CN110467190A - A kind of device and method for recycling boron in radioactivity borate waste solution - Google Patents
A kind of device and method for recycling boron in radioactivity borate waste solution Download PDFInfo
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- CN110467190A CN110467190A CN201810438815.6A CN201810438815A CN110467190A CN 110467190 A CN110467190 A CN 110467190A CN 201810438815 A CN201810438815 A CN 201810438815A CN 110467190 A CN110467190 A CN 110467190A
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- boron
- membrane module
- nucleic
- water pot
- intake pump
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 112
- 239000002699 waste material Substances 0.000 title claims abstract description 31
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000012528 membrane Substances 0.000 claims abstract description 61
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 230000002285 radioactive effect Effects 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 9
- 239000010808 liquid waste Substances 0.000 claims description 9
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 238000009738 saturating Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 9
- 239000002910 solid waste Substances 0.000 abstract description 3
- 238000012958 reprocessing Methods 0.000 abstract description 2
- 210000004379 membrane Anatomy 0.000 description 32
- 238000010612 desalination reaction Methods 0.000 description 16
- 238000001223 reverse osmosis Methods 0.000 description 13
- 238000000926 separation method Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 7
- 239000004745 nonwoven fabric Substances 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004971 Cross linker Substances 0.000 description 4
- 210000002469 basement membrane Anatomy 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000004760 aramid Substances 0.000 description 3
- 229920003235 aromatic polyamide Polymers 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JFRFBQBKLASHBY-UHFFFAOYSA-N (2-aminopiperazin-1-yl)-phenylmethanone Chemical compound NC1N(CCNC1)C(C1=CC=CC=C1)=O JFRFBQBKLASHBY-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- 238000012356 Product development Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/02—Boron; Borides
- C01B35/023—Boron
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides a kind of for recycling the device of boron in radioactivity borate waste solution comprising: raw water tank, separative unit intake pump, the separative unit membrane module for being separated to boron and nucleic, intermediate water pot, upgrading unit intake pump, upgrading unit membrane module and production water pot；The raw water tank, separative unit intake pump, separative unit membrane module, intermediate water pot, upgrading unit intake pump, upgrading unit membrane module and production water pot are sequentially connected.Provided by the present invention for recycling the device of boron in radioactivity borate waste solution, nucleic and impurity while boron is concentrated in the traditional boron recovery process of solution is simple and efficient also to be concentrated, it improves the purity for being concentrated boron and reduces its activity concentration, avoid nucleic that reprocessing is concentrated again, increase solid waste yield, according to project actual demand, the boron concentration of simple and flexible control recycling.
Description
Technical field
The present invention relates to a kind of device and method for recycling boron in radioactivity borate waste solution.
Background technique
In conventional pressurized water heap nuclear power plant, reactive chemical shimming control is carried out using boron.During power plant runs, due to adjusting boron
Frequent operation is let out under appearance system with changing, a large amount of borate waste solutions will be generated.The borate waste solution of discharge largely passes through boron recovery system
After concentration and purification, the reuse in power plant.But every heap year, still there is also about 0.4 ton of boron to arrange to environment.
The reactive control mode of CAP series nuclear power plant is similar with general PWR nuclear power plant, but CAP series nuclear power plant exists
Mechanical compensation operational mode is additionally used in reactivity control, soluble boron is only used for compensation reactivity due to caused by reactor core burnup
Variation, and fast reactivity variation control and Steam Generator in Load Follow are carried out using the movement of control rod, reduce borate waste solution from source
Generation.To simplify system design, the boron recovery system of conventional pressurized water heap power plant is eliminated in original design, if borate waste solution is not
Processing, every heap year, about about 1 ton of boron was by being discharged into environment after Liquid Radwaste Treatment processing.
Although temporarily without the emission limit of boron in national standard, after Fukushima event, requirement of the state supervision to environmental protection
It is increasingly strict, the emission control of boron in liquid effluent is focused more on.The side of evaluating wishes to improve by design, makes nuclear power plant
Boron concentration of emission and boron total emission volumn are further controlled.In order to control the boron concentration and total amount finally arranged to environment, solve
Scheme first is that this part of boron of reuse.In addition, the application characteristic based on enrichment boric acid, might have more and more nuclear powers in the future
Factory is using enrichment boric acid, it is contemplated that is enriched with the high value of boron, also it is necessary to recycle this part of boron.
