CN104810071B - Method and equipment for deep purifying of boron-containing radioactive waste liquid and recovery of boric acid - Google Patents
Method and equipment for deep purifying of boron-containing radioactive waste liquid and recovery of boric acid Download PDFInfo
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- CN104810071B CN104810071B CN201510181562.5A CN201510181562A CN104810071B CN 104810071 B CN104810071 B CN 104810071B CN 201510181562 A CN201510181562 A CN 201510181562A CN 104810071 B CN104810071 B CN 104810071B
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- G—PHYSICS
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- 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
- G21F9/06—Processing
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- 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
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- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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Abstract
The invention relates to a method for deep purifying of boron-containing radioactive waste liquid and recovery of boric acid. The method comprises the following steps of performing filtering, heat exchange, high-pressure reverse osmosis and low-pressure reverse osmosis on the boron-containing radioactive waste liquid to form a concentrated liquid and a permeate liquid, and directly sending the permeate liquid into a monitoring discharging tank to discharge; evaporating and boiling the concentrated liquid under the vacuum condition, performing mist and foam separating, condensing and cooling on secondary steam generated by the steam to form a condensed liquid, sending the condensed liquid into the monitoring discharging tank to discharge, and sending the remained concentrated boron liquid after evaporating to perform the boric acid crystallizing and recovery treatment; cooling and crystallizing the concentrated boron liquid generated by the concentration of the boric acid, so as to obtain a crystal slurry containing boric acid crystals; separating the solid and liquid of the crystal slurry to obtain a boric acid solid product; capturing radioactive nuclides in a clarified mother liquid after solid and liquid separating of the crystal slurry by an ion exchange column, returning back to perform the boric acid concentration, and then concentrating. The method has the advantages that while the boric acid is recovered, the waste liquid can be deeply purified; the size of equipment is greatly reduced, the treatment energy consumption is greatly decreased, and the discharging of secondary waste liquid to the outside is avoided.
Description
Technical field
The present invention relates to a kind of boron-containing radioactive waste liquid deep purifying reclaims the method and apparatus of boric acid simultaneously.
Background technology
Nuclear power plant can produce a large amount of radioactive liquid wastes in operation and maintenance stage, in the waste liquid that wherein power plant's primary Ioops are discharged
Also containing soluble neutron absorber boric acid so that the waste liquid that primary Ioops are discharged becomes boron-containing radioactive waste liquid.Boracic is put
Penetrating property waste liquid has to pass through except boron, removing could be to environmental emission after radioactivity.In order to reduce discharging of waste liquid to greatest extent to ring
The impact in border, some nuclear power plants also require to carry out deep purifying to the treated waste liquid reaching discharge standard.For in waste liquid
Boric acid, some nuclear power plants are provided with boron recovery system, can reclaim after borate waste solution is condensed into dense boron liquid by evaporation technology
Multiplexing；Some nuclear power plants are not provided with boron recovery system, discharge after needing to purify borate waste solution.
At present, the process of nuclear power plant's boron-containing radioactive waste liquid uses ion exchange or evaporation technology mostly.Ion
Exchange process is adsorbed to radionuclide in waste liquid using ion exchange resin, can be reduced to the radioactive concentration of waste liquid
Below emission limit.Ion-exchange process is ripe, but cannot remove the boric acid in waste liquid.Evaporation technology is then to be steamed by heating
Vapour ebuillition of heated vaporization in evaporimeter by waste liquid, the indirect steam condensate liquid that vaporization produces is after radioactive concentration is qualified after testing
Discharged, steam raffinate and then carry out cement solidification process.The good purification of evaporation technology, but shortcoming big, the place that is thermal energy consumption
Manage costly, and vapo(u)rization system is more complicated, run and the workload of maintaining is all very big.
Also there is the report processing borate waste solution using additive method, but be all not suitable for nuclear power plant's boron-containing radioactive waste liquid
Deep purifying is reclaimed with boric acid.Such as Chinese patent 02108593.5, it adopts two-stage oxidizing/flocculation process to process boracic radiation
Property waste water, first add oxidant and inorganic flocculating agent in waste water, through first order oxidation/flocculation, add macromolecule wadding
Solidifying agent carries out separation of solid and liquid, then adds medicament and carries out second level oxidation/flocculation.The complex process of this method, needs to consume
Substantial amounts of chemical agent, produces substantial amounts of radioactivity mud, secondary Waste disposal high cost simultaneously.
