
- 239000003814 drugs Substances 0.000 claims description 8
- 229910001427 strontium ion Inorganic materials 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 238000001471 micro-filtration Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 5
- 238000005276 aerator Methods 0.000 claims description 4
- MWNQXXOSWHCCOZ-UHFFFAOYSA-M Sodium percarbonate Chemical compound 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[Na+].OOC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000007792 addition Methods 0.000 claims description 2
- 239000011514 iron Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940045872 sodium percarbonate Drugs 0.000 claims description 2
- 238000005202 decontamination Methods 0.000 abstract description 10
- 230000003588 decontaminative Effects 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 10
- 238000009388 chemical precipitation Methods 0.000 abstract description 5
- LEDMRZGFZIAGGB-UHFFFAOYSA-L Strontium carbonate Chemical compound 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Abstract
The present invention relates to a kind of radioactivity processing method containing strontium waste water and device; The radioactivity in hydraulic cyclone reactor is made to carry out chemical reaction with calcium carbonate crystal seed, sodium carbonate by hydraulic cyclone stirring containing strontium waste water, strontium carbonate is made to deposit at calcium carbonate seed surface, form the closely knit crystal grain thing rapid precipitation of big particle diameter bottom hydraulic cyclone, to remove part radiostrontium ion; Short grained strontium carbonate and crystal seed enter membrane separator with supernatant, and react with iron chloride, and particulate matter removes radiostrontium ion further after Middle hollow fiber membrane, makes the radioactivity of water outlet be greatly lowered. The particle size that the method is formed is big, structure is closely knit, settling property good, effectively overcome the shortcoming that chemical precipitation method decontamination factor is low, sludge output is big, also solve the drawback that in membrane separation process, fouling membrane is serious, be that a kind of economical and practical radioactivity is containing strontium method of wastewater treatment.
Description
Technical field
The present invention relates to a kind of Spent Radioactive water technology, be exactly removal radiostrontium ion from waste water.
Background technology
Radiostrontium (90Sr and89Sr) be by235U and239Pu nuclear fission produces, and is widely present in radioactive wastewater. In March, 2011, Fukushima, Japan nuclear power station caused radioactive substance leakage because of earthquake, contained substantial amounts of radiostrontium in the waste water of discharge.90The Sr half-life, bio-toxicity was strong, is gathered in skeleton and is difficult to discharge, it is therefore desirable to it removed from radioactive wastewater, to protect environmental and human health impacts up to 28.9.
Chemical precipitation method technological process is simple, and easy to operate, operating cost is low, it is adaptable to the radioactive wastewater that strontium concentration is constant or trace processes; But, the mud particle diameter that chemical precipitation method is formed is little, settling property is poor, thus the mud volume production of the method is big, the cycles of concentration ratio of remaining radioactivity sludge volume (the radioactive wastewater cumulative volume of process 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 relatively low.Chemical precipitation-microfiltration (or ultrafiltration) group technology, although solve the shortcoming of solid-liquid separation difficulty in chemical precipitation method, make cycles of concentration be enhanced, but its cost is to cause serious fouling membrane, and the limited extent that decontamination factor increases.
When adopting chemical precipitation method or chemical precipitation-microfiltration (or ultrafiltration) group technology to process the relatively low waste water of radiostrontium ion concentration, according to solubility product principle, for reaching identical radiostrontium ion remaval effect, it is necessary to enlarge markedly the dosage of precipitant. For this problem, usual radiotropism waste water adds inactive strontium ion, utilizing radiostrontium ion and on-radiation strontium ion to have the feature of identical chemical property, making radiostrontium ion and on-radiation strontium ion precipitate removal, thus reducing the dosage of precipitant simultaneously.
Compared with the conventional chemical sedimentation method, although mechanical agitation coprecipitation improves cycles of concentration and decontamination factor, but the amplitude of raising is notable, and radiation proof requirement is improved by the plant equipment increased, operation, maintenance, operational management difficulty. Reverse osmosis technology is higher except strontium operating cost; Waste water salinity is had strict restriction by ion exchange and continuous electric desalination, and the former can produce substantial amounts of radioactive spent resin, causes subsequent solid refuse difficult treatment, costly, and the power consumption of the latter is higher.
Summary of the invention
For problems of the prior art, the present invention proposes the method for hydraulic cyclone stirring and the Middle hollow fiber membrane coupling radiostrontium ion to remove in waste water. Adopt hydraulic cyclone stirring and microfiltration (or ultrafiltration) coupling, expense is low, simple to operation, automaticity is high, both the particulate matter that the mud containing strontium forms big particle diameter, structure is closely knit, settling property is good can have been made, reduce the pollution of follow-up micro-filtration membrane (or ultrafilter membrane), improve again decontamination factor and the cycles of concentration of strontium, be that a kind of economical and practical radioactive wastewater is except strontium method.