The technique of adoptable recycling boron mainly has evaporation and reverse osmosis membrane technique at present.It is evaporated to and is returned at this stage without boron
What the nuclear power station of receipts system used removes boron technique, its advantage is that technical maturity, engineering operation greater experience, the disadvantage is that occupied area
Greatly, energy consumption is high, radionuclide specific activity is high in concentrate, radionuclide and it is non-put impurity (including silicon) concentration together with boron,
Even if purifying again by resin bed, solid waste yield will increase, and since selectivity of the resin to silicon in foreign ion is low, can lead
Silica in circuit is caused to gradually rise.Membrane technology is a physically separate process, will not introduce additional impurity, but at existing film
Although reason technology mainly has simple process, except boron is high-efficient, low power consumption and other advantages, boron and nucleic can be concentrated simultaneously.Core
The maximum concentration of boron is likely to be breached 2700ppm in power plant's coolant efflux, and mean boron concentrations are about 1000ppm, boron after concentration
Concentration is even up to 5000ppm, and only ppb grades of radioactive liquid Radionuclide ion concentration even lower, needs to be separated
Boron and nuclide concentration contrast are too big, and the borate waste solution processing of conventional reverse osmosis film nuclide concentration low for high boron concentration lacks application
Example, and also concentration boron can be caused not to be able to satisfy reuse requirement there is a phenomenon where nucleic and boron while by concentration.
How to solve to avoid nucleic and other impurities ion concentration while boron is concentrated, and raising film is dense to water inlet boron
The scope of application of degree, while also only having the solution of 1000ppm or so to be concentrated as the high-purity of 5000ppm or so mean boron concentrations
B solution becomes emphasis of the invention.There is by using a kind of nuclear power plant to boron and nucleic the film product and one kind of high separation rate
There is the film product mix application of high rejection to boron, boron is carried out after efficiently separating nuclear power plant's radioactivity borate waste solution Radionuclide
Efficient concentration, while meeting the concentration and purity requirement of engineer application recycling, it realizes and the efficient and high-quality of boron is recycled.
Summary of the invention
In view of the deficiencies of the prior art, the present invention proposes a kind of for recycling device and the side of boron in radioactivity borate waste solution
Method.
The present invention provides a kind of for recycling the device of boron in radioactivity borate waste solution characterized by comprising raw water
Tank, separative unit intake pump, the separative unit membrane module for being separated to boron and nucleic, intermediate water pot, upgrading unit into
Water pump, upgrading unit membrane module and production water pot；The raw water tank, separative unit intake pump, separative unit membrane module, intermediate water
Tank, upgrading unit intake pump, upgrading unit membrane module and production water pot are sequentially connected；The separative unit membrane module and the raw water
Tank is connected；The upgrading unit membrane module and the intermediate water pot are connected；Wherein:
The separative unit membrane module is greater than 90% to the transmitance of boron, is greater than 95% to the rejection of nucleic；
The upgrading unit membrane module is greater than 95% to the rejection of boron.
Preferably, the separative unit intake pump is configured to the Spent Radioactive of boracic and nucleic in the raw water tank
Liquid pump enters the separative unit membrane module.
Preferably, the upgrading unit intake pump is configured to for the borate waste solution in the intermediate water pot being pumped into described dense
Contracting unit membrane module.
Preferably, the separative unit membrane module include a kind of complex reverse osmosis membrane, which is characterized in that including non-woven fabrics,
Base, active desalination layer and separating layer are supported, the non-woven fabrics, support base, active desalination layer and separating layer are sequentially overlapped；Institute
Stating nonwoven thickness is 80-150 μm, and the support base is superimposed upon on non-woven fabrics, with a thickness of 20-50 μm；The activity desalination
Layer and separating layer are in turn attached in the support base, with a thickness of 0.1-0.5 μm.
The present invention provides a kind of preparation method of complex reverse osmosis membrane, including the desalination layer is the fine and close crosslinking knot of full fragrance
Structure, and there are charged functional groups to adjust the charge density on the aramid layer surface；The support base is porous knot
Structure；The support base uses polysulfones and hydroxy methacrylate additive, and wherein polysulfones is raw material, the control of hydroxy methacrylate additive concentration
5~50%.