Content of the invention
The present invention provides a kind of boron-containing radioactive waste liquid deep purifying to reclaim the method and apparatus of boric acid simultaneously, can reclaim
While boric acid, waste liquid is carried out deep purifying, a large amount of chemical agents need not be consumed, equipment volume and process energy consumption greatly decline,
Waste liquid radioactive concentration after purification is significantly less than the emission limit of national Specification, and can avoid outwards discharging secondary giving up
Liquid.
A kind of method that boron-containing radioactive waste liquid deep purifying reclaims boric acid simultaneously, comprises the steps：
Deep purifying and boric acid pre-concentration：Boron-containing radioactive waste liquid is anti-through filtration, heat exchange, high pressure counter-infiltration and low pressure
Infiltration is processed into concentrate and two strands of materials of permeate, and wherein in permeate, boron mass concentration is less than 50mg/L, radioactive concentration
Less than the 1/10 of input concentration, be sent directly into monitoring letdown tank discharge, in concentrate boron mass concentration be 5000mg/L～
8000mg/L, sends into boric acid concentration step and is concentrated further；
Boric acid concentrates：Boron mass concentration is that the concentrate of 5000mg/L～8000mg/L evaporates boiling under vacuum,
The indirect steam that evaporation produces forms condensate liquid after mist separates, condensation cools down, and the radioactive concentration of condensate liquid is reduced to
Below 10Bq/L, send into monitoring letdown tank discharge, after evaporation residual dense boron liquid in boron mass concentration reach 22000mg/L～
26000mg/L, is sent to boric acid crystallization and is processed with recycling step；
Boric acid crystallization and recovery：The dense boron liquid that boric acid concentration step produces is cooled, crystallization, obtains the crystalline substance of boracic acid crystal
Slurry, magma is after separation of solid and liquid, you can obtain boric acid solid product with recycle and reuse, the clarification after magma separation of solid and liquid
Mother liquor returns again to boric acid concentration step after ion exchange column retention radionuclide and re-starts concentration.
Method as above, described deep purifying and boric acid preconcentration steps adopt waste liquid deep purifying and boric acid pre- dense
Contracting unit is realized, middle exhausted bath box that described waste liquid deep purifying and boric acid pre-concentration unit include being sequentially connected, booster pump, in advance
Filter, heat exchanger, one-level high-pressure pump, recuperator, high pressure counter-osmosis device, two grades of high-pressure pumps, low pressure reverse osmosis device and dense
Contracting liquid case, the permeate port of export of its mesohigh counter-osmosis device is connected with low pressure reverse osmosis device by two grades of high-pressure pumps, and high pressure is anti-
The concentrated solution outlet end of permeator is passed through recuperator and is connected with middle exhausted bath box or concentration liquid case, low pressure reverse osmosis device dense
The contracting liquid port of export is connected with middle exhausted bath box or concentration liquid case.
Method as above, boron-containing radioactive waste liquid is first stored in middle exhausted bath box, is then pumped into pre- by supercharging
Filter is filtered, the suspended impurity that may remain in retention waste liquid, and the waste liquid after filtration passes through heat exchanger, by heating medium
Waste liquid temperature is heated between 15～35 DEG C, then the pressure of waste liquid is brought up to by 1.0～4.0MPa by one-level high-pressure pump, plus
Pressure is further increased to 2.0～5.0MPa through recuperator by waste liquid after pressure again, and the waste liquid after pressurization enters high pressure
Counter-osmosis device carries out process and obtains permeate and concentrate, and it is laggard that permeate is forced into 0.5～2.0MPa through two grades of high-pressure pumps again
Enter low pressure reverse osmosis device to be processed, concentrate is introduced into recuperator, transfer energy to one-level in recuperator
The water outlet of high-pressure pump, high pressure counter-osmosis device concentrate, after recuperator outflow, returns to middle exhausted bath box or drains into dense
Contracting liquid case, the concentrate of low pressure reverse osmosis device also returns to middle exhausted bath box or drains into concentration liquid case.