The method makes the radioactivity in hydraulic cyclone reactor carry out chemical reaction with calcium carbonate crystal seed, sodium carbonate by hydraulic cyclone stirring containing strontium waste water, strontium carbonate is made to deposit at calcium carbonate seed surface, form the closely knit crystal grain thing rapid precipitation of big particle diameter bottom hydraulic cyclone, to remove part radiostrontium ion; Short grained strontium carbonate and crystal seed enter membrane separator with supernatant, and react with iron chloride, and particulate matter removes radiostrontium ion further after Middle hollow fiber membrane, makes the radioactivity of water outlet be greatly lowered.
Technical scheme is as follows:
A kind of radioactivity is containing the processing method of strontium waste water, and step is as follows:
1) add crystal seed: to the disposable addition 300-800mg/L of the hydraulic cyclone reactor calcium carbonate crystal seed prepared in advance, before hydraulic cyclone reactor empties, no longer add crystal seed;
2) hydraulic mixing pretreatment: add the sodium carbonate of 1000mg/L to hydraulic cyclone reactor, make the strontium ion in radioactive wastewater generate big particle diameter compact grain thing with calcium carbonate crystal seed, sodium carbonate by hydraulic cyclone stirring, deposit to hydraulic cyclone reactor bottom;
3) radioactive wastewater processed enters membrane separator, adds with Fe simultaneously3+The iron salt 3.0mg/L of meter, continues reaction under aeration agitation effect and generates particulate matter, water outlet after Middle hollow fiber membrane.
In described radioactive wastewater, the mass concentration of strontium ion is 5-10mg/L.
Described radioactivity time of staying in hydraulic cyclone reactor containing strontium waste water is 45-60 minute.
The described radioactivity waste water containing the strontium time of staying in membrane separator is 45-60 minute.
The radioactivity of the present invention process device containing strontium waste water, wastewater storage tank 1 is connected to the import of hydraulic cyclone reactor 3 cone base, hydraulic cyclone reactor 3 supernatant pipeline junctional membrane separator 6 import through elevator pump 2 and feed water flow gauge 14; Hollow-fibre membrane 7 outlet pipe in membrane separator 6 is connected with electromagnetic valve 13 through going out water pump 11 and water flow meter 16; 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, and aerator 8 is connected to the air inlet bottom membrane separator through mass air flow sensor 15. Liquidometer 12 is arranged on the top of membrane separator 6.
Described hydraulic cyclone reactor is made up of cone and cylinder, and cone angle is 38 ° ± 2 °, and cone and cylindrical volume ratio are 1:3.
Described hollow-fibre membrane is conventional micro-filtration membrane or ultrafilter membrane during water processes.
The beneficial effects of the present invention is: by the enforcement of the present invention, decontamination factor and the cycles of concentration of radiostrontium can be significantly improved, while improving strontium removal effect, reduce the yield of radwaste, reduce the radioactive pollution potential hazard to environment and the public. Reactor based on the method can be designed to fixed or wheeled apparatus as required, design scale can also be chosen flexibly, during suitable in 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: for the present invention: Experimental equipment.
In figure: 1-wastewater storage tank; 2-elevator pump; 3-hydraulic cyclone reactor; 4-sodium carbonate dosing pump; 5-sodium carbonate medicine storing drum; 6-membrane separator; 7-doughnut mocromembrane; 8-aerator; 9-iron chloride dosing pump; 10-iron chloride medicine storing drum; 11-goes out water pump; 12-liquidometer; 13-electromagnetic valve; 14-feed water flow gauge; 15-mass air flow sensor; 16-water flow meter.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the present invention are illustrated. It should be noted that the present embodiment is narrative, rather than determinate, do not limit protection scope of the present invention with this embodiment.
The device of present example is shown in accompanying drawing. Wastewater storage tank size Φ × H=1100 × 2150mm; Hydraulic cyclone reactor bottom is cone, cone angle 38 °, height 260mm; Top is cylinder Φ × H=200 × 300mm; Membrane separator Φ × H=120 × 150mm, equipped with 1 hollow fiber microfiltration membrane assembly, nominal pore size is 0.22 μm, and effective area is 0.5m2, intake pump and to go out water pump be peristaltic pump, water inlet, water outlet, mass air flow sensor are spinner flowmeter. Device adopt PLC(Programmable Logic Controller) control, fully automatic operation, PLC adopt current techique programming. Device be every day 24h run continuously, wherein hydraulic cyclone reactor is continuum micromeehanics, and membrane separator is interval water outlet, in the circulation of every 10 minutes, water outlet 9 minutes, empty aeration 1 minute.
