CN104810071A - 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
- Publication number
- CN104810071A CN104810071A CN201510181562.5A CN201510181562A CN104810071A CN 104810071 A CN104810071 A CN 104810071A CN 201510181562 A CN201510181562 A CN 201510181562A CN 104810071 A CN104810071 A CN 104810071A
- Authority
- CN
- China
- Prior art keywords
- boric acid
- liquid
- concentrate
- waste liquid
- boron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- G21F9/06—Processing
-
- 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
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
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 the method and apparatus that a kind of boron-containing radioactive waste liquid deep purifying reclaims boric acid simultaneously.
Background technology
Nuclear power plant can produce a large amount of radioactive liquid waste in the operation and maintenance stage, and also contain soluble neutron absorber---boric acid in the waste liquid that wherein power plant's primary Ioops is discharged, the waste liquid that primary Ioops is discharged becomes boron-containing radioactive waste liquid.Boron-containing radioactive waste liquid have to pass through except boron, could to environmental emission except after radioactivity.In order to reduce the impact of discharging of waste liquid on environment to greatest extent, some nuclear power plants also require to carry out deep purifying to the treated waste liquid reaching emission standard.For the boric acid in waste liquid, some nuclear power plants are provided with boron recovery system, borate waste solution are condensed into utilization and recycle after dense boron liquid by evaporation technology; Some nuclear power plants do not arrange boron recovery system, need discharge after borate waste solution purification.
At present, what the process of nuclear power plant's boron-containing radioactive waste liquid adopted mostly is ion-exchange or evaporation technology.Ion-exchange process utilizes ion exchange resin to adsorb radioactive nuclide in waste liquid, the radioactive concentration of waste liquid can be reduced to below emission limit.Ion-exchange process is ripe, but cannot remove the boric acid in waste liquid.Evaporation technology be then by heating steam by waste liquid in evaporator ebuillition of heated vaporization, vaporization produce secondary steam condensed fluid after testing radioactive concentration qualified after discharged, steam raffinate then carry out cement solidification process.The good purification of evaporation technology, but shortcoming to be thermal energy consumption large, disposal cost is very high, and vapo(u)rization system more complicated, and the workload of operation and maintenance maintenance is all very large.
Also there is the report adopting additive method process borate waste solution, but be all not suitable for the deep purifying of nuclear power plant's boron-containing radioactive waste liquid and boric acid reclaims.Such as Chinese patent 02108593.5, it adopts two-stage oxidizing/flocculation process process boron-containing radioactive waste water, namely first in waste water, oxygenant and inorganic flocculating agent is added, through first order oxidation/flocculation, add polymeric flocculant again and carry out Separation of Solid and Liquid, and then add medicament and carry out second level oxidation/flocculation.The complex process of this method, need consume a large amount of chemical agents, produces a large amount of radioactivity mud simultaneously, secondary Waste disposal high cost.
Summary of the invention
The invention provides the method and apparatus that a kind of boron-containing radioactive waste liquid deep purifying reclaims boric acid simultaneously, while recovery boric acid, waste liquid can be carried out deep purifying, without the need to consuming a large amount of chemical agent, 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 liquid waste.
Boron-containing radioactive waste liquid deep purifying reclaims a method for boric acid simultaneously, comprises the steps:
Deep purifying and boric acid pre-concentration: boron-containing radioactive waste liquid is processed into concentrate and permeate two strands of materials through filtration, heat exchange, high pressure counter-infiltration and low pressure reverse osmosis, wherein in permeate, boron mass concentration is less than 50mg/L, radioactive concentration is less than 1/10 of input concentration, directly send into the discharge of monitoring letdown tank, in concentrate, boron mass concentration is 5000mg/L ~ 8000mg/L, sends into boric acid concentration step and concentrates further;
Boric acid concentrates: boron mass concentration is that the concentrate of 5000mg/L ~ 8000mg/L evaporates boiling under vacuum, the secondary steam that evaporation produces forms condensed fluid after mist separation, condensing cooling, the radioactive concentration of condensed fluid is reduced to below 10Bq/L, send into the discharge of monitoring letdown tank, in dense boron liquid residual after evaporation, boron mass concentration reaches 22000mg/L ~ 26000mg/L, is sent to boric acid crystallization and recycling step process;
Boric acid crystallization and recovery: the dense boron liquid that boric acid concentration step produces is cooled, crystallization, obtain the magma of boronic acid containing crystal, magma is after Separation of Solid and Liquid, can obtain boric acid solid product with recycle and reuse, the clarified mother liquor after magma Separation of Solid and Liquid retains through ion exchange column and returns boric acid concentration step again after radioactive nuclide and re-start concentrated.