Method as above, described boric acid concentration step adopts boric acid upgrading unit to realize, described boric acid upgrading unit
Including charging pump, heater, evaporimeter, circulating pump, demister, clarifier, condenser, surge tank, concentrate discharging pump, depth
The concentrate of purification and the generation of boric acid preconcentration steps accesses the entrance point of circulating pump, the steam (vapor) outlet of evaporimeter by charging pump
End is sequentially connected with demister, clarifier, condenser, surge tank, and circulating pump is passed through at the liquid outlet end of demister and clarifier
It is connected with the entrance point of heater, the port of export of heater is connected with the liquor inlet end of evaporimeter, the bottom feed liquid of evaporimeter
Outlet is connected with concentrate discharging pump, for discharging boron concentrate.
Method as above, reverse osmosis concentrated in the concentration liquid case of waste liquid deep purifying and boric acid pre-concentration unit
Contracting liquid injects the entrance point of circulating pump by charging pump, and the liquid of demister and clarifier collection pumps through circulation from liquid outlet end
Enter heater, enter, after heated 50～70 DEG C in heater of material, the indirect steam producing in evaporimeter, evaporimeter advanced
Enter demister, by the drop separation carried secretly in indirect steam out, then passing through clarifier again may will remain in indirect steam
Fine mist retention, thus indirect steam is purified, the indirect steam after purification is condensed into condensate liquid by condenser, condense
Liquid enters surge tank and keeps in, and evaporimeter maintains certain vacuum it is ensured that the operating pressure in evaporimeter is 10～40kPa, makes
Liquid energy must be concentrated and carry out explosive evaporation at 50～70 DEG C.
Method as above, boric acid crystallization and recycling step adopt boric acid crystallization and recovery unit to realize, described boric acid
Crystallization with recovery unit include heat exchanger, circulating pump, crystallizer, magma discharging pump, transfer tank, mother liquor tank, filter centrifugal, from
Sub- exchange column, the material liquid outlet end of crystallizer is connected with the entrance point of heat exchanger by circulating pump, and described boric acid concentration step produces
Raw concentrate accesses the entrance point of heat exchanger, and the magma port of export of crystallizer is connected with transfer tank by magma discharging pump, brilliant
The magma that crystallizer produces is drained into transfer tank by slurry discharging pump, and transfer tank is used for carrying out separation of solid and liquid to magma, the clarification obtaining
Mother liquor drains into mother liquor tank, and solid then filters the residual liquid in solid by filter centrifugal, and the liquid leaching drains into mother liquor
Groove, the solid of retention then first passes through ion exchange column as the solution receiving in final boric acid product, mother liquor tank and is radiated
Property nucleic retention, remove radioactive mother liquor and return again to boric acid concentration step and be circulated process.
A kind of boron-containing radioactive waste liquid deep purifying reclaim simultaneously boric acid equipment it is characterised in that：Including waste liquid depth
Purify and boric acid pre-concentration unit, boric acid upgrading unit and boric acid recovery unit,
Middle exhausted bath box that waste liquid deep purifying and boric acid pre-concentration unit include being sequentially connected, booster pump, prefilter,
Heat exchanger, one-level high-pressure pump, recuperator, high pressure counter-osmosis device, two grades of high-pressure pumps, low pressure reverse osmosis devices and concentrate liquid case,
The permeate port of export of its mesohigh counter-osmosis device is connected with low pressure reverse osmosis device by two grades of high-pressure pumps, high pressure counter-osmosis device
Concentrated solution outlet end is connect with middle exhausted bath box or concentration liquid case by recuperator, the concentrated solution outlet end of low pressure reverse osmosis device
It is connected with middle exhausted bath box or concentration liquid case；
Boric acid upgrading unit includes charging pump, heater, evaporimeter, circulating pump, demister, clarifier, condenser, buffering
Tank, concentrate discharging pump, concentrate liquid case be connected with the entrance point of circulating pump by charging pump, the steam (vapor) outlet end of evaporimeter with remove
Foam device, clarifier, condenser, surge tank are sequentially connected, and circulating pump and heating are passed through in the liquid outlet end of demister and clarifier
The entrance point of device connects, and the port of export of heater is connected with the liquor inlet end of evaporimeter, the bottom material liquid outlet of evaporimeter and
Concentrate discharging pump connects, for discharging boron concentrate；
Boric acid crystallization with recovery unit include heat exchanger, circulating pump, crystallizer, magma discharging pump, transfer tank, mother liquor tank and
Filter centrifugal, ion exchange column, the material liquid outlet end of crystallizer is connected with the entrance point of heat exchanger by circulating pump, and boric acid is dense
The pipe outlet of the concentrate discharging pump of contracting cell end accesses the pipeline between circulating pump and the entrance point of heat exchanger, heat exchanger
The port of export be connected with the entrance point of crystallizer, the magma port of export of crystallizer is connected with transfer tank by magma discharging pump, in
Turn trough is used for carrying out separation of solid and liquid to magma, and the clarified mother liquor obtaining drains into mother liquor tank, and solid then enters filter centrifugal, from
Residual liquid in solid is filtered by heart filter, and the liquid leaching drains into mother liquor tank, and the solid retaining is then as final
Boric acid product, the solution receiving in mother liquor tank first passes through ion exchange column and is processed, and radionuclide retention in mother liquor is gone
Except the rear concentration liquid case that returns is circulated process.