It is molten as oil as the pyromellitic trimethylsilyl chloride of aqueous phase monomers, 2~8% using 1~10% aminobenzoyl piperazine
Property monomer carry out interface polymerization reaction, the reaction time control in 30-90s.Ensure to be formed fine and close active layer, while also guaranteeing to close
The flux of reason, optimizing surface charge density ensure that high separation rate film has high rejection to extremely low concentration nucleic, while can be saturating
Perboric acid reaches excellent separating effect.
Preferably, the upgrading unit membrane module includes a kind of complex reverse osmosis membrane, which is characterized in that including non-woven fabrics,
Base, active desalination layer and boron removal layer are supported, the non-woven fabrics, support base, active desalination layer and boron removal layer are sequentially overlapped；Institute
Stating nonwoven thickness is 80-150 μm, and the support base is superimposed upon on non-woven fabrics, with a thickness of 20-50 μm；The activity desalination
Layer and boron removal layer are in turn attached in the support base, with a thickness of 0.1-0.5 μm.
There is the desalination layer of the fine and close cross-linked structure of full fragrance by design construction, and combine charged functional groups tune in desalination layer
The charge density on whole aramid layer surface.Complex reverse osmosis membrane is by support base, active desalination layer and boron removal layer group in the present invention
At.It supports base and active desalination layer preparation method and traditional membrane preparation method almost the same.Boron removal layer preparation method:
By the addition of the crosslinking agent glutaraldehyde of the ethylene glycol monomethyl ether of 15-25% concentration, catalyst HCl and 2-10% concentration go from
In sub- water, heating stirring obtains ethylene glycol monomethyl ether crosslinker solution to being completely dissolved；
Then the complex reverse osmosis membrane of above-mentioned preparation is immersed in ethylene glycol monomethyl ether crosslinker solution, will then passes through ethylene glycol
The reverse osmosis membrane that methyl ether solution impregnates, which is placed in baking oven, to be heat-treated to get the complex reverse osmosis membrane containing boron removal layer is arrived.
The present invention provides a kind of method for recycling boron in radioactivity borate waste solution comprising following steps:
The radioactive liquid waste of boracic and nucleic is pumped into the separation for capableing of separating boron and nucleic by separative unit intake pump
Unit membrane module；
By the separative unit membrane module by waste liquid nucleic and impurity retention after return to raw water tank, will be in waste liquid
Boron penetrates film heel row to intermediate water pot；
The B solution in the intermediate water pot is pumped into upgrading unit membrane module by upgrading unit intake pump, in B solution
Boron be concentrated after return to the intermediate water pot, until reach default value.
Preferably, using the radioactive liquid waste of raw water tank storage boracic and nucleic.
Compared with prior art, the invention has the following advantages:
1, provided by the present invention for the device of recycling boron in radioactivity borate waste solution, it is simple and efficient the traditional boron recycling of solution
Nucleic and impurity are also concentrated while boron is concentrated in technique, improve the purity for being concentrated boron and its radioactive activity of reduction is dense
Degree avoids nucleic that reprocessing is concentrated again, increases solid waste yield, according to project actual demand, simple and flexible control recycling
Boron concentration.
2, it provided by the present invention for the device of recycling boron in radioactivity borate waste solution, solves in nuclear power plant's borate waste solution
The problem of nucleic is also concentrated while boron is concentrated reduces B solution Radionuclide concentration, for boron reuse provide purity is high,
The scheme that impurity concentration is low, process waste yield is small, system operation is simple, occupied area is few.
3, provided by the present invention for the device of recycling boron in radioactivity borate waste solution, different type nuclear power plant pair is solved
It recycles the different of boron concentration to require, the concentration of boron can finally be concentrated according to the type regulating system of practical engineering application and boron；
The total emission volumn of nuclear power plant's boron is reduced for nuclear power plant and concentration provides solution；Borate waste solution total amount is generated according to nuclear power plant,
Technique requirement can be realized by adjusting membrane component combination and quantity, improve the flexibility of technique application.
Detailed description of the invention
Fig. 1 is the process signal for meeting the device for recycling boron in radioactivity borate waste solution of the preferred embodiment of the present invention
Figure.