Specific operation process is: before when device starts, and adds strontium chloride in simulated emission wastewater storage tank 1, and preparation sets the simulated emission of concentration containing strontium waste water. When device starts, add, to hydraulic cyclone reactor 3 is disposable, the calcium carbonate crystal seed prepared in advance. Then under PLC control, elevator pump 2 aspirates containing strontium waste water from wastewater storage tank 1, current are tangentially into the bottom of hydraulic cyclone reactor 3, sodium carbonate in sodium carbonate medicine storing drum 5 is added bottom hydraulic cyclone reactor 3 by sodium carbonate dosing pump 4 simultaneously, containing strontium waste water, crystal seed and sodium carbonate collision mutually, reaction under hydraulic cyclone stirring action, form big particle diameter, the particulate matter that closely knit, settling property is good, being deposited to the bottom of hydraulic cyclone reactor 3 gradually, supernatant is from flowing into membrane separator 6.For slowing down the pollution of doughnut mocromembrane 7, aerator 8 to membrane separator 6 aeration to provide air stirring, iron chloride in iron chloride medicine storing drum 10 is added membrane separator 6 by iron chloride dosing pump 9 simultaneously, make the small particle in mixed liquor react formation bulky grain floccule body further, separate through doughnut mocromembrane 7, go out water outlet after water pump 11 aspirates. Liquidometer 12 is for controlling the keying of start and stop and the electromagnetic valve 13 water pump 11. Feed water flow gauge 14 is for controlling the flow of inlet water of hydraulic cyclone reactor, and mass air flow sensor 14 is for controlling the aeration rate of membrane separator 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, total residence time is 90 minutes, and wherein the time of staying 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 containing strontium waste water. Experiment adds the 300mg/L calcium carbonate crystal seed prepared in advance when starting in hydraulic cyclone reactor; In experiment, sodium carbonate dosage is 1000mg/L, iron chloride dosage is that 3.0mg/L(is with Fe3+Meter) time, water outlet strontium mass concentration is stable at 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, total residence time is 120 minutes, and wherein the time of staying of hydraulic cyclone reactor is 60 minutes, and the hydraulic detention time of membrane separator is 60 minutes. Utilize the simulated emission that this device process strontium concentration is 10mg/L containing strontium waste water. Experiment adds the 800mg/L calcium carbonate crystal seed prepared in advance when starting in hydraulic cyclone reactor; In experiment, sodium carbonate dosage is 1000mg/L, iron chloride dosage is that 3.0mg/L(is with Fe3+Meter) time, water outlet strontium mass concentration is stable at 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, total residence time is 100 minutes, and wherein the time of staying of hydraulic cyclone reactor is 50 minutes, and the hydraulic detention time of membrane separator is 50 minutes. Utilize the simulated emission that this device process strontium concentration is 8mg/L containing strontium waste water. Experiment adds the 500mg/L calcium carbonate crystal seed prepared in advance when starting in hydraulic cyclone reactor; In experiment, sodium carbonate dosage is 1000mg/L, iron chloride dosage is that 3.0mg/L(is with Fe3+Meter) time, water outlet strontium mass concentration is stable at 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, total residence time is 90 minutes, and wherein the time of staying 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 containing strontium waste water. Experiment adds the 300mg/L calcium carbonate crystal seed prepared in advance when starting in hydraulic cyclone reactor; In experiment sodium carbonate dosage be 1000mg/L, when not adding iron chloride, water outlet strontium mass concentration is stable at 7 μ g/L. The cycles of concentration of this technique is 2800, and decontamination factor is 710.
Claims (7)
1. radioactivity is containing a processing method for strontium waste water, it is characterized in that step is as follows:
1) add crystal seed: to the disposable addition 300-800mg/L of the hydraulic cyclone reactor calcium carbonate crystal seed prepared in advance, before hydraulic cyclone reactor empties, no longer add crystal seed;
2) hydraulic mixing pretreatment: add the sodium carbonate of 1000mg/L to hydraulic cyclone reactor, make the strontium ion in radioactive wastewater generate big particle diameter compact grain thing with calcium carbonate crystal seed, sodium carbonate by hydraulic cyclone stirring, deposit to hydraulic cyclone reactor bottom;
3) radioactive wastewater processed enters membrane separator, adds with Fe simultaneously3+The iron salt 3.0mg/L of meter, continues reaction under aeration agitation effect and generates particulate matter, water outlet after Middle hollow fiber membrane.
2. the method for claim 1, is characterized in that in radioactive wastewater, the mass concentration of strontium ion is 5-10mg/L.
3. the method for claim 1, is characterized in that described radioactivity time of staying in hydraulic cyclone reactor containing strontium waste water is 45-60 minute.
4. the method for claim 1, is characterized in that the described radioactivity waste water containing the strontium time of staying in membrane separator is 45-60 minute.
5. realize the radioactivity process device containing strontium waste water of claim 1, it is characterized in that wastewater storage tank (1) is connected to the import of hydraulic cyclone reactor (3) cone base, pipeline junctional membrane separator (6) import of hydraulic cyclone reactor (3) supernatant through elevator pump (2) and feed water flow gauge (14); Hollow-fibre membrane (7) outlet pipe in membrane separator (6) is connected with electromagnetic valve (13) through going out water pump (11) and water flow meter (16); 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), and aerator (8) is connected to the air inlet bottom membrane separator through mass air flow sensor (15); Liquidometer (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 made up of cone and 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 conventional micro-filtration membrane or ultrafilter membrane during water processes.
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| 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 |
| CN106057262B (en) * | 2016-06-14 | 2017-11-24 | 泉州泉港润美环保科技有限公司 | A kind of processing method of radioactivity waste water containing strontium |
| 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 |
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