Method as above, described deep purifying and boric acid preconcentration steps adopt waste liquid deep purifying and boric acid pre-concentration unit to realize, described waste liquid deep purifying and boric acid pre-concentration unit comprise the middle exhausted bath box connected successively, supercharge pump, prefilter, heat interchanger, one-level high-pressure pump, recuperator, high pressure counter-osmosis device, secondary high-pressure pump, low pressure reverse osmosis device and concentrate case, the permeate endpiece of its mesohigh counter-osmosis device is connected with low pressure reverse osmosis device by secondary high-pressure pump, the concentrated solution outlet end of high pressure counter-osmosis device is connected with middle exhausted bath box or concentrate case by recuperator, the concentrated solution outlet end of low pressure reverse osmosis device is connected with middle exhausted bath box or concentrate case.
Method as above, boron-containing radioactive waste liquid is first stored in middle exhausted bath box, then send into prefilter by supercharge pump to filter, retain the suspended impurity that may remain in waste liquid, waste liquid after filtration passes through heat interchanger, by heating medium, waste liquid temperature is heated between 15 ~ 35 DEG C, then by one-level high-pressure pump, the pressure of waste liquid is brought up to 1.0 ~ 4.0MPa, pressure is brought up to 2.0 ~ 5.0MPa through recuperator by waste liquid after pressurization more further, waste liquid after pressurization enters high pressure counter-osmosis device to carry out process and obtains permeate and concentrate, permeate is forced into through secondary high-pressure pump and enters low pressure reverse osmosis device after 0.5 ~ 2.0MPa and process, concentrate is introduced into recuperator, in recuperator by energy transferring to the water outlet of one-level high-pressure pump, after high pressure counter-osmosis device concentrate flows out from recuperator, turn back to middle exhausted bath box or drain into concentrate case, the concentrate of low pressure reverse osmosis device also turns back to middle exhausted bath box or drains into concentrate case.
Method as above, described boric acid concentration step adopts boric acid upgrading unit to realize, described boric acid upgrading unit comprises charging pump, well heater, evaporator, ebullator, demister, clarifier, condenser, surge tank, concentrate discharging pump, the concentrate that deep purifying and boric acid preconcentration steps produce is by the entrance point of charging pump access ebullator, the steam (vapor) outlet end of evaporator and demister, clarifier, condenser, surge tank connects successively, demister is connected with the entrance point of well heater by ebullator with the liquid outlet end of clarifier, the endpiece of well heater is connected with the liquor inlet end of evaporator, the bottom material liquid outlet of evaporator is connected with concentrate discharging pump, for boron concentrate is discharged.
Method as above, injected the entrance point of ebullator by charging pump from the reverse osmosis concentrated liquid in the concentrate case of waste liquid deep purifying and boric acid pre-concentration unit, the liquid that demister and clarifier are collected sends into well heater from liquid outlet end through ebullator, material is entered evaporator by after heating 50 ~ 70 DEG C in well heater, the secondary steam produced in evaporator is introduced into demister, by the drop separation of carrying secretly in secondary steam out, and then by clarifier, the fine mist that may remain in secondary steam is retained, thus secondary steam is purified, secondary steam after purification becomes condensed fluid by condenser condenses, condensed fluid enters surge tank and keeps in, evaporator maintains certain vacuum tightness, ensure that the working pressure in evaporator is 10 ~ 40kPa, make concentrate can carry out explosive evaporatoin 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 and recovery unit comprise heat interchanger, ebullator, crystallizer, magma discharging pump, transfer tank, mother liquor tank, filter centrifugal, ion exchange column, the material liquid outlet end of crystallizer is connected with the entrance point of heat interchanger by ebullator, the entrance point of the concentrate access heat interchanger that described boric acid concentration step produces, the magma endpiece of crystallizer is connected with transfer tank by magma discharging pump, the magma that crystallizer produces is drained into transfer tank by magma discharging pump, transfer tank is used for carrying out Separation of Solid and Liquid to magma, the clarified mother liquor obtained drains into mother liquor tank, solid then filters the residual liquid in solid by filter centrifugal, the liquid leached drains into mother liquor tank, the solid retained is then as final boric acid product, the solution received in mother liquor tank first carries out radioactive nuclide by ion exchange column and retains, remove radioactive mother liquor to return boric acid concentration step again and carry out circular treatment.