Equipment as above, evaporimeter maintain certain vacuum it is ensured that the operating pressure in evaporimeter be 10～
40kPa
Using technical solution of the present invention, the effect brought and advantage are：
(1) while reclaiming boric acid, waste liquid can be carried out deep purifying, the waste liquid radioactive concentration after purification is significantly
Less than the emission limit of national Specification, and radionuclide will not accumulate in concentrate it is ensured that system normal
Run；
(2) after deep purifying and boric acid pre-concentration are processed, the volume of waste liquid is reduced to original 1/10～1/15, dense
The treating capacity of contracting unit greatly reduces, and not only can substantially reduce the energy consumption of upgrading unit, it is also possible that upgrading unit equipment
Miniaturization；
(3) in addition to boric acid crystal and the qualified scavenging solution reaching discharge standard of purification, outwards do not discharge secondary liquid waste.
Brief description
Fig. 1 is the schematic flow sheet of the method that boron-containing radioactive waste liquid deep purifying of the present invention reclaims boric acid simultaneously；
Fig. 2 is that boron-containing radioactive waste liquid deep purifying of the present invention reclaims waste liquid deep purifying and boron in the equipment of boric acid simultaneously
The structural representation of sour pre-concentration unit；
Fig. 3 is the knot of the equipment mesoboric acid upgrading unit that boron-containing radioactive waste liquid deep purifying of the present invention reclaims boric acid simultaneously
Structure schematic diagram；
Fig. 4 is the crystallization of equipment mesoboric acid and the recovery list that boron-containing radioactive waste liquid deep purifying of the present invention reclaims boric acid simultaneously
The structural representation of unit.
In figure：1 waste liquid deep purifying and boric acid pre-concentration unit, 2 boric acid upgrading units, 3 boric acid crystallize and return
Receipts unit, 11 middle exhausted bath box, 12 booster pumps, 13 prefilters, 14 heat exchangers, 15 one-level high-pressure pumps, 16
Recuperator, 17 high pressure counter-osmosis devices, 18 2 grades of high-pressure pumps, 19 low pressure reverse osmosis devices, 20 concentration liquid cases, 21
Charging pump, 22 heaters, 23 evaporimeters, 24 circulating pumps, 25 demisters, 26 clarifiers, 27 condensers, 28
Surge tank, 29 concentrate discharging pumps, 31 heat exchangers, 32 circulating pumps, 33 crystallizers, 34 magma discharging pumps, 35
Transfer tank, 36 mother liquor tanks, 37 filter centrifugals, 38 ion exchange columns.
Specific embodiment
Below in conjunction with the accompanying drawing in the present invention, the technical scheme in the present invention is clearly and completely described.
As shown in figure 1, the present invention provides a kind of method that boron-containing radioactive waste liquid deep purifying reclaims boric acid simultaneously, including
Following steps：
Deep purifying and boric acid pre-concentration：By boron-containing radioactive waste liquid, (wherein boron mass concentration is 50mg/L～3000mg/
L) first processed using deep purifying and boric acid pre-concentration process step, in this step, waste liquid is through filtration, heat exchange, high pressure
The method such as counter-infiltration and low pressure reverse osmosis, is processed into concentrate and two strands of materials of permeate.Wherein in permeate, boron quality is dense
Degree is less than 50mg/L, and radioactive concentration is less than the 1/10 of input concentration, can be sent directly into monitoring letdown tank discharge；In concentrate
Boron mass concentration is 5000mg/L～8000mg/L, sends into boric acid concentration step and is concentrated further.
Boric acid concentrates：In boric acid concentration step, boron mass concentration is the concentrate of 5000mg/L～8000mg/L true
Evaporation boiling under empty condition, the indirect steam that evaporation produces forms condensate liquid after mist separation, condensation cooling, condensate liquid
Radioactive concentration is reduced to below 10Bq/L, is also fed into monitoring letdown tank discharge；In the dense boron liquid of residual after evaporation, boron quality is dense
Degree reaches 22000mg/L～26000mg/L, then is sent to boric acid crystallization and recycling step process.
Boric acid crystallization and recovery：In boric acid crystallization with recycling step, dense boron liquid is cooled, crystallization, obtains boracic acid crystals
The magma of body, magma is after separation of solid and liquid, you can obtain boric acid solid product, and boric acid solid can be with recycle and reuse.Brilliant
Clarified mother liquor after slurry separation of solid and liquid, after ion exchange column retention radionuclide, returns again to boric acid concentration step and again enters
Row concentrates.
Please continue to refer to Fig. 2-4, the present invention also provides a kind of boron-containing radioactive waste liquid deep purifying to reclaim boric acid simultaneously
Equipment, including waste liquid deep purifying and boric acid pre-concentration unit 1, boric acid upgrading unit 2 and boric acid recovery unit 3.
Middle exhausted bath box 11 that waste liquid deep purifying and boric acid pre-concentration unit 1 include being sequentially connected, booster pump 12, pre- mistake
Filter 13, heat exchanger 14, one-level high-pressure pump 15, recuperator 16,17, two grades of high-pressure pumps 18, low pressure of high pressure counter-osmosis device are anti-
Permeator 19 and concentration liquid case 20, the permeate port of export of its mesohigh counter-osmosis device 17 is anti-with low pressure by two grades of high-pressure pumps 18
Permeator 19 connects, and recuperator 16 and middle exhausted bath box 11 or concentration are passed through in the concentrated solution outlet end of high pressure counter-osmosis device 17
Liquid case 20 connects, and the concentrated solution outlet end of low pressure reverse osmosis device 19 is connected with middle exhausted bath box 11 or concentration liquid case 20.
As shown in Fig. 2 being first stored in middle exhausted bath box 11 through the boron-containing radioactive waste liquid of preliminary treatment, then by increasing
Press pump 12 is sent into prefilter 13 and is filtered, the suspended impurity that may remain in retention waste liquid.Waste liquid after filtration passes through one
Platform heat exchanger 14, by heating medium, waste liquid temperature is heated between 15～35 DEG C, then by one-level high-pressure pump 15 by waste liquid
Pressure brings up to 1.0～4.0MPa, and pressure is further increased to 2.0 through a recuperator 16 by waste liquid after pressurization again
～5.0MPa.Waste liquid entrance high pressure counter-osmosis device 17 after pressurization carries out process and obtains permeate and concentrate, high pressure counter-infiltration
The radioactive concentration of the permeate of device 17 can substantially reduce；Meanwhile, in waste liquid, 90%～98% boron is trapped within high pressure reverse osmosis
Thoroughly in the concentrate of device 17, and only 2%～10% boron remains in permeate.The permeate of high pressure counter-osmosis device 17 warp again
Two grades of high-pressure pumps 18 be forced into 0.5～2.0MPa after enter low pressure reverse osmosis device 19 processed, low pressure reverse osmosis device 19 saturating
The radioactive concentration crossing liquid reduces further；Meanwhile, the boron entering in the waste liquid of low pressure reverse osmosis device 19 40%～60% is cut
Stay in the concentrate of low pressure reverse osmosis device 19, and the permeate boron concentration of low pressure reverse osmosis device 19 also reduces further.Low pressure
The permeate of counter-osmosis device 19, as the waste liquid after final process, is sent in nuclear power plant's discharging of waste liquid groove, discharge to be detected.
High pressure counter-osmosis device 17 concentrate is introduced into recuperator 16, transfers energy to one in recuperator 16
The water outlet of level high-pressure pump 15, to improve the inlet pressure of high pressure counter-osmosis device 17.High pressure counter-osmosis device 17 concentrate returns from energy
After receiving device 16 outflow, return to middle exhausted bath box 11 or drain into concentration liquid case 20.The concentrate of low pressure reverse osmosis device 19 also returns
Return to middle exhausted bath box 11 or drain into concentration liquid case 20.
Concentrate liquid case 20 in electric heating tube or heating coil are installed it is ensured that in the winter time low temperature when, concentrate liquid temp not
Less than 15 DEG C, prevent the boric acid in concentrate from crystallizing and separate out.
As shown in figure 3, boric acid upgrading unit 2 includes charging pump 21, heater 22, evaporimeter 23, circulating pump 24, demister
25th, clarifier 26, condenser 27, surge tank 28, concentrate discharging pump 29.
Concentrate liquid case 20 to be connected with the entrance point of evaporimeter 23 by charging pump 21, so, from waste liquid deep purifying and
Reverse osmosis concentrated liquid in the concentration liquid case 20 of boric acid pre-concentration unit 1 is injected the entrance point of circulating pump 24 by charging pump 21, steams
The steam (vapor) outlet end sending out device 23 is sequentially connected with demister 25, clarifier 26, condenser 27, surge tank 28, demister 25 and only
The liquid outlet end changing device 26 is connected with the entrance point of heater 22 by circulating pump 24, the port of export of heater 22 and evaporimeter
23 liquor inlet end connects.The liquid of demister 25 and clarifier 26 collection is also fed into adding through circulating pump 24 from liquid outlet end
Hot device 22, material enters evaporimeter 23 after being heated to 60 DEG C in heater 22.The heating medium of heater 22 can be added
Vapours or conduction oil.The indirect steam producing in evaporimeter 23 is introduced into demister 25, will carry secretly in indirect steam
Drop separation out, then again pass through a clarifier 26, by indirect steam may residual fine mist retention, thus
Indirect steam is purified.Indirect steam after purification passes through a condenser 27, is condensed into condensate liquid, and condensate liquid enters surge tank
28 keep in.Evaporimeter 23 generally maintain certain vacuum it is ensured that operating pressure in evaporimeter 23 be 10～40kPa so that
Concentrate liquid energy and carry out explosive evaporation at 50～70 DEG C.The bottom material liquid outlet of evaporimeter 23 is connected with concentrate discharging pump 29,
For boron concentrate is discharged.
As shown in figure 4, boric acid crystallization includes heat exchanger 31, circulating pump 32, crystallizer 33, magma discharging with recovery unit 3
Pump 34, transfer tank 35, mother liquor tank 36, filter centrifugal 37, ion exchange column 38.Circulation is passed through at the material liquid outlet end of crystallizer 33
Pump 32 is connected with the entrance point of heat exchanger 31, and the pipeline of the concentrate discharging pump 29 of boric acid upgrading unit 2 end accesses circulating pump
Pipeline between 32 and the entrance point of heat exchanger 31, so, by boric acid upgrading unit 2 evaporate generation concentration be 22000～
2600ppm, temperature are to enter heat exchanger 31 together with the circulating mother liquor that 50～70 DEG C of boron concentrate is exported with circulating pump 32.Changing
In hot device 31, the feed liquid that boron concentrate and circulating mother liquor are mixed to get is cooled to 10 DEG C, sends under the promotion of circulating pump 32
Crystallizer 33.In crystallizer 33, feed liquid along certain channel flow, iterative cycles, keep uniform degree of supersaturation and relatively
Low degree of supercooling, completes crystallization process.The port of export of heat exchanger 31 is connected with the entrance point of crystallizer 33.
The magma port of export of crystallizer 33 is connected with transfer tank 35 by magma discharging pump 34, and magma discharging pump 34 will crystallize
The magma that device 33 produces drains into transfer tank 35.Transfer tank 35 is used for carrying out separation of solid and liquid to magma, and the clarified mother liquor obtaining drains into
Mother liquor tank 36, and solid then enters filter centrifugal 37 and is further processed, filter centrifugal 37 is by the residual solution in solid
Body filters, and the liquid leaching also drains into mother liquor tank 36, and the solid retaining, then as final boric acid product, can be reclaimed profit
With.The solution receiving in mother liquor tank 36 first passes through an ion exchange column 38 and is processed, and radionuclide in mother liquor is retained
Remove.Remove radioactive mother liquor to return again to concentrate liquid case 20, send into boric acid upgrading unit 2 and be circulated process.
The above, the only specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and any
Belong to those skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in, all answer
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.
Claims (4)
1. a kind of boron-containing radioactive waste liquid deep purifying reclaim simultaneously boric acid method it is characterised in that：Comprise the steps：
Deep purifying and boric acid pre-concentration：By boron-containing radioactive waste liquid through filtration, heat exchange, high pressure counter-infiltration and low pressure reverse osmosis
It is processed into concentrate and two strands of materials of permeate, wherein in permeate, boron mass concentration is less than 50mg/L, radioactive concentration is less than
The 1/10 of input concentration, is sent directly into monitoring letdown tank discharge, in concentrate, boron mass concentration is 5000mg/L～8000mg/L,
Send into boric acid concentration step to be concentrated further；
Boric acid concentrates：Boron mass concentration is that the concentrate of 5000mg/L～8000mg/L evaporates boiling under vacuum, evaporation
The indirect steam producing forms condensate liquid after mist separates, condensation cools down, and the radioactive concentration of condensate liquid is reduced to 10Bq/
Below L, send into monitoring letdown tank discharge, after evaporation residual dense boron liquid in boron mass concentration reach 22000mg/L～
26000mg/L, is sent to boric acid crystallization and is processed with recycling step；
Boric acid crystallization and recovery：The dense boron liquid that boric acid concentration step produces is cooled, crystallization, obtains the magma of boracic acid crystal,
Magma is after separation of solid and liquid, you can obtain boric acid solid product with recycle and reuse, the clarification after magma separation of solid and liquid is female
Liquid returns again to boric acid concentration step after ion exchange column retention radionuclide and re-starts concentration；
Described deep purifying and boric acid preconcentration steps adopt waste liquid deep purifying and boric acid pre-concentration unit (1) to realize, described
Waste liquid deep purifying and boric acid pre-concentration unit (1) inclusion be sequentially connected middle exhausted bath box (11), booster pump (12), pre-filtering
Device (13), heat exchanger (14), one-level high-pressure pump (15), recuperator (16), high pressure counter-osmosis device (17), two grades of high-pressure pumps
(18), low pressure reverse osmosis device (19) and concentration liquid case (20), the permeate port of export of its mesohigh counter-osmosis device (17) passes through two
Level high-pressure pump 18 is connected with low pressure reverse osmosis device (19), and recuperator is passed through at the concentrated solution outlet end of high pressure counter-osmosis device (17)
(16) it is connected with middle exhausted bath box (11) or concentration liquid case (20), give up in the concentrated solution outlet end of low pressure reverse osmosis device (19) and centre
Liquid case (11) or concentration liquid case (20) connect；
Boron-containing radioactive waste liquid is first stored in middle exhausted bath box (11), then sends into prefilter (13) by booster pump (12) and enters
Row filters, the suspended impurity that may remain in retention waste liquid, and the waste liquid after filtration passes through heat exchanger (14), will be given up by heating medium
Liquid temp is heated between 15～35 DEG C, then by one-level high-pressure pump (15), the pressure of waste liquid is brought up to 1.0～4.0MPa, plus
Pressure is further increased to 2.0～5.0MPa through recuperator (16) by waste liquid after pressure again, and the waste liquid after pressurization enters
High pressure counter-osmosis device (17) carries out process and obtains permeate and concentrate, and permeate is forced into 0.5 through two grades of high-pressure pumps (18) again
Enter low pressure reverse osmosis device (19) after～2.0MPa to be processed, concentrate is introduced into recuperator (16), in energy regenerating
The water outlet of one-level high-pressure pump (15) is transferred energy to, high pressure counter-osmosis device (17) concentrate is from recuperator in device (16)
(16), after flowing out, return to middle exhausted bath box (11) or drain into concentration liquid case (20), the concentrate of low pressure reverse osmosis device (19)
Also return to middle exhausted bath box (11) or drain into concentration liquid case (20).