Wherein, 1: raw water tank 2: separative unit intake pump 3: separative unit membrane module 4: intermediate water pot 5: upgrading unit
Intake pump 6: upgrading unit membrane module 7: water pot is produced
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing and specific real
Applying mode, the present invention is described in further detail.
As shown in Figure 1, one embodiment of the invention provides the membrane treatment appts of a kind of radioactive liquid waste boron and nucleic separation,
By raw water tank, separative unit intake pump, the separative unit membrane module to boron and nucleic with high separation rate, intermediate water pot, concentration
Unit intake pump, upgrading unit membrane module produce water pot and associated conduit, valve and instrument composition.The radioactivity of boracic and nucleic
Waste liquid enters boron and nucleic separating film module by separative unit intake pump, and nucleic and impurity return to raw water tank after being rejected by,
Boron through film heel row to intermediate water pot, high-purity in intermediate water pot, low concentration B solution entered by upgrading unit intake pump
Upgrading unit membrane module, boron returns to intermediate water pot after being constantly concentrated, until reaching default value, concentration film unit produces water row
To water pot is produced, wait arrange.
The membrane processing method feature of boron is as follows in reuse radioactive liquid waste:
1. a kind of nuclear power station-service of invention has the film product of high separation rate to the nucleic such as boron and caesium, strontium, by being able to achieve boron
It is 100~5000ppm for water inlet boron concentration with efficiently separating for nucleic, in the pH value for not adjusting solution, single branch film original part is returned
When yield 10%, 90% is greater than to the transmitance of boron, 95% is greater than to the rejection of nucleic and impurity；
Wherein: film product development technical way:
1) control and optimization of based film structure:
The basement membrane of composite membrane primarily serves supporting role, and high performance support membrane is the necessary item for preparing high performance composite membrane
Part.Composite membrane with high performance in order to obtain, it is desirable to support counterdie that there is porosity appropriate, pore size and pore size distribution.
Support layer material should have good chemical stability, thermal stability and mechanical performance simultaneously.The present invention using it is cheap and easy to get,
Film is simple, has good mechanical strength and the close property of resistance to compression, has good chemical stability, and is resistant to biodegradable polysulfones and does
For the raw material of porous support membrane, the control of hydroxy methacrylate additive concentration guarantees that basement membrane without obvious paper-like hole, guarantees exploitation 25%
Film product basement membrane pass structure is uniform, cortex is complete and mechanical performance with higher, extend film product service life.
2) control and optimization of active desalination layer structure
Interface polymerization reaction is the key that prepare compound film activity desalination layer.The principal element for influencing interfacial polymerization has: water
The dip time of monomer concentration, basement membrane in two-phase of phase and organic phase, temperature and time in heat treatment process etc..In order to mention
Height has a better separating effect to film and nucleic, the present invention using 6% aminobenzoyl piperazine as aqueous phase monomers, 3%
Pyromellitic trimethylsilyl chloride as oil-soluble monomer, the interface polymerization reaction time controls at zone of reasonableness (30-90s), it is ensured that is formed
Fine and close active layer, while also guaranteeing reasonable flux, optimizing surface charge density ensures high separation rate film to extremely low concentration core
Element has high rejection, while can penetrate boric acid, reaches excellent separating effect.
2. being produced in water after separation, boron concentration, boron total amount and raw water are close, utmostly reduce the total emission volumn of boron.Work as water inlet
1000ppm B, when the system rate of recovery reaches 50-95%, producing boron concentration in water is 925-980ppm, and the overall recovery of boron reaches
46-93%,；
3. producing water Radionuclide concentration after separation to be substantially reduced, the purity of reuse boron is greatly improved.When water inlet radioactive activity
When concentration is 1000Bq/L, when the system rate of recovery reaches 50-95%, productions water Radionuclide concentration is 76-134Bq/L, nucleic and miscellaneous
Matter total amount reduces 96-88%；
4. separating B solution after nucleic, through boron upgrading unit, the final boron concentration that is concentrated be can achieve higher than water inlet boron concentration
Arbitrary value, when be concentrated boron concentration reach 4000-7000ppm when, the system boron rate of recovery can achieve 80% or more, dense B solution
Middle radionuclide specific activity concentration can satisfy the requirement of the low-level less than 1000Bq/L；
In addition, upgrading unit, which mainly relies on, develops the film product that a kind of nuclear power station-service has high rejection to high concentration boron,
It is 100-5000ppm for water inlet boron concentration, in the pH value for not adjusting solution, single branch film original part rate of recovery 10%, to boron
Rejection is greater than 95%.Film product development technical way: there is the de- of the fine and close cross-linked structure of full fragrance by design construction
Salt deposit, and combine the charge density on charged functional groups adjustment aramid layer surface in desalination layer.
Preferably, complex reverse osmosis membrane is made of support base, active desalination layer and boron removal layer in the present invention.Its branch support group
Layer and active desalination layer preparation method and traditional membrane preparation method are almost the same.Boron removal layer preparation method: by it is a certain amount of (15~
25%) ethylene glycol monomethyl ether, catalyst HCl and crosslinking agent glutaraldehyde (2~10%) is added in suitable deionized water, and heating is stirred
It mixes to being completely dissolved, obtains ethylene glycol monomethyl ether crosslinker solution.Then the complex reverse osmosis membrane tentatively prepared is immersed into ethylene glycol monomethyl ether
The reverse osmosis membrane impregnated by ethylene glycol monomethyl ether solution is placed in one timing of heat treatment in baking oven by certain time in crosslinker solution
Between, the complex reverse osmosis membrane containing boron removal layer can be obtained.
5. using batch separating treatment, the film number of system use can be reduced to the full extent；
6. can be according to traffic requirement to be processed, film original part number and combination side in flexible modulation separative unit membrane module
Formula；
7. separation terminal can be controlled flexibly, by the rate of recovery or the water quality indicator terminal controlled can be needed to be controlled
System.
Those skilled in the art can use different methods to achieve the described function each specific application, but
It is that such implementation should not be considered as beyond the scope of the present invention.
Obviously, those skilled in the art can carry out various modification and variations without departing from spirit of the invention to invention
And range.If in this way, these modifications and changes of the present invention belong to the claims in the present invention and its equivalent technologies range it
Interior, then the invention is also intended to include including these modification and variations.
Claims (5)
1. it is a kind of in radioactivity borate waste solution recycle boron device characterized by comprising raw water tank, separative unit into
Water pump, the separative unit membrane module for being separated to boron and nucleic, intermediate water pot, upgrading unit intake pump, upgrading unit
Membrane module and production water pot；The raw water tank, separative unit intake pump, separative unit membrane module, intermediate water pot, upgrading unit water inlet
Pump, upgrading unit membrane module and production water pot are sequentially connected；The separative unit membrane module is connected with the raw water tank；The concentration
Unit membrane module and the intermediate water pot are connected；
Wherein: the separative unit membrane module is greater than 90% to the transmitance of boron, is greater than 95% to the rejection of nucleic；
The upgrading unit membrane module is greater than 95% to the rejection of boron.
2. the device that radioactive liquid waste as described in claim 1 removes boron, which is characterized in that the separative unit intake pump is through matching
It sets so that the radioactive liquid waste of boracic and nucleic in the raw water tank is pumped into the separative unit membrane module.
3. the device that radioactive liquid waste as described in claim 1 removes boron, which is characterized in that the upgrading unit intake pump is through matching
It sets so that the borate waste solution in the intermediate water pot is pumped into the upgrading unit membrane module.
4. a kind of method for recycling boron in radioactivity borate waste solution, which comprises the steps of:
The radioactive liquid waste of boracic and nucleic is pumped into the separative unit for capableing of separating boron and nucleic by separative unit intake pump
Membrane module；
By the separative unit membrane module by waste liquid nucleic and impurity retention after return to raw water tank, the boron in waste liquid is saturating
Film heel row is crossed to intermediate water pot；
The B solution in the intermediate water pot is pumped into upgrading unit membrane module by upgrading unit intake pump, the boron in B solution
The intermediate water pot is returned to after being concentrated, until reaching default value.
5. the method for recycling boron in radioactivity borate waste solution as claimed in claim 4, which is characterized in that use the original
The radioactive liquid waste of water pot storage boracic and nucleic.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117038138A (en) * | 2023-08-16 | 2023-11-10 | 西南科技大学 | Deep purification and boron resource recovery method for high-boron radioactive wastewater of nuclear power station |
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