Boron-containing radioactive waste liquid deep purifying reclaims an equipment for boric acid simultaneously, it is characterized in that: comprise waste liquid deep purifying and boric acid pre-concentration unit, boric acid upgrading unit and boric acid recovery unit,
Waste liquid deep purifying and boric acid pre-concentration unit comprise the middle exhausted bath box, supercharge pump, prefilter, heat interchanger, one-level high-pressure pump, recuperator, high pressure counter-osmosis device, secondary high-pressure pump, low pressure reverse osmosis device and the concentrate case that connect successively, the permeate endpiece of its mesohigh counter-osmosis device is connected with low pressure reverse osmosis device by secondary high-pressure pump, the concentrated solution outlet end of high pressure counter-osmosis device is connect by recuperator and middle exhausted bath box or concentrate case, and the concentrated solution outlet end of low pressure reverse osmosis device is connected with middle exhausted bath box or concentrate case;
Boric acid upgrading unit comprises charging pump, well heater, evaporator, ebullator, demister, clarifier, condenser, surge tank, concentrate discharging pump, concentrate case is connected with the entrance point of ebullator by charging pump, the steam (vapor) outlet end of evaporator and demister, clarifier, condenser, surge tank connects successively, demister is connected with the entrance point of well heater by ebullator with the liquid outlet end of clarifier, the endpiece of well heater is connected with the liquor inlet end of evaporator, the bottom material liquid outlet of evaporator is connected with concentrate discharging pump, for boron concentrate is discharged,
Boric acid crystallization and recovery unit comprise heat interchanger, ebullator, 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 interchanger by ebullator, pipeline between the pipe outlet access ebullator of the concentrate discharging pump of boric acid upgrading unit end and the entrance point of heat interchanger, the endpiece of heat interchanger is connected with the entrance point of crystallizer, the magma endpiece of crystallizer is connected with transfer tank by magma discharging pump, transfer tank is used for carrying out Separation of Solid and Liquid to magma, the clarified mother liquor obtained drains into mother liquor tank, solid then enters filter centrifugal, residual liquid in solid filters by filter centrifugal, the liquid leached drains into mother liquor tank, the solid retained is then as final boric acid product, the solution received in mother liquor tank is first processed by ion exchange column, return concentrate case after radioactive nuclide in mother liquor is retained removal and carry out circular treatment.
Equipment as above, evaporator maintains certain vacuum tightness, ensures that the working pressure in evaporator is 10 ~ 40kPa
The effect adopting technical solution of the present invention to bring and advantage are:
(1) while recovery 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 radioactive nuclide can not be accumulated in concentrate, can ensure the normal operation of system;
(2) after deep purifying and the process of boric acid pre-concentration, the volume of waste liquid is reduced to original 1/10 ~ 1/15, and the treatment capacity of upgrading unit reduces greatly, not only greatly can reduce the energy consumption of upgrading unit, can also make upgrading unit device miniaturization;
(3) except boric acid crystal reaches except the scavenging solution of emission standard with purification is qualified, outwards secondary liquid waste is not discharged.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that boron-containing radioactive waste liquid deep purifying of the present invention reclaims the method for boric acid simultaneously;
Fig. 2 is the structural representation that boron-containing radioactive waste liquid deep purifying of the present invention reclaims waste liquid deep purifying and boric acid pre-concentration unit in the equipment of boric acid simultaneously;
Fig. 3 is the structural representation that boron-containing radioactive waste liquid deep purifying of the present invention reclaims the equipment mesoboric acid upgrading unit of boric acid simultaneously;
Fig. 4 is that boron-containing radioactive waste liquid deep purifying of the present invention reclaims the equipment mesoboric acid crystallization of boric acid and the structural representation of recovery unit simultaneously.
In figure: 1-waste liquid deep purifying and boric acid pre-concentration unit, 2-boric acid upgrading unit, the crystallization of 3-boric acid and recovery unit, 11-middle exhausted bath box, 12-supercharge pump, 13-prefilter, 14-heat interchanger, 15-one-level high-pressure pump, 16-recuperator, 17-high pressure counter-osmosis device, 18-secondary high-pressure pump, 19-low pressure reverse osmosis device, 20-concentrate case, 21-charging pump, 22-well heater, 23-evaporator, 24-ebullator, 25-demister, 26-clarifier, 27-condenser, 28-surge tank, 29-concentrate discharging pump, 31-heat interchanger, 32-ebullator, 33-crystallizer, 34-magma discharging pump, 35-transfer tank, 36-mother liquor tank, 37-filter centrifugal, 38-ion exchange column.
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 invention provides a kind of method that boron-containing radioactive waste liquid deep purifying reclaims boric acid simultaneously, comprise the steps:
Deep purifying and boric acid pre-concentration: first adopted by boron-containing radioactive waste liquid (wherein boron mass concentration is 50mg/L ~ 3000mg/L) deep purifying and boric acid pre-concentration treatment step to process, in this step, waste liquid, through methods such as filtration, heat exchange, high pressure counter-infiltration and low pressure reverse osmosis, is processed into concentrate and permeate two strands of materials.Wherein in permeate, boron mass concentration is less than 50mg/L, and radioactive concentration is less than 1/10 of input concentration, directly can send into the discharge of monitoring letdown tank; In concentrate, boron mass concentration is 5000mg/L ~ 8000mg/L, sends into boric acid concentration step and concentrates further.