2. boron-containing radioactive waste liquid deep purifying as claimed in claim 1 reclaim simultaneously boric acid method it is characterised in that：Institute
Stating boric acid concentration step adopts boric acid upgrading unit (2) to realize, and described boric acid upgrading unit (2) includes charging pump (21), heating
Device (22), evaporimeter (23), circulating pump (24), demister (25), clarifier (26), condenser (27), surge tank (28), concentration
The concentrate that liquid discharging pump (29), deep purifying and boric acid preconcentration steps produce accesses circulating pump (24) by charging pump (21)
Entrance point, the steam (vapor) outlet end of evaporimeter (23) and demister (25), clarifier (26), condenser (27), surge tank (28)
It is sequentially connected, the entrance point of circulating pump (24) and heater (22) is passed through at the liquid outlet end of demister (25) and clarifier (26)
Connect, the port of export of heater (22) is connected with the liquor inlet end of evaporimeter (23), the bottom material liquid outlet of evaporimeter (23)
It is connected with concentrate discharging pump (29), for discharging boron concentrate.
3. boron-containing radioactive waste liquid deep purifying as claimed in claim 2 reclaim simultaneously boric acid method it is characterised in that：Come
Reverse osmosis concentrated liquid from the concentration liquid case (20) of waste liquid deep purifying and boric acid pre-concentration unit (1) is noted by charging pump (21)
Enter the entrance point of circulating pump (24), the liquid that demister (25) and clarifier (26) are collected is from liquid outlet end through circulating pump (24)
Send into heater (22), material enters evaporimeter (23), evaporimeter (23) after being heated to 50～70 DEG C in heater (22)
The indirect steam of interior generation is introduced into demister (25), by the drop separation carried secretly in indirect steam out, then passes through net again
Change device (26) to retain the fine mist that may remain in indirect steam, the secondary steaming thus indirect steam is purified, after purification
Vapour is condensed into condensate liquid by condenser (27), and condensate liquid enters surge tank (28) and keeps in, and evaporimeter (23) remains certain true
Reciprocal of duty cycle is it is ensured that the operating pressure in evaporimeter (23) is 10～40kPa so that concentrating liquid energy to carry out boiling steaming at 50～70 DEG C
Send out.
4. boron-containing radioactive waste liquid deep purifying as claimed in claim 1 reclaim simultaneously boric acid method it is characterised in that：Boron
Acid crystal and recycling step adopt boric acid crystallization and recovery unit (3) to realize, and described boric acid crystallization includes changing with recovery unit (3)
Hot device (31), circulating pump (32), crystallizer (33), magma discharging pump (34), transfer tank (35), mother liquor tank (36), centrifugal filtration
Machine (37), ion exchange column (38), the import of circulating pump (32) and heat exchanger (31) is passed through at the material liquid outlet end of crystallizer (33)
End connects, and the concentrate that described boric acid concentration step produces accesses the entrance point of heat exchanger (31), and the magma of crystallizer (33) goes out
Mouth end is connected with transfer tank (35) by magma discharging pump (34), and the magma that crystallizer (33) produces is arranged by magma discharging pump (34)
To transfer tank (35), transfer tank (35) is used for carrying out separation of solid and liquid to magma, and the clarified mother liquor obtaining drains into mother liquor tank (36), and
Solid then filters the residual liquid in solid by filter centrifugal (37), and the liquid leaching drains into mother liquor tank (36), retention
Solid then first passes through ion exchange column (38) as the solution receiving in final boric acid product, mother liquor tank (36) and carries out radioactivity
Nucleic retains, and the radioactive mother liquor of removal returns again to boric acid concentration step and is circulated process.
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| CN110467190B (en) * | 2018-05-09 | 2024-04-09 | 上海核工程研究设计院股份有限公司 | Device and method for recycling boron from radioactive boron-containing waste liquid |
| WO2019220001A1 (en) * | 2018-05-18 | 2019-11-21 | Fortum Power And Heat Oy | Method of treating liquid radioactive waste containing boron |
| CN110277183A (en) * | 2019-07-09 | 2019-09-24 | 上海核工程研究设计院有限公司 | A kind of nuclear power plant technique system of recyclable enrichment boric acid |
| CN117038138B (en) * | 2023-08-16 | 2024-02-23 | 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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