Boric acid concentrates: in boric acid concentration step, boron mass concentration is that the concentrate of 5000mg/L ~ 8000mg/L evaporates boiling under vacuum, the secondary steam that evaporation produces forms condensed fluid after mist separation, condensing cooling, the radioactive concentration of condensed fluid is reduced to below 10Bq/L, also sends into the discharge of monitoring letdown tank; In dense boron liquid residual after evaporation, boron mass concentration 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 and recycling step, dense boron liquid is cooled, crystallization, and obtain the magma of boronic acid containing crystal, magma, after Separation of Solid and Liquid, can obtain boric acid solid product, and boric acid solid can recycle and reuse.Clarified mother liquor after magma Separation of Solid and Liquid retains after radioactive nuclide through ion exchange column, then returns boric acid concentration step and re-start concentrated.
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 the equipment of boric acid simultaneously, comprises waste liquid deep purifying and boric acid pre-concentration unit 1, boric acid upgrading unit 2 and boric acid recovery unit 3.
Waste liquid deep purifying and boric acid pre-concentration unit 1 comprise the middle exhausted bath box 11 connected successively, supercharge pump 12, prefilter 13, heat interchanger 14, one-level high-pressure pump 15, recuperator 16, high pressure counter-osmosis device 17, secondary high-pressure pump 18, low pressure reverse osmosis device 19 and concentrate case 20, the permeate endpiece of its mesohigh counter-osmosis device 17 is connected with low pressure reverse osmosis device 19 by secondary high-pressure pump 18, the concentrated solution outlet end of high pressure counter-osmosis device 17 is connected with middle exhausted bath box 11 or concentrate case 20 by recuperator 16, the concentrated solution outlet end of low pressure reverse osmosis device 19 is connected with middle exhausted bath box 11 or concentrate case 20.
As shown in Figure 2, the boron-containing radioactive waste liquid through rough handling is first stored in middle exhausted bath box 11, then sends into prefilter 13 by supercharge pump 12 and filters, retain the suspended impurity that may remain in waste liquid.Waste liquid after filtration is by a heat interchanger 14, by heating medium, waste liquid temperature 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, pressure is brought up to 2.0 ~ 5.0MPa through a recuperator 16 by waste liquid after pressurization more further.Waste liquid after pressurization enters high pressure counter-osmosis device 17 to carry out process and obtains permeate and concentrate, and the radioactive concentration of the permeate of high pressure counter-osmosis device 17 can reduce greatly; Meanwhile, in waste liquid, the boron of 90% ~ 98% is trapped within the concentrate of high pressure counter-osmosis device 17, and only has the boron of 2% ~ 10% to remain in permeate.The permeate of high pressure counter-osmosis device 17 is forced into through secondary high-pressure pump 18 and enters low pressure reverse osmosis device 19 after 0.5 ~ 2.0MPa and process, and the radioactive concentration of the permeate of low pressure reverse osmosis device 19 reduces further; Meanwhile, the boron entering in the waste liquid of low pressure reverse osmosis device 19 40% ~ 60% is trapped within the concentrate of low pressure reverse osmosis device 19, and the permeate boron concentration of low pressure reverse osmosis device 19 also reduces further.The permeate of low pressure reverse 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, in recuperator 16 by energy transferring to the water outlet of one-level high-pressure pump 15, to improve the intake pressure of high pressure counter-osmosis device 17.High pressure counter-osmosis device 17 concentrate turns back to middle exhausted bath box 11 or drains into concentrate case 20 after flowing out from recuperator 16.The concentrate of low pressure reverse osmosis device 19 also turns back to middle exhausted bath box 11 or drains into concentrate case 20.
Electric heating tube or heating coil are installed in concentrate case 20, ensure in the winter time low temperature time, concentrate temperature is not less than 15 DEG C, prevents the boric acid crystallization in concentrate.
As shown in Figure 3, boric acid upgrading unit 2 comprises charging pump 21, well heater 22, evaporator 23, ebullator 24, demister 25, clarifier 26, condenser 27, surge tank 28, concentrate discharging pump 29.
Concentrate case 20 is connected with the entrance point of evaporator 23 by charging pump 21, like this, injected the entrance point of ebullator 24 by charging pump 21 from the reverse osmosis concentrated liquid in the concentrate case 20 of waste liquid deep purifying and boric acid pre-concentration unit 1, the steam (vapor) outlet end of evaporator 23 is connected successively with demister 25, clarifier 26, condenser 27, surge tank 28, demister 25 is connected by the entrance point of ebullator 24 with well heater 22 with the liquid outlet end of clarifier 26, and the endpiece of well heater 22 is connected with the liquor inlet end of evaporator 23.The liquid that demister 25 and clarifier 26 are collected also sends into well heater 22 from liquid outlet end through ebullator 24, and material enters evaporator 23 be heated to 60 DEG C in well heater 22 after.The heating medium of well heater 22 can be heating steam, also can be conduction oil.The secondary steam produced in evaporator 23 is introduced into demister 25, by the drop separation of carrying secretly in secondary steam out, and then by a clarifier 26, the fine mist that may remain in secondary steam is retained, thus is purified by secondary steam.Secondary steam after purification, by a condenser 27, is condensed into condensed fluid, and condensed fluid enters surge tank 28 and keeps in.Evaporator 23 maintains certain vacuum tightness usually, ensures that the working pressure in evaporator 23 is 10 ~ 40kPa, makes concentrate can carry out explosive evaporatoin at 50 ~ 70 DEG C.The bottom material liquid outlet of evaporator 23 is connected with concentrate discharging pump 29, for being discharged by boron concentrate.
As shown in Figure 4, boric acid crystallization and recovery unit 3 comprise heat interchanger 31, ebullator 32, crystallizer 33, magma discharging pump 34, transfer tank 35, mother liquor tank 36, filter centrifugal 37, ion exchange column 38.The material liquid outlet end of crystallizer 33 is connected with the entrance point of heat interchanger 31 by ebullator 32, pipeline between the pipeline access ebullator 32 of the concentrate discharging pump 29 of boric acid upgrading unit 2 end and the entrance point of heat interchanger 31, like this, heat interchanger 31 is entered together with the circulating mother liquor that the concentration of evaporating generation by boric acid upgrading unit 2 is 22000 ~ 2600ppm, temperature is 50 ~ 70 DEG C boron concentrate and ebullator 32 export.In heat interchanger 31, the feed liquid that boron concentrate and circulating mother liquor are mixed to get is cooled to 10 DEG C, under the promotion of ebullator 32, send into crystallizer 33.In crystallizer 33, feed liquid is along certain channel flow, and iterative cycles, keeps uniform degree of supersaturation and lower degree of supercooling, complete crystallization process.The endpiece of heat interchanger 31 is connected with the entrance point of crystallizer 33.
The magma endpiece of crystallizer 33 is connected with transfer tank 35 by magma discharging pump 34, and the magma that crystallizer 33 produces is drained into transfer tank 35 by magma discharging pump 34.Transfer tank 35 is for carrying out Separation of Solid and Liquid to magma, the clarified mother liquor obtained drains into mother liquor tank 36, solid then enters filter centrifugal 37 and is further processed, residual liquid in solid filters by filter centrifugal 37, the liquid leached also drains into mother liquor tank 36, the solid retained then as final boric acid product, can be recycled.The solution received in mother liquor tank 36 is first processed by an ion exchange column 38, and radioactive nuclide in mother liquor is retained removal.Remove radioactive mother liquor and return concentrate case 20 again, send into boric acid upgrading unit 2 and carry out circular treatment.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, anyly belongs to those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (8)
1. boron-containing radioactive waste liquid deep purifying reclaims a method for boric acid simultaneously, it is characterized in that: comprise the steps:
Deep purifying and boric acid pre-concentration: boron-containing radioactive waste liquid is processed into concentrate and permeate two strands of materials through filtration, heat exchange, high pressure counter-infiltration and low pressure reverse osmosis, wherein in permeate, boron mass concentration is less than 50mg/L, radioactive concentration is less than 1/10 of input concentration, directly send into the discharge of monitoring letdown tank, in concentrate, boron mass concentration is 5000mg/L ~ 8000mg/L, sends into boric acid concentration step and concentrates further;
Boric acid concentrates: boron mass concentration is that the concentrate of 5000mg/L ~ 8000mg/L evaporates boiling under vacuum, the secondary steam that evaporation produces forms condensed fluid after mist separation, condensing cooling, the radioactive concentration of condensed fluid is reduced to below 10Bq/L, send into the discharge of monitoring letdown tank, in dense boron liquid residual after evaporation, boron mass concentration reaches 22000mg/L ~ 26000mg/L, is sent to boric acid crystallization and recycling step process;
Boric acid crystallization and recovery: the dense boron liquid that boric acid concentration step produces is cooled, crystallization, obtain the magma of boronic acid containing crystal, magma is after Separation of Solid and Liquid, can obtain boric acid solid product with recycle and reuse, the clarified mother liquor after magma Separation of Solid and Liquid retains through ion exchange column and returns boric acid concentration step again after radioactive nuclide and re-start concentrated.
2. boron-containing radioactive waste liquid deep purifying as claimed in claim 1 reclaims the method for boric acid simultaneously, it is characterized in that: 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) comprise the middle exhausted bath box (11) connected successively, supercharge pump (12), prefilter (13), heat interchanger (14), one-level high-pressure pump (15), recuperator (16), high pressure counter-osmosis device (17), secondary high-pressure pump (18), low pressure reverse osmosis device (19) and concentrate case (20), the permeate endpiece of its mesohigh counter-osmosis device (17) is connected with low pressure reverse osmosis device (19) by secondary high-pressure pump 18, the concentrated solution outlet end of high pressure counter-osmosis device (17) is connected with middle exhausted bath box (11) or concentrate case (20) by recuperator (16), the concentrated solution outlet end of low pressure reverse osmosis device (19) is connected with middle exhausted bath box (11) or concentrate case (20).
3. boron-containing radioactive waste liquid deep purifying as claimed in claim 2 reclaims the method for boric acid simultaneously, it is characterized in that:
Boron-containing radioactive waste liquid is first stored in middle exhausted bath box (11), then send into prefilter (13) by supercharge pump (12) to filter, retain the suspended impurity that may remain in waste liquid, waste liquid after filtration is by heat interchanger (14), by heating medium, waste liquid temperature 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, pressure is brought up to 2.0 ~ 5.0MPa through recuperator (16) by waste liquid after pressurization more further, waste liquid after pressurization enters high pressure counter-osmosis device (17) to carry out process and obtains permeate and concentrate, permeate enters low pressure reverse osmosis device (19) again and processes after secondary high-pressure pump (18) is forced into 0.5 ~ 2.0MPa, concentrate is introduced into recuperator (16), in recuperator (16) by energy transferring to the water outlet of one-level high-pressure pump (15), after high pressure counter-osmosis device (17) concentrate flows out from recuperator (16), turn back to middle exhausted bath box (11) or drain into concentrate case (20), the concentrate of low pressure reverse osmosis device (19) also turns back to middle exhausted bath box (11) or drains into concentrate case (20).
4. boron-containing radioactive waste liquid deep purifying as claimed in claim 1 reclaims the method for boric acid simultaneously, it is characterized in that: described boric acid concentration step adopts boric acid upgrading unit (2) to realize, described boric acid upgrading unit (2) comprises charging pump (21), well heater (22), evaporator (23), ebullator (24), demister (25), clarifier (26), condenser (27), surge tank (28), concentrate discharging pump (29), the concentrate that deep purifying and boric acid preconcentration steps produce is by the entrance point of charging pump (21) access ebullator (24), the steam (vapor) outlet end of evaporator (23) and demister (25), clarifier (26), condenser (27), surge tank (28) connects successively, demister (25) is connected by the entrance point of ebullator (24) with well heater (22) with the liquid outlet end of clarifier (26), the endpiece of well heater (22) is connected with the liquor inlet end of evaporator (23), the bottom material liquid outlet of evaporator (23) is connected with concentrate discharging pump (29), for boron concentrate is discharged.
5. boron-containing radioactive waste liquid deep purifying as claimed in claim 4 reclaims the method for boric acid simultaneously, it is characterized in that: the entrance point being injected ebullator (24) from the reverse osmosis concentrated liquid in the concentrate case (20) of waste liquid deep purifying and boric acid pre-concentration unit (1) by charging pump (21), the liquid that demister (25) and clarifier (26) are collected sends into well heater (22) from liquid outlet end through ebullator (24), material enters evaporator (23) be heated to 50 ~ 70 DEG C in well heater (22) after, the secondary steam produced in evaporator (23) is introduced into demister (25), by the drop separation of carrying secretly in secondary steam out, and then by clarifier (26), the fine mist that may remain in secondary steam is retained, thus secondary steam is purified, secondary steam after purification is condensed into condensed fluid by condenser (27), condensed fluid enters surge tank (28) and keeps in, evaporator (23) maintains certain vacuum tightness, ensure that the working pressure in evaporator (23) is 10 ~ 40kPa, make concentrate can carry out explosive evaporatoin at 50 ~ 70 DEG C.
6. boron-containing radioactive waste liquid deep purifying as claimed in claim 1 reclaims the method for boric acid simultaneously, it is characterized in that: boric acid crystallization and recycling step adopt boric acid crystallization and recovery unit (3) to realize, described boric acid crystallization and recovery unit (3) comprise heat interchanger (31), ebullator (32), crystallizer (33), magma discharging pump (34), transfer tank (35), mother liquor tank (36), filter centrifugal (37), ion exchange column (38), the material liquid outlet end of crystallizer (33) is connected with the entrance point of heat interchanger (31) by ebullator (32), the entrance point of concentrate access heat interchanger (31) that described boric acid concentration step produces, the magma endpiece of crystallizer (33) is connected with transfer tank (35) by magma discharging pump (34), the magma that crystallizer (33) produces is drained into transfer tank (35) by magma discharging pump (34), transfer tank (35) is for carrying out Separation of Solid and Liquid to magma, the clarified mother liquor obtained drains into mother liquor tank (36), solid then filters the residual liquid in solid by filter centrifugal (37), the liquid leached drains into mother liquor tank (36), the solid retained is then as final boric acid product, the solution received in mother liquor tank (36) first carries out radioactive nuclide by ion exchange column (38) and retains, remove radioactive mother liquor to return boric acid concentration step again and carry out circular treatment.
7. boron-containing radioactive waste liquid deep purifying reclaims an equipment for boric acid simultaneously, it is characterized in that: comprise waste liquid deep purifying and boric acid pre-concentration unit (1), boric acid upgrading unit (2) and boric acid recovery unit (3),
Waste liquid deep purifying and boric acid pre-concentration unit (1) comprise the middle exhausted bath box (11) connected successively, supercharge pump (12), prefilter (13), heat interchanger (14), one-level high-pressure pump (15), recuperator (16), high pressure counter-osmosis device (17), secondary high-pressure pump (18), low pressure reverse osmosis device (19) and concentrate case (20), the permeate endpiece of its mesohigh counter-osmosis device (17) is connected with low pressure reverse osmosis device (19) by secondary high-pressure pump (18), the concentrated solution outlet end of high pressure counter-osmosis device (17) is connect by recuperator (16) and middle exhausted bath box (11) or concentrate case (20), the concentrated solution outlet end of low pressure reverse osmosis device (19) is connected with middle exhausted bath box (11) or concentrate case (20),
Boric acid upgrading unit (2) comprises charging pump (21), well heater (22), evaporator (23), ebullator (24), demister (25), clarifier (26), condenser (27), surge tank (28), concentrate discharging pump (29), concentrate case (20) is connected by the entrance point of charging pump (21) with ebullator (24), the steam (vapor) outlet end of evaporator (23) and demister (25), clarifier (26), condenser (27), surge tank (28) connects successively, demister (25) is connected by the entrance point of ebullator (24) with well heater (22) with the liquid outlet end of clarifier (26), the endpiece of well heater (22) is connected with the liquor inlet end of evaporator (23), the bottom material liquid outlet of evaporator (23) is connected with concentrate discharging pump (29), for boron concentrate is discharged,
Boric acid crystallization and recovery unit (3) comprise heat interchanger (31), ebullator (32), crystallizer (33), magma discharging pump (34), transfer tank (35), mother liquor tank (36) and filter centrifugal (37), ion exchange column (38), the material liquid outlet end of crystallizer (33) is connected with the entrance point of heat interchanger (31) by ebullator (32), pipeline between pipe outlet access ebullator (32) of the concentrate discharging pump (29) of boric acid upgrading unit (2) end and the entrance point of heat interchanger (31), the endpiece of heat interchanger (31) is connected with the entrance point of crystallizer (33), the magma endpiece of crystallizer (33) is connected with transfer tank (35) by magma discharging pump (34), transfer tank (35) is for carrying out Separation of Solid and Liquid to magma, the clarified mother liquor obtained drains into mother liquor tank (36), solid then enters filter centrifugal (37), residual liquid in solid filters by filter centrifugal (37), the liquid leached drains into mother liquor tank (36), the solid retained is then as final boric acid product, the solution received in mother liquor tank (36) is first processed by ion exchange column (38), return concentrate case (20) after radioactive nuclide in mother liquor is retained removal and carry out circular treatment.
8. boron-containing radioactive waste liquid deep purifying as claimed in claim 7 reclaims the equipment of boric acid simultaneously, it is characterized in that: evaporator (23) maintains certain vacuum tightness, ensures that the working pressure in evaporator (23) is 10 ~ 40kPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510181562.5A CN104810071B (en) | 2015-04-16 | 2015-04-16 | Method and equipment for deep purifying of boron-containing radioactive waste liquid and recovery of boric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510181562.5A CN104810071B (en) | 2015-04-16 | 2015-04-16 | Method and equipment for deep purifying of boron-containing radioactive waste liquid and recovery of boric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104810071A true CN104810071A (en) | 2015-07-29 |
| CN104810071B CN104810071B (en) | 2017-02-22 |
Family
ID=53694844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510181562.5A Active CN104810071B (en) | 2015-04-16 | 2015-04-16 | Method and equipment for deep purifying of boron-containing radioactive waste liquid and recovery of boric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104810071B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467190A (en) * | 2018-05-09 | 2019-11-19 | 上海核工程研究设计院有限公司 | A kind of device and method for recycling boron in radioactivity borate waste solution |
| WO2019220001A1 (en) * | 2018-05-18 | 2019-11-21 | Fortum Power And Heat Oy | Method of treating liquid radioactive waste containing boron |
| 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 |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3634180A1 (en) * | 1985-05-13 | 1987-05-27 | Tatabanyai Szenbanyak | Process for recovering boric-acid solutions that can be re-used in nuclear power stations from radioactive wastes and solutions arising in nuclear power stations |
| CN103408030A (en) * | 2013-07-31 | 2013-11-27 | 中科华核电技术研究院有限公司 | Method and device for separating boric acid in reactor coolant for nuclear power station |
| CN103418151A (en) * | 2013-08-19 | 2013-12-04 | 中科华核电技术研究院有限公司 | Distilling device |
| CN203545801U (en) * | 2013-11-11 | 2014-04-16 | 湖南桃花江核电有限公司 | Boron-containing radioactive wastewater treatment device |
| CN103794260A (en) * | 2012-10-31 | 2014-05-14 | 中国广东核电集团有限公司 | Evaporation treatment method for radioactive waste liquids of nuclear power plant |
| KR101399365B1 (en) * | 2013-08-27 | 2014-05-27 | (주)이엔이 | Apparatus for disposal of liquid radioactive waste |
| CN203839061U (en) * | 2014-02-25 | 2014-09-17 | 中国核电工程有限公司 | Reverse osmosis boron concentrating device for waste liquid processing system of nuclear power plant |
| CN204204438U (en) * | 2014-11-26 | 2015-03-11 | 湖南桃花江核电有限公司 | A kind of nuclear power plant radioactive wastewater ion-exchange treatment system |
| CN204614460U (en) * | 2015-04-16 | 2015-09-02 | 湖南桃花江核电有限公司 | Boron-containing radioactive waste liquid deep purifying reclaims the equipment of boric acid simultaneously |
-
2015
- 2015-04-16 CN CN201510181562.5A patent/CN104810071B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3634180A1 (en) * | 1985-05-13 | 1987-05-27 | Tatabanyai Szenbanyak | Process for recovering boric-acid solutions that can be re-used in nuclear power stations from radioactive wastes and solutions arising in nuclear power stations |
| CN103794260A (en) * | 2012-10-31 | 2014-05-14 | 中国广东核电集团有限公司 | Evaporation treatment method for radioactive waste liquids of nuclear power plant |
| CN103408030A (en) * | 2013-07-31 | 2013-11-27 | 中科华核电技术研究院有限公司 | Method and device for separating boric acid in reactor coolant for nuclear power station |
| CN103418151A (en) * | 2013-08-19 | 2013-12-04 | 中科华核电技术研究院有限公司 | Distilling device |
| KR101399365B1 (en) * | 2013-08-27 | 2014-05-27 | (주)이엔이 | Apparatus for disposal of liquid radioactive waste |
| CN203545801U (en) * | 2013-11-11 | 2014-04-16 | 湖南桃花江核电有限公司 | Boron-containing radioactive wastewater treatment device |
| CN203839061U (en) * | 2014-02-25 | 2014-09-17 | 中国核电工程有限公司 | Reverse osmosis boron concentrating device for waste liquid processing system of nuclear power plant |
| CN204204438U (en) * | 2014-11-26 | 2015-03-11 | 湖南桃花江核电有限公司 | A kind of nuclear power plant radioactive wastewater ion-exchange treatment system |
| CN204614460U (en) * | 2015-04-16 | 2015-09-02 | 湖南桃花江核电有限公司 | Boron-containing radioactive waste liquid deep purifying reclaims the equipment of boric acid simultaneously |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467190A (en) * | 2018-05-09 | 2019-11-19 | 上海核工程研究设计院有限公司 | A kind of device and method for recycling boron in radioactivity borate waste solution |
| 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 |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104810071B (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN204614460U (en) | Boron-containing radioactive waste liquid deep purifying reclaims the equipment of boric acid simultaneously | |
| CN103204601B (en) | Wastewater treatment method | |
| CN105293772A (en) | Method for recovering of rare earth and resource utilization of ammonia nitrogen from rare earth processing and smelting wastewater | |
| CN107140779A (en) | The zero-discharge treatment system and its processing method of a kind of nuclear power plant evaporator sewer | |
| CN105948359B (en) | A kind of processing method of rare-earth industry waste water | |
| CN104810071A (en) | Method and equipment for deep purifying of boron-containing radioactive waste liquid and recovery of boric acid | |
| CN104310687A (en) | Efficient MVR integrated seawater desalination device and seawater desalination method | |
| CN104909494A (en) | Process for impurity removal and purification of industrial high-concentration brine and special equipment of process | |
| CN110853790B (en) | Treatment method and treatment system for production waste liquid of high-temperature gas cooled reactor fuel element | |
| CN105906132A (en) | Rare-earth saponification wastewater comprehensive treatment system | |
| CN103723736A (en) | Resource recovery method in white carbon black production process | |
| CN207108723U (en) | A kind of zero-discharge treatment system of nuclear power plant evaporator sewer | |
| CN103316588A (en) | Multiple-effect membrane distillation device and method | |
| JP2011521781A (en) | Amine recovery method from amine-containing wastewater | |
| CN207619159U (en) | A kind of condensate polishing treatment regenerative wastewater ammonia recovery system | |
| CN107459021B (en) | Apparatus and method for decomposing nitrate solution | |
| CN105645490A (en) | Rare-earth processing wastewater treatment plant and technique | |
| CN106977037A (en) | A kind of industrial wastewater treatment device and method | |
| CN210764418U (en) | Evaporation crystallization separation integration system | |
| CN111681797B (en) | Method for treating radioactive wastewater of retired field of small nuclear facility | |
| CN104973581A (en) | Treatment method of phosphoric acid waste liquid | |
| CN103831022A (en) | Device and method for recycling ammonia nitrogen from coking wastewater | |
| CN102295380A (en) | Processing and recovering method of aromatic nitro-compound wastewater | |
| CN105948361B (en) | The recovery system of rare-earth industry waste water | |
| CN105906131A (en) | Method for recycling magnesium chloride from rare earth industrial wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |