WO2019196143A1 - Radioactive waste liquid treatment method and apparatus - Google Patents

Radioactive waste liquid treatment method and apparatus Download PDF

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Publication number
WO2019196143A1
WO2019196143A1 PCT/CN2018/085069 CN2018085069W WO2019196143A1 WO 2019196143 A1 WO2019196143 A1 WO 2019196143A1 CN 2018085069 W CN2018085069 W CN 2018085069W WO 2019196143 A1 WO2019196143 A1 WO 2019196143A1
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Prior art keywords
reverse osmosis
stage
liquid
continuous electric
subunit
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PCT/CN2018/085069
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French (fr)
Chinese (zh)
Inventor
赵璇
李福志
张猛
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清华大学
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Publication of WO2019196143A1 publication Critical patent/WO2019196143A1/en

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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04Treating liquids
    • G21F9/06Processing
    • GPHYSICS
    • G21NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21FPROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04Treating liquids
    • G21F9/06Processing
    • G21F9/12Processing by absorption; by adsorption; by ion-exchange
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124Water desalination
    • Y02A20/131Reverse-osmosis

Definitions

  • the present application relates to the technical field of radioactive waste liquid treatment, and in particular, to a method and a device for treating radioactive waste liquid.
  • the radioactive waste liquid can be divided into three categories: (1) low salinity radioactive waste liquid with a salt content of 0g ⁇ L -1 to 2g ⁇ L -1 ; (2) salt content is Medium-salt radioactive waste liquid of 2g ⁇ L -1 to 10g ⁇ L -1 ; (3) High-salt radioactive waste liquid with a salt content of 10g ⁇ L -1 or more.
  • the salt and the radionuclide are generally treated together as a treatment target.
  • the ratio of the amount of non-radioactive salts to the amount of radionuclides is usually greater than 10 5 or even higher, non-radioactive salts and radionuclides are treated together as treatment targets.
  • Most of the concentrate is non-radioactive, which greatly increases the amount of secondary radioactive waste.
  • a method and apparatus for treating a radioactive waste liquid which have a higher level of purification, and at the same time, can significantly reduce the amount of radioactive waste generated, and achieve a small quantification of radioactive waste.
  • the radioactive waste liquid treatment method and apparatus according to the embodiments of the present application are particularly suitable for the treatment of high salinity radioactive waste liquid.
  • a method for treating a radioactive waste liquid comprising: separating a radioactive waste liquid to obtain a first purifying liquid and a concentrated liquid; and removing the radioactive nuclides from the concentrated liquid, Obtaining a second purifying liquid, wherein the removing the radioactive nuclides from the concentrated liquid comprises: the concentrated liquid is subjected to a chemical precipitation process; and the first purified liquid and the second purified liquid are discharged.
  • the first purification liquid that meets or even exceeds the discharge standard is obtained by separating the radioactive waste liquid, and the majority of the radioactive nuclide is retained in the concentrate, the concentrate It has a high radionuclide concentration and is treated by a chemical precipitation process to selectively remove radionuclides.
  • Non-radioactive salts are discharged together with the purification liquid, and no radioactive concentrate is produced, thus greatly reducing non-radioactive The amount of salt entering the radioactive waste, thereby significantly reducing the amount of secondary radioactive waste generated.
  • the radioactive waste liquid in the method of the present application is greatly concentrated, the volume of the radioactive waste liquid to be treated is greatly reduced, and the concentration of the target radionuclide ion to be removed in the concentrated liquid is increased. It can greatly improve the decontamination factor of radioactive nuclides in the chemical precipitation process, thereby significantly reducing the amount of radioactive waste generated.
  • a radioactive waste liquid processing apparatus comprising a separation unit, a chemical precipitation unit and a drainage unit, wherein a concentrate outlet of the separation unit is connected to an inlet of the chemical precipitation unit;
  • the purification liquid outlet of the separation unit and the purification liquid outlet of the chemical precipitation unit are respectively connected to the drainage unit.
  • FIG. 1 is a schematic view showing a process flow of a method for treating a radioactive waste liquid provided by an embodiment of the present application.
  • FIG. 2 is a schematic view showing a process flow of a method for treating a radioactive waste liquid provided by another embodiment of the present application.
  • FIG. 3 is a schematic view showing a process flow of a method for treating a radioactive waste liquid provided by still another embodiment of the present application.
  • FIG. 4 is a schematic diagram showing the process flow of a radioactive waste liquid processing apparatus provided by an embodiment of the present application.
  • FIG. 5 is a schematic diagram showing the process flow of a radioactive waste liquid processing apparatus according to another embodiment of the present application.
  • FIG. 6 is a schematic view showing the process flow of a radioactive waste liquid processing apparatus according to still another embodiment of the present application.
  • FIG. 7 is a flow chart showing the process of a radioactive waste liquid processing apparatus provided by another embodiment of the present application.
  • 101 a degreasing filter
  • 102 an inorganic membrane filter
  • 201 buffer water tank; 202, security filter; 203, high pressure pump; 204, buffer water tank; 205, circulation pump;
  • reverse osmosis subunit 211, first stage reverse osmosis equipment; 212, second stage reverse osmosis equipment; 213, reverse osmosis equipment;
  • first-stage continuous electric desalination equipment 221, first-stage continuous electric desalination equipment; 222, second-stage continuous electric desalination equipment; 223, continuous electric desalination equipment; 224, intermediate water tank; 225, activator tank;
  • the concentration of radionuclide ions in radioactive wastewater is extremely low, and the concentration of radionuclide ions is further reduced to achieve an environmental emission requirement of less than 10 Bq/L, which is very important for the treatment capacity of radioactive wastewater treatment technology.
  • Some radioactive waste waters have a non-radioactive salt content of 10g ⁇ L -1 or more, or even higher.
  • the prior art treats non-radioactive salts together with radionuclides as treatment targets, so that the amount of secondary radioactive waste is greatly increased.
  • An important principle of radioactive wastewater treatment is the requirement for small quantification of radioactive waste. In addition, the operability and maintainability of the equipment under radioactive conditions need to be considered.
  • the embodiments of the present application provide a radioactive waste liquid treatment method and device, which have a higher purification level, and significantly reduce the amount of radioactive waste generated, thereby achieving a small quantification of radioactive waste.
  • the "concentration factor” is calculated as (influent volume) / (volume of concentrate); "removal rate” is (by mass concentration of radionuclide in the influent - mass concentration of radionuclide in the produced water) / ( Calculation of the mass concentration of radionuclides in the influent; “recovery rate” is calculated as (water production) / (influent water); “decontamination factor” is (radiation activity of influent water) / (radiation activity of water production) ) Calculation.
  • the method and device for treating radioactive waste liquid provided by the embodiments of the present application are particularly suitable for the treatment of high salinity radioactive waste liquid.
  • FIG. 1 is a schematic view showing a process flow of a method for treating a radioactive waste liquid provided by an embodiment of the present application, according to which:
  • the radioactive waste water is first separated and treated to obtain a first purified liquid and a concentrated liquid.
  • the concentration factor can be more than 2 times, such as 2 to 10 times, and most of the radioactive nuclides in the radioactive waste water are retained in the concentrate, so that the mass concentration of the radionuclide in the concentrate can reach the radioactivity in the radioactive waste liquid.
  • the mass concentration of the radionuclide is more than twice that of the radionuclides, and the mass concentration of the radionuclide in the first purification liquid is lower than the mass concentration of the radionuclide in the radioactive waste water, which is even better than the emission standard and is discharged.
  • the concentrated liquid is subjected to removal of radionuclide treatment to obtain a second purification liquid.
  • the method comprises the steps of: subjecting the concentrated liquid to a chemical precipitation process, and removing the radionuclide by adding a chemical precipitating agent to the concentrated liquid to promote the conversion of the radioactive nuclide ions into a poorly soluble substance to precipitate and precipitate.
  • the chemical precipitant may be one or more of carbonate, phosphate, sulfide, sulfate, hydroxide, metal oxide, oxalic acid, oxalate, but is not limited thereto, as long as it can achieve radioactivity
  • the nuclide is converted into a poorly soluble substance and precipitated.
  • Non-radioactive salts are discharged together with the purification liquid, and no radioactive concentrated waste liquid is produced. This greatly reduces the amount of non-radioactive salts entering the radioactive waste, thereby significantly reducing the amount of secondary radioactive waste generated. .
  • the dosage of the chemical precipitant in the chemical precipitation is directly related to the ion concentration of the radionuclide in the solution and the removal rate required. Since the concentrate has a high concentration of radionuclides, it is treated by a chemical precipitation process.
  • the radioactive waste liquid is greatly concentrated, the volume of the radioactive waste liquid to be treated is greatly reduced, and the concentration of the target radionuclide ion to be removed in the concentrate is increased, and the chemical can be greatly improved.
  • the precipitation process has a significant reduction in the decontamination factor of the radionuclide, the chemical precipitant required to achieve the same removal rate, or the removal rate of the same chemical precipitant dosage, thereby significantly reducing the amount of radioactive waste generated.
  • the discharge treatment may be performed, and the first purification liquid and the second purification liquid may be directly discharged, that is, the first purification liquid is discharged through one pipeline, and the second purification is performed.
  • the liquid is discharged through the second line; or the two may be mixed and discharged, that is, the second purified liquid is merged with the first purified liquid through the first line, and then drained.
  • the second purification liquid is mixed with the first purification liquid through the first pipeline and then discharged.
  • the chemical precipitation process can further remove the radionuclide by selective inorganic adsorption, thereby improving Decontamination factor for radionuclides.
  • the concentrated liquid is subjected to a chemical precipitation process and then subjected to an inorganic adsorption process, which can reduce the processing load of the inorganic adsorption process.
  • the separation treatment may adopt one or more of a nanofiltration process, a reverse osmosis process, and a continuous electric desalination process according to actual conditions such as the composition, content, and processing requirements of the radioactive waste water.
  • the first-stage or two-stage reverse osmosis process can be used, but it is not limited thereto, and the three-stage reverse osmosis process can also be adopted according to the actual situation.
  • the separation treatment process adopts a first-stage reverse osmosis process, specifically, the radioactive waste liquid is subjected to a first-stage reverse osmosis process to obtain a first-stage reverse osmosis purification liquid and a first-stage reverse osmosis concentrate as the first purification liquid and Concentrate.
  • the reverse osmosis process may employ one or two or more stages of reverse osmosis treatment.
  • the upper stage reverse osmosis treatment intermediate concentrate is used as the feed water of the next stage of reverse osmosis treatment, ie
  • the radioactive waste liquid is subjected to reverse osmosis treatment in two or more stages to obtain a concentrated liquid.
  • the purified liquid is sent out from each section, and the purified liquid sent from all the sections is combined into a first-stage reverse osmosis purification liquid, which can improve the recovery rate of reverse osmosis. .
  • the separation treatment process adopts a two-stage reverse osmosis process to further improve the level of reverse osmosis purification.
  • the radioactive waste liquid is first sent to the first-stage reverse osmosis process to obtain the first-stage reverse osmosis purification liquid and
  • the first stage reverse osmosis concentrate is sent to the second stage reverse osmosis process to obtain the second stage reverse osmosis purification liquid and the second stage reverse osmosis concentrate.
  • the second-stage reverse osmosis concentrate is returned to the first-stage reverse osmosis process, and the first-stage reverse osmosis concentrate is sent to the chemical precipitation process as the concentrated liquid;
  • the second-stage reverse osmosis purification liquid is lower than 10 Bq/ L, in line with the requirements of the discharge standard, as the first purification liquid for discharge treatment.
  • the first-stage reverse osmosis process may adopt one or two or more stages of reverse osmosis treatment.
  • the stage-level concentrate produced by the reverse osmosis treatment of the previous stage is used as the next stage of reverse osmosis treatment.
  • the influent water, that is, the radioactive waste liquid is sequentially subjected to reverse osmosis treatment of two or more stages to obtain a concentrated liquid, and at the same time, the purified liquid is sent out from each section, and the purified liquid sent from all the sections is merged into the first-stage reverse osmosis purification liquid.
  • the second-stage reverse osmosis process may employ one or two or more stages of reverse osmosis treatment.
  • the stage-stage concentrate produced by the previous stage of reverse osmosis treatment is used as the next stage.
  • the influent treated by reverse osmosis that is, the radioactive waste liquid is subjected to reverse osmosis treatment of two or more stages in turn to obtain a second-stage reverse osmosis concentrate, and the purified liquid is sent from each section, and the purified liquid sent from all the sections is merged into the second.
  • Grade reverse osmosis purification solution is provided.
  • the first-stage reverse osmosis process and the second-stage reverse osmosis process all adopt three-stage reverse osmosis treatment to form a “two-stage three-stage” reverse osmosis process for separation of radioactive wastewater pairs, which has high purification. Capacity and concentration factor reduce the load on the chemical precipitation treatment process while increasing recovery.
  • the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis process or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process has a radioactivity of more than 10 Bq/L, or if the first emission is pursued
  • the purification liquid can achieve lower radioactivity
  • the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis process or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process can be sent to the continuous electric elimination.
  • the salt process (shown in Figure 2) or the ion exchange process (shown in Figure 3) is further refined.
  • the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis process or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process is subjected to a first-stage continuous electric desalination process for fine treatment to obtain the first Purification liquids often meet the requirements of emission standards, even reach the natural background level, contain almost no radionuclides, and discharge treatment.
  • the first-stage continuous electric desalting concentrate is returned to the first-stage reverse osmosis process or two-stage reverse osmosis.
  • the first stage reverse osmosis process in the process is subjected to a first-stage continuous electric desalination process for fine treatment to obtain the first Purification liquids often meet the requirements of emission standards, even reach the natural background level, contain almost no radionuclides, and discharge treatment.
  • the first-stage continuous electric desalting concentrate is returned to the first-stage reverse osmosis process or two-stage reverse osmosis.
  • the activator may be added to the second-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis process or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process, and then sent.
  • the activator can be prepared from pure water having a resistivity of more than 0.5 M ⁇ cm and different kinds of inorganic salts, and the activator contains ions Ca 2+ , Na + , Sr 2+ , Zn 2+ , Mg 2+ , Fe 2 .
  • the type of anion is not limited, the concentration of the activator stock solution is related to the dosage, ensuring that the ion concentration in the radioactive waste water is as follows after the activator is added to the radioactive waste water and mixed uniformly: Ca 2+ 0.1 mg / L ⁇ 0.2 mg/L, Na + 0.2 mg/L to 0.3 mg/L, Sr 2+ 8 mg/L to 9 mg/L, Zn 2+ 18 mg/L to 20 mg/L, Mg 2+ 0.2 mg/L to 0.25 mg/ L, Fe 2+ 0.04 mg/L to 0.05 mg/L and K + 100 mg/L to 150 mg/L.
  • the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis process or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process is subjected to a two-stage continuous electric desalination process for fine treatment, specifically Firstly, the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis process or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process is sent to the first-stage continuous electric desalination process to obtain the first-stage continuous process.
  • the continuous electric desalting concentrate and the second-stage continuous electric desalting concentrate return to the first-stage reverse osmosis process in the first-stage reverse osmosis process or the two-stage reverse osmosis process.
  • an activator may be added to the first-stage continuous electric desalination purification liquid, and then sent to a second-stage continuous electric desalination process for purification treatment.
  • the activator may be selected from an activator as described above.
  • the fine treatment may also be an ion exchange process using one or more stages.
  • the purified liquid obtained by the first-stage or two-stage reverse osmosis process is sequentially subjected to one or more ion exchange processes to obtain a first purified liquid.
  • the separation treatment process is not limited to adopting the above process, for example, it may be a continuous electric desalination process of more than one level; a nanofiltration-reverse osmosis combination process; a nanofiltration-continuous electric desalination combination process; Reverse osmosis-continuous electric desalination combined process; nanofiltration-reverse osmosis-ion exchange combination process, etc., can be determined by those skilled in the art according to actual conditions.
  • the radioactive waste water is optionally pretreated before the radioactive waste water is separated, but this is not an essential process.
  • radioactive waste water may also contain impurities such as oils, colloids, and particulate matter. Most of these impurities are non-radioactive, but they may affect processes such as reverse osmosis, chemical precipitation, and inorganic adsorption. The removal of these impurities can prolong the life cycle of the reverse osmosis membrane and the inorganic adsorbent, reduce the replacement of the reverse osmosis membrane and the inorganic adsorbent, improve the efficiency of the chemical precipitant, and further reduce the amount of radioactive waste inorganic adsorbent and radioactive chemical precipitation. The amount of matter produced.
  • the embodiment of the present application further provides a radioactive waste liquid processing apparatus, which will be described in detail below with reference to FIGS. 4 to 7.
  • FIG. 4 is a schematic diagram showing the process flow of a radioactive waste liquid processing apparatus provided by an embodiment of the present application.
  • the apparatus includes a separation unit 200, a chemical precipitation unit 310, and a drainage unit 400, wherein the concentrate outlet of the separation unit 200 is connected to the inlet of the chemical precipitation unit 310; the purification liquid outlet of the separation unit 200 and the purification liquid outlet of the chemical precipitation unit 310 Connected to the drain unit 400, respectively.
  • the drainage unit 400 includes a first drainage subunit and a second drainage subunit (not shown), the purification liquid outlet of the separation unit 200 is connected to the first drainage subunit, and the purification liquid outlet of the chemical precipitation unit 310 Connected to the second drainage subunit, the first drainage subunit and the second drainage subunit may be in communication.
  • the first purification liquid and the second purification liquid may be directly discharged according to different requirements, or may be discharged after mixing the two;
  • the second purification liquid is mixed with the first purification liquid and meets the requirements of the discharge standard, the second purification liquid is mixed with the first purification liquid and discharged.
  • the drainage unit 400 may be only a drainage pipe, or may be connected to the drainage discharge tank 410 (as shown in FIG. 6 and FIG. 7) on the drainage pipe to monitor the drainage activity, or other purification liquid.
  • the form of discharge is not limited in this application.
  • the apparatus further includes an inorganic adsorption unit 320; the purification liquid outlet of the chemical precipitation unit 310 is connected to the drainage unit 400 via the inorganic adsorption unit 320.
  • the chemical precipitation unit 310 employs a chemical precipitation reactor 311, which may be an integrated precipitation device capable of performing dosing, chemical precipitation reaction, and separation, and the chemical precipitant may be Using one or more of carbonate, phosphate, sulfide, sulfate, hydroxide, metal oxide, oxalic acid, oxalate, but not limited thereto, as long as the radionuclide can be converted into Insoluble matter can be precipitated.
  • a chemical precipitation reactor 311 may be an integrated precipitation device capable of performing dosing, chemical precipitation reaction, and separation
  • the chemical precipitant may be Using one or more of carbonate, phosphate, sulfide, sulfate, hydroxide, metal oxide, oxalic acid, oxalate, but not limited thereto, as long as the radionuclide can be converted into Insoluble matter can be precipitated.
  • the inorganic adsorption unit 320 adopts an inorganic adsorption column 321 , and may adopt an inorganic adsorption column for ruthenium, an inorganic adsorption column for ruthenium, and an inorganic adsorption column for ruthenium and osmium. More than one of them.
  • the separation unit 200 includes one or a combination of two or more of a nanofiltration unit, a reverse osmosis subunit, a continuous electric desalting subunit. According to further embodiments of the present application, the separation unit 200 includes one or more of a nanofiltration unit, a reverse osmosis subunit, a continuous electric desalting subunit, and a combination of ion exchange subunits.
  • the separation unit 200 includes a reverse osmosis subunit 210, and the reverse osmosis subunit 210 adopts a first- or two-stage reverse osmosis device, but is not limited thereto, and may be adopted according to actual conditions. Three-stage reverse osmosis equipment.
  • a reverse osmosis unit 210 employs a primary reverse osmosis device, and a concentrate outlet of the reverse osmosis device 213 is coupled to the inlet of the chemical precipitation unit 310.
  • the purification liquid sent from the reverse osmosis apparatus 213 has been lower than 10 Bq/L, which meets the requirements of the discharge standard, and can be discharged. At this time, the purification liquid outlet of the reverse osmosis apparatus 213 is connected to the drainage unit 400.
  • the concentrate outlet of the reverse osmosis apparatus 213 is divided into two branches via a pipe, one branch is connected to the inlet of the reverse osmosis device 213, and the other branch is connected to the inlet of the chemical precipitation unit 310. This also reduces the discharge amount of the concentrate, reduces the load of the chemical precipitation unit 310, further improves the utilization rate of the chemical precipitant, and avoids energy waste and saves energy.
  • the reverse osmosis device 213 may employ one reverse osmosis membrane module or two or more reverse osmosis membrane modules in series.
  • the concentrate outlet of the previous reverse osmosis membrane module is next to the next
  • the inlet of the reverse osmosis membrane module is connected, that is, the stage-level concentrate produced by the previous reverse osmosis membrane module is used as the inlet water of the next reverse osmosis membrane module, and the stage-level purification liquids sent from all the reverse osmosis membrane modules are merged into the reverse osmosis apparatus 213. Purification fluid.
  • the reverse osmosis subunit 210 employs a two-stage reverse osmosis apparatus, wherein the first stage reverse osmosis apparatus 211 and The second reverse osmosis device 212 is connected in two stages.
  • the purified liquid outlet of the first-stage reverse osmosis device 211 is connected to the inlet of the second-stage reverse osmosis device 212, and the concentrated liquid outlet of the second-stage reverse osmosis device 212 is
  • the inlet of the primary reverse osmosis apparatus 211 is connected, and the concentrate outlet of the first stage reverse osmosis apparatus 211 is connected to the inlet of the chemical precipitation unit 310.
  • the purification liquid sent from the second-stage reverse osmosis apparatus 212 is lower than 10 Bq/L, and meets the requirements of the discharge standard, and the discharge treatment can be performed.
  • the purification liquid outlet of the first-stage reverse osmosis apparatus 212 is connected to the drainage unit 400.
  • the concentrate outlet of the first-stage reverse osmosis apparatus 211 is divided into two branches via a pipeline, one branch is connected to the inlet of the first-stage reverse osmosis apparatus 211, and the other branch is chemically precipitated.
  • the inlets of unit 310 are connected. This also reduces the discharge amount of the concentrate, reduces the load of the chemical precipitation unit 310, further improves the utilization rate of the chemical precipitant, and avoids energy waste and saves energy.
  • the first-stage reverse osmosis device 211 may adopt a reverse osmosis membrane module or two or more reverse osmosis membrane modules connected in series, and when more than two reverse osmosis membrane modules are used, the concentrate outlet of the previous reverse osmosis membrane module Connected to the inlet of the next reverse osmosis membrane module, that is, the stage-level concentrate produced by the previous reverse osmosis membrane module is used as the inlet water of the next reverse osmosis membrane module, and the stage-level purification liquids sent from all the reverse osmosis membrane modules are merged into the first The purification liquid of the reverse osmosis apparatus 211.
  • the second stage reverse osmosis apparatus 212 may also be in series with one reverse osmosis membrane module or two or more reverse osmosis membrane modules, and similarly, when two or more reverse osmosis membrane modules are used, the last reverse osmosis membrane module
  • the concentrate outlet is connected to the inlet of the next reverse osmosis membrane module, that is, the stage-level concentrate produced by the previous reverse osmosis membrane module is used as the inlet water of the next reverse osmosis membrane module, and the stage-level purification liquids sent from all the reverse osmosis membrane modules are combined. It is a purification liquid of the second-stage reverse osmosis device 212.
  • the first-stage reverse osmosis device 211 and the second-stage reverse osmosis device 212 are all connected in series by a three-stage reverse osmosis membrane module to form a "two-stage three-stage" reverse osmosis subunit 210 for separating and treating radioactive waste water. It has a higher purification capacity and concentration factor, reduces the load of the chemical precipitation unit 310, and increases the recovery rate of reverse osmosis.
  • first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis equipment or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis equipment has a radioactivity of more than 10 Bq/L, or when pursuing the discharged purification liquid
  • a continuous electric desalting subunit as shown in Figures 6 and 7) or an ion exchange subunit 230 (shown in Figure 5) can be disposed downstream of the reverse osmosis subunit.
  • the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis apparatus or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process is sent to the continuous electric desalination unit or the ion exchange subunit 230 for further fine processing. .
  • the continuous electric desalination unit uses a first-stage continuous electric desalination apparatus, and the purification liquid outlet of the reverse osmosis subunit 210 is connected to the inlet of the continuous electric desalination apparatus 223 for continuous electric desalination.
  • the purge liquid outlet of the apparatus 223 is connected to the drain unit 400, and the concentrate outlet of the continuous electric desalination apparatus 223 is connected to the inlet of the reverse osmosis subunit 210.
  • the reverse osmosis subunit 210 employs a primary reverse osmosis apparatus, please refer to FIG. 6.
  • the inlet of the reverse osmosis subunit 210 refers to the inlet of the reverse osmosis apparatus 213; when the reverse osmosis subunit 210 employs a two-stage reverse osmosis apparatus, Referring to FIG. 7, the inlet of the reverse osmosis subunit 210 refers to the inlet of the first stage reverse osmosis apparatus 211.
  • the continuous electric desalination unit uses a two-stage continuous electric desalination apparatus, wherein the first-stage continuous electric desalination apparatus 221 is connected in series with the second-stage continuous electric desalination apparatus 222, specifically
  • the purification liquid outlet of the reverse osmosis subunit 210 is connected to the inlet of the first stage continuous electric desalination apparatus 221, and the purification liquid outlet of the first stage continuous electric desalination apparatus 221 is connected to the inlet of the second stage continuous electric desalination apparatus 222.
  • the purification liquid outlet of the second-stage continuous electric desalination apparatus 222 is connected to the drainage unit 400, and the concentrated liquid outlet of the first-stage continuous electric desalination apparatus 221 and the concentrated liquid outlet of the second-stage continuous electric desalination apparatus 222 are respectively reversed
  • the inlets of the permeation subunits 210 are connected.
  • an intermediate water tank may be connected between the reverse osmosis subunit and the continuous electric desalination unit.
  • the intermediate tank is connected to the activator tank.
  • an intermediate water tank can be connected between the first-stage continuous electric desalination device 221 and the second-stage continuous electric desalination device 222.
  • the intermediate water tank 224 is connected to the activator tank 225, and a dosing pump is provided to control the amount of the activator to be added, so that the purified liquid produced by the continuous electric desalination unit can reach the natural background level.
  • the fine treatment of the ion exchange subunit 230 may be performed by using one or more ion exchangers in series, and the first, two, three, four or more ion exchangers may be used according to actual conditions.
  • the pre-processing unit 100 may be provided upstream of the separation unit 200, but is not essential. If necessary, the pre-processing unit 100 may be one or a combination of a degreasing filter, an activated carbon filter, an inorganic membrane filter, a security filter, a paper core filter, a self-cleaning filter, and an ultrafilter. .
  • radioactive waste water may also contain impurities such as oils, colloids, and particulate matter. Most of these impurities are non-radioactive, but they will affect subsequent processes. Pretreatment to remove these impurities can extend The use period of the reverse osmosis membrane and the inorganic adsorbent reduces the replacement of the inorganic adsorbent and the reverse osmosis membrane, improves the utilization efficiency of the chemical precipitant, and further reduces the amount of radioactive waste inorganic adsorbent generated and the amount of radioactive chemical precipitated sludge.
  • impurities such as oils, colloids, and particulate matter. Most of these impurities are non-radioactive, but they will affect subsequent processes. Pretreatment to remove these impurities can extend The use period of the reverse osmosis membrane and the inorganic adsorbent reduces the replacement of the inorganic adsorbent and the reverse osmosis membrane, improves the utilization efficiency of the chemical precipitant, and further reduces the amount
  • the degreasing filter 101 can stably remove oil in the radioactive waste water for a long period of time, and the inorganic membrane filter 102 can further remove oil in the radioactive waste water, and can effectively remove colloids and particulate matter in the radioactive waste water, as shown in FIG. 5 to FIG. 7 .
  • the degreasing filter 101 and the inorganic membrane filter 102 are sequentially connected to pretreat the radioactive waste water, and the turbidity is strong, and the pretreatment process equipment and the flow are simplified.
  • the separation unit 200 also includes a buffer tank 201 to buffer the radioactive wastewater from the pretreatment unit 100.
  • a security filter 202 is further coupled between the buffer tank 201 and the reverse osmosis subunit 210 for protecting the reverse osmosis apparatus of the subsequent process.
  • the separation unit 200 may further include a buffer tank 204 to buffer the purge liquid sent from the reverse osmosis subunit 210.
  • the apparatus also includes a suitable water supply pump 20, a high pressure pump 203, and a circulation pump 205, which may be various pumps commonly used in the art, such as a plunger pump, a centrifugal pump, and the like.
  • the apparatus may also include a water inlet buffer tank 10 to buffer the radioactive waste water.
  • the above-mentioned radioactive waste water method can be implemented to achieve a high level of radioactive waste liquid purification, and at the same time, the amount of radioactive waste generated can be significantly reduced, and the radioactive waste can be quantified.
  • the ion concentrations in the following examples were determined by inductively coupled plasma-mass spectrometry (ICP-MS), and the concentrations of the oils were characterized using a total organic carbon TOC analyzer.
  • ICP-MS inductively coupled plasma-mass spectrometry
  • the radioactive waste water treatment device used in this embodiment is different from the device shown in FIG. 6 in that no continuous electric desalination device 223 is provided, that is, the purification liquid outlet of the reverse osmosis device 213 is directly connected to the monitoring discharge tank 410, and other parts and figures are shown.
  • the device shown in 6 is the same.
  • the reverse osmosis device 213 is a three-stage reverse osmosis device formed by connecting three reverse osmosis membrane modules in series, the chemical precipitation reactor 311 adopts an integrated precipitation device, and the inorganic membrane filter 102 uses a ceramic membrane.
  • the simulated radioactive waste water treated in this example contained Cs + 10 mg/L, Sr 2+ 10 mg/L, NaCl 10 g/L, and the oil content was 100 ppm.
  • the designed treatment capacity of the radioactive waste water treatment device is 1 m 3 /h.
  • the oil content was reduced from 100 ppm to 5 ppm. After further passing through the inorganic membrane filter 102, the oil content was lowered to 1 ppm to satisfy the subsequent influent conditions.
  • the reverse osmosis operating pressure is 5 MPa, and the simulated radioactive wastewater is highly concentrated by the first-stage reverse osmosis process.
  • the recovery rate of reverse osmosis is set to 80%, the concentration multiple is 5 times, and the concentration of radionuclide in the concentrate is increased by 5 times, of which Cs + concentration
  • the concentration was 49 mg/L, Sr 2+ was 50 mg/L, and the NaCl concentration was 49.5 g/L.
  • the chemical precipitation reaction can be carried out in an integrated precipitation apparatus, and the chemical precipitating agent can be one or a combination of two or more of ferrous hydroxide, calcium carbonate, manganese dioxide, barium sulfate, and the like.
  • the chemical precipitant used calcium carbonate.
  • the concentration of Sr 2+ is reduced to 0.5 mg/L, while the chemical precipitation process has no removal effect on NaCl.
  • the NaCl concentration is kept at 49.5 g/L, so NaCl is not present in the solid waste. Reduced solid waste content.
  • the chemical precipitation process Since the chemical precipitation process has a low decontamination effect on Cs + , the chemical precipitation process produces water further into the ⁇ adsorption bed for inorganic adsorption to remove ⁇ , the decontamination factor reaches 10 3 , and the inorganic adsorption process produces water (ie, the second purification liquid).
  • the concentration of Cs + was decreased to 49 ⁇ g / L, the concentration of Sr 2+ was 0.5 mg / L, the concentration of NaCl was 49.5 g / L, and the water yield was 0.2 m 3 / h.
  • the concentration of Cs + in the reverse osmosis process water production (ie, the first purification liquid) was 100 ⁇ g/L, the concentration of Sr 2+ was 10 ⁇ g/L, the concentration of NaCl was 0.125 g/L, and the water production was 0.8 m 3 /h.
  • the first purification liquid is mixed with the second purification liquid and discharged, and the concentration of Cs + is 89.8 ⁇ g/L, the concentration of Sr 2+ is 108 ⁇ g/L, the concentration of NaCl is 10 g/L, and the whole device is decontaminated against sputum and sputum.
  • the factor is approximately 100.

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Abstract

Disclosed in the present application are a radioactive waste liquid treatment method and apparatus. The method comprises: performing separation on a radioactive waste liquid to obtain a first purified liquid and a concentrated liquid; removing radioactive nuclide from the concentrated liquid to obtain a second purified liquid, wherein removing radioactive nuclide from the concentrated liquid comprises performing a chemical precipitation process on the concentrated liquid; and discharging the first purified liquid and the second purified liquid. The radioactive waste liquid treatment method and apparatus in the present application have a high radioactive waste liquid purification level, and also significantly reduce the yield of radioactive waste, thereby minimizing the radioactive waste.

Description

放射性废液处理方法及装置Radioactive waste liquid processing method and device
相关申请的交叉引用Cross-reference to related applications
本申请要求享有于2018年04月13日提交的名称为“放射性废液处理方法及装置”的中国专利申请201810333535.9的优先权,该申请的全部内容通过引用并入本文中。The present application claims the benefit of priority to the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the
技术领域Technical field
本申请涉及放射性废液处理技术领域,尤其涉及一种放射性废液处理方法及装置。The present application relates to the technical field of radioactive waste liquid treatment, and in particular, to a method and a device for treating radioactive waste liquid.
背景技术Background technique
根据含盐量,可以将放射性废液分为三大类:(1)含盐量为0g·L -1~2g·L -1的低含盐量放射性废液;(2)含盐量为2g·L -1~10g·L -1的中等含盐量放射性废液;(3)含盐量达10g·L -1以上的高含盐量放射性废液。 According to the salt content, the radioactive waste liquid can be divided into three categories: (1) low salinity radioactive waste liquid with a salt content of 0g·L -1 to 2g·L -1 ; (2) salt content is Medium-salt radioactive waste liquid of 2g·L -1 to 10g·L -1 ; (3) High-salt radioactive waste liquid with a salt content of 10g·L -1 or more.
将盐和放射性核素完全分离的难度很大,因此在放射性废液处理中,对于含盐量低的放射性废液,一般是将盐和放射性核素一起作为处理对象进行处理。但是对于含盐量高的放射性废液,由于其非放射性盐的量与放射性核素的量的比值通常大于10 5甚至更高,将非放射性盐和放射性核素一起作为处理对象进行处理,会导致浓缩液中大部分都是非放射性盐,从而大大增加二次放射性废物的产生量。 It is very difficult to completely separate the salt and the radionuclide. Therefore, in the treatment of the radioactive waste liquid, for the radioactive waste liquid having a low salt content, the salt and the radionuclide are generally treated together as a treatment target. However, for radioactive waste liquids with high salt content, since the ratio of the amount of non-radioactive salts to the amount of radionuclides is usually greater than 10 5 or even higher, non-radioactive salts and radionuclides are treated together as treatment targets. Most of the concentrate is non-radioactive, which greatly increases the amount of secondary radioactive waste.
因此,需要一种新的放射性废液处理方法及装置,以解决上述技术问题。Therefore, there is a need for a new method and apparatus for treating radioactive waste liquids to solve the above technical problems.
发明内容Summary of the invention
根据本申请的实施例,提供了一种放射性废液处理方法及装置,具有更高的净化水平,同时能够显著降低放射性废物的产生量,实现放射性废 物的小量化。According to an embodiment of the present application, a method and apparatus for treating a radioactive waste liquid are provided, which have a higher level of purification, and at the same time, can significantly reduce the amount of radioactive waste generated, and achieve a small quantification of radioactive waste.
根据本申请的实施例的放射性废液处理方法及装置,尤其适用于高含盐量放射性废液的处理。The radioactive waste liquid treatment method and apparatus according to the embodiments of the present application are particularly suitable for the treatment of high salinity radioactive waste liquid.
根据本申请实施例的一个方面,提供了一种放射性废液处理方法,该方法包括:将放射性废液进行分离处理,得到第一净化液和浓缩液;对浓缩液进行去除放射性核素处理,得到第二净化液,其中,对浓缩液进行去除放射性核素处理包括浓缩液经过化学沉淀工艺处理;将第一净化液与第二净化液排放处理。According to an aspect of an embodiment of the present application, a method for treating a radioactive waste liquid is provided, the method comprising: separating a radioactive waste liquid to obtain a first purifying liquid and a concentrated liquid; and removing the radioactive nuclides from the concentrated liquid, Obtaining a second purifying liquid, wherein the removing the radioactive nuclides from the concentrated liquid comprises: the concentrated liquid is subjected to a chemical precipitation process; and the first purified liquid and the second purified liquid are discharged.
根据本申请实施例的放射性废液处理方法,通过对放射性废液进行分离处理,得到符合甚至优于排放标准的第一净化液,将绝大部分的放射性核素保留在浓缩液中,浓缩液具有较高的放射性核素浓度,将其经化学沉淀工艺处理,只选择性地去除放射性核素,非放射性盐随净化液一起排放,且不会产生放射性浓缩液,这样就大大减少了非放射性盐进入放射性废物的量,从而显著降低二次放射性废物的产生量。相比直接将放射性废液进行化学沉淀处理,本申请方法中的放射性废液被大幅度浓缩,需要处理的放射性废液体积大幅度减少,浓缩液中需要去除的标的放射性核素离子的浓度提高,能够大幅度提高化学沉淀工艺对放射性核素的去污因子,从而显著减少放射性废物的产生量。According to the radioactive waste liquid treatment method of the embodiment of the present application, the first purification liquid that meets or even exceeds the discharge standard is obtained by separating the radioactive waste liquid, and the majority of the radioactive nuclide is retained in the concentrate, the concentrate It has a high radionuclide concentration and is treated by a chemical precipitation process to selectively remove radionuclides. Non-radioactive salts are discharged together with the purification liquid, and no radioactive concentrate is produced, thus greatly reducing non-radioactive The amount of salt entering the radioactive waste, thereby significantly reducing the amount of secondary radioactive waste generated. Compared with the direct chemical precipitation treatment of the radioactive waste liquid, the radioactive waste liquid in the method of the present application is greatly concentrated, the volume of the radioactive waste liquid to be treated is greatly reduced, and the concentration of the target radionuclide ion to be removed in the concentrated liquid is increased. It can greatly improve the decontamination factor of radioactive nuclides in the chemical precipitation process, thereby significantly reducing the amount of radioactive waste generated.
根据本申请实施例的另一个方面,还提供了一种放射性废液处理装置,该装置包括分离单元、化学沉淀单元和排水单元,其中,分离单元的浓缩液出口与化学沉淀单元的进口相连;分离单元的净化液出口与化学沉淀单元的净化液出口分别连接至排水单元。According to another aspect of embodiments of the present application, there is also provided a radioactive waste liquid processing apparatus, the apparatus comprising a separation unit, a chemical precipitation unit and a drainage unit, wherein a concentrate outlet of the separation unit is connected to an inlet of the chemical precipitation unit; The purification liquid outlet of the separation unit and the purification liquid outlet of the chemical precipitation unit are respectively connected to the drainage unit.
附图说明DRAWINGS
为了更清楚地说明本申请实施例的技术方案,下面将对本申请实施例中所需要使用的附图作简单地介绍,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。In order to explain the technical solutions of the embodiments of the present application, the drawings used in the embodiments of the present application will be briefly introduced. For those skilled in the art, without any creative work, Other drawings can be obtained from these figures.
图1示出了本申请一个实施例提供的放射性废液处理方法工艺流程示意图。FIG. 1 is a schematic view showing a process flow of a method for treating a radioactive waste liquid provided by an embodiment of the present application.
图2示出了本申请另一个实施例提供的放射性废液处理方法工艺流程示意图。FIG. 2 is a schematic view showing a process flow of a method for treating a radioactive waste liquid provided by another embodiment of the present application.
图3示出了本申请又一个实施例提供的放射性废液处理方法工艺流程示意图。FIG. 3 is a schematic view showing a process flow of a method for treating a radioactive waste liquid provided by still another embodiment of the present application.
图4示出了本申请一个实施例提供的放射性废液处理装置工艺流程示意图。FIG. 4 is a schematic diagram showing the process flow of a radioactive waste liquid processing apparatus provided by an embodiment of the present application.
图5示出了本申请另一个实施例提供的放射性废液处理装置工艺流程示意图。FIG. 5 is a schematic diagram showing the process flow of a radioactive waste liquid processing apparatus according to another embodiment of the present application.
图6示出了本申请又一个实施例提供的放射性废液处理装置工艺流程示意图。FIG. 6 is a schematic view showing the process flow of a radioactive waste liquid processing apparatus according to still another embodiment of the present application.
图7示出了本申请另一个实施例提供的放射性废液处理装置工艺流程图。FIG. 7 is a flow chart showing the process of a radioactive waste liquid processing apparatus provided by another embodiment of the present application.
标号说明:Label description:
10,进水缓冲罐;10, water inlet buffer tank;
20,供水泵;20, water supply pump;
100,预处理单元;100, a preprocessing unit;
101,除油过滤器;102,无机膜过滤器;101, a degreasing filter; 102, an inorganic membrane filter;
200,分离单元;200, a separation unit;
201,缓冲水箱;202,保安过滤器;203,高压泵;204,缓冲水箱;205,循环泵;201, buffer water tank; 202, security filter; 203, high pressure pump; 204, buffer water tank; 205, circulation pump;
210,反渗透子单元;211,第一级反渗透设备;212,第二级反渗透设备;213,反渗透设备;210, reverse osmosis subunit; 211, first stage reverse osmosis equipment; 212, second stage reverse osmosis equipment; 213, reverse osmosis equipment;
221,第一级连续电除盐设备;222,第二级连续电除盐设备;223,连续电除盐设备;224,中间水箱;225,活化剂箱;221, first-stage continuous electric desalination equipment; 222, second-stage continuous electric desalination equipment; 223, continuous electric desalination equipment; 224, intermediate water tank; 225, activator tank;
230,离子交换子单元;230, an ion exchange subunit;
310,化学沉淀单元;311,化学沉淀反应器;310, a chemical precipitation unit; 311, a chemical precipitation reactor;
320,无机吸附单元;321,无机吸附柱;320, an inorganic adsorption unit; 321, an inorganic adsorption column;
400,排水单元;410,监测排放罐。400, drainage unit; 410, monitoring the discharge tank.
具体实施方式detailed description
下面将详细描述本申请的各个方面的特征和示例性实施例,为了使本申请的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本申请进行进一步详细描述。应理解,此处所描述的具体实施例仅被配置为解释本申请,并不被配置为限定本申请。对于本领域技术人员来说,本申请可以在不需要这些具体细节中的一些细节的情况下实施。下面对实施例的描述仅仅是为了通过示出本申请的示例来提供对本申请更好的理解。The present application will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are only to be construed as illustrative and not limiting. The application may be practiced without some of these specific details, as will be apparent to those skilled in the art. The following description of the embodiments is merely provided to provide a better understanding of the invention
需要说明的是,在本文中,诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来,而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下,由语句“包括……”限定的要素,并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。It should be noted that, in this context, relational terms such as first and second are used merely to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply such entities or operations. There is any such actual relationship or order between them. Furthermore, the term "comprises" or "comprises" or "comprises" or any other variations thereof is intended to encompass a non-exclusive inclusion, such that a process, method, article, or device that comprises a plurality of elements includes not only those elements but also Other elements, or elements that are inherent to such a process, method, item, or device. An element that is defined by the phrase "comprising", without limiting the invention, does not exclude the presence of additional elements in the process, method, article, or device.
放射性废水中放射性核素离子的质量浓度极低,而进一步降低放射性核素离子的浓度,以达到环境排放要求的放射性活度低于10Bq/L,这就对放射性废水处理技术的处理能力提出非常高的要求。一些放射性废水中非放射性盐含量达10g·L -1以上,甚至更高,现有技术是将非放射性盐与放射性核素一起作为处理对象进行处理,使得二次放射性废物的产生量大大增加,而放射性废水处理的一个重要原则是要求放射性废物小量化。另外,还需要考虑放射性条件下设备的可操作性和可维护性。 The concentration of radionuclide ions in radioactive wastewater is extremely low, and the concentration of radionuclide ions is further reduced to achieve an environmental emission requirement of less than 10 Bq/L, which is very important for the treatment capacity of radioactive wastewater treatment technology. High requirements. Some radioactive waste waters have a non-radioactive salt content of 10g·L -1 or more, or even higher. The prior art treats non-radioactive salts together with radionuclides as treatment targets, so that the amount of secondary radioactive waste is greatly increased. An important principle of radioactive wastewater treatment is the requirement for small quantification of radioactive waste. In addition, the operability and maintainability of the equipment under radioactive conditions need to be considered.
基于放射性废水处理的以上特殊要求,本申请实施例提供了一种放射性废液处理方法及装置,具有更高的净化水平,同时显著降低放射性废物的产生量,实现放射性废物的小量化。Based on the above special requirements of radioactive wastewater treatment, the embodiments of the present application provide a radioactive waste liquid treatment method and device, which have a higher purification level, and significantly reduce the amount of radioactive waste generated, thereby achieving a small quantification of radioactive waste.
在本文中,“浓缩倍数”按(进水体积)/(浓缩液的体积)计算;“去除率”按(进水中放射性核素的质量浓度-产水中放射性核素的质量浓度)/(进水中放射性核素的质量浓度)计算;“回收率”按(产水量)/ (进水量)计算;“去污因子”按(进水的放射性活度)/(产水的放射性活度)计算。In this paper, the "concentration factor" is calculated as (influent volume) / (volume of concentrate); "removal rate" is (by mass concentration of radionuclide in the influent - mass concentration of radionuclide in the produced water) / ( Calculation of the mass concentration of radionuclides in the influent; "recovery rate" is calculated as (water production) / (influent water); "decontamination factor" is (radiation activity of influent water) / (radiation activity of water production) ) Calculation.
本申请实施例提供的放射性废液处理方法及装置,尤其适用于高含盐量放射性废液的处理。The method and device for treating radioactive waste liquid provided by the embodiments of the present application are particularly suitable for the treatment of high salinity radioactive waste liquid.
图1示出了本申请一个实施例提供的放射性废液处理方法工艺流程示意图,根据该方法:FIG. 1 is a schematic view showing a process flow of a method for treating a radioactive waste liquid provided by an embodiment of the present application, according to which:
首先将放射性废水进行分离处理,得到第一净化液和浓缩液。其中,浓缩倍数可以为2倍以上,如2~10倍,放射性废水中的绝大多数放射性核素被保留在浓缩液中,可以使浓缩液中放射性核素的质量浓度达到放射性废液中放射性核素的质量浓度的2倍以上,第一净化液中放射性核素的质量浓度则低于放射性废水中放射性核素的质量浓度,达到甚至优于排放标准的要求,进行排放处理。The radioactive waste water is first separated and treated to obtain a first purified liquid and a concentrated liquid. Wherein, the concentration factor can be more than 2 times, such as 2 to 10 times, and most of the radioactive nuclides in the radioactive waste water are retained in the concentrate, so that the mass concentration of the radionuclide in the concentrate can reach the radioactivity in the radioactive waste liquid. The mass concentration of the radionuclide is more than twice that of the radionuclides, and the mass concentration of the radionuclide in the first purification liquid is lower than the mass concentration of the radionuclide in the radioactive waste water, which is even better than the emission standard and is discharged.
进一步地,对浓缩液进行去除放射性核素处理,得到第二净化液。其中包括将浓缩液经过化学沉淀工艺处理,通过向浓缩液中添加化学沉淀剂,以促进放射性核素离子转化成难溶物质而沉淀析出,从而去除放射性核素。化学沉淀剂可以采用碳酸盐、磷酸盐、硫化物、硫酸盐、氢氧化物、金属氧化物、草酸、草酸盐中的一种或几种,但并不限于此,只要能实现将放射性核素转化成难溶物质并沉淀出来即可。由于化学沉淀只选择性地去除放射性核素,而对水中占绝大多数的非放射性离子如Na +、K +、Cl -
Figure PCTCN2018085069-appb-000001
OH -等并不起作用,非放射性盐随净化液一起排放,且不会产生放射性浓缩废液,这样就大大减少了非放射性盐进入放射性废物的量,从而显著降低二次放射性废物的产生量。化学沉淀中化学沉淀剂的投加量与溶液中放射性核素的离子浓度以及所需要达到的去除率直接相关,由于浓缩液具有较高的放射性核素浓度,将其经化学沉淀工艺处理,相比直接将放射性废液进行化学沉淀处理,放射性废液被大幅度浓缩,需要处理的放射性废液体积大幅度减少,浓缩液中需要去除的标的放射性核素离子的浓度提高,能够大幅度提高化学沉淀工艺对放射性核素的去污因子,达到相同去除率所需的化学沉淀剂大幅度减少、或者相同化学沉淀剂投加量去除率大幅度提高,从而能够显著减少放射性废物 的产生量。
Further, the concentrated liquid is subjected to removal of radionuclide treatment to obtain a second purification liquid. The method comprises the steps of: subjecting the concentrated liquid to a chemical precipitation process, and removing the radionuclide by adding a chemical precipitating agent to the concentrated liquid to promote the conversion of the radioactive nuclide ions into a poorly soluble substance to precipitate and precipitate. The chemical precipitant may be one or more of carbonate, phosphate, sulfide, sulfate, hydroxide, metal oxide, oxalic acid, oxalate, but is not limited thereto, as long as it can achieve radioactivity The nuclide is converted into a poorly soluble substance and precipitated. Because chemical precipitation only selectively removes radionuclides, the majority of non-radioactive ions such as Na + , K + , Cl - ,
Figure PCTCN2018085069-appb-000001
OH - etc. does not work. Non-radioactive salts are discharged together with the purification liquid, and no radioactive concentrated waste liquid is produced. This greatly reduces the amount of non-radioactive salts entering the radioactive waste, thereby significantly reducing the amount of secondary radioactive waste generated. . The dosage of the chemical precipitant in the chemical precipitation is directly related to the ion concentration of the radionuclide in the solution and the removal rate required. Since the concentrate has a high concentration of radionuclides, it is treated by a chemical precipitation process. Compared with directly discharging the radioactive waste liquid, the radioactive waste liquid is greatly concentrated, the volume of the radioactive waste liquid to be treated is greatly reduced, and the concentration of the target radionuclide ion to be removed in the concentrate is increased, and the chemical can be greatly improved. The precipitation process has a significant reduction in the decontamination factor of the radionuclide, the chemical precipitant required to achieve the same removal rate, or the removal rate of the same chemical precipitant dosage, thereby significantly reducing the amount of radioactive waste generated.
经检测第二净化液的放射性活度符合排放标准的要求,则进行排放处理,可以是将第一净化液和第二净化液分别直接排放,即第一净化液经一路管线排出,第二净化液经第II管线排出;也可以是将两者混合后排放,即将第二净化液经第I管线与第一净化液汇合,然后进行排水处理。经检测第二净化液与第一净化液混合后符合排放标准的要求,则将第二净化液经第I管线与第一净化液混合后进行排放处理。After detecting that the activity of the second purification liquid meets the requirements of the discharge standard, the discharge treatment may be performed, and the first purification liquid and the second purification liquid may be directly discharged, that is, the first purification liquid is discharged through one pipeline, and the second purification is performed. The liquid is discharged through the second line; or the two may be mixed and discharged, that is, the second purified liquid is merged with the first purified liquid through the first line, and then drained. After detecting that the second purification liquid is mixed with the first purification liquid and meets the requirements of the discharge standard, the second purification liquid is mixed with the first purification liquid through the first pipeline and then discharged.
化学沉淀通常难以获得高的去污因子,如果追求所排放的第二净化液能够达到更低的放射性活度时,可以将化学沉淀工艺产水进一步通过选择性无机吸附去除放射性核素,从而提高对放射性核素的去污因子。其中,浓缩液先经过化学沉淀工艺处理之后,再经过无机吸附工艺处理,这样能够减轻无机吸附工艺的处理负荷。It is often difficult to obtain a high decontamination factor by chemical precipitation. If the second purification liquid discharged can achieve a lower activity, the chemical precipitation process can further remove the radionuclide by selective inorganic adsorption, thereby improving Decontamination factor for radionuclides. Among them, the concentrated liquid is subjected to a chemical precipitation process and then subjected to an inorganic adsorption process, which can reduce the processing load of the inorganic adsorption process.
根据本申请的一些实施例,分离处理可以根据放射性废水的组分、含量、及处理要求等实际情况,采用纳滤工艺、反渗透工艺、连续电除盐工艺中的一种或两种以上的组合工艺,或者,采用纳滤工艺、反渗透工艺、连续电除盐工艺中的一种或两种以上与离子交换工艺的组合工艺。According to some embodiments of the present application, the separation treatment may adopt one or more of a nanofiltration process, a reverse osmosis process, and a continuous electric desalination process according to actual conditions such as the composition, content, and processing requirements of the radioactive waste water. The combined process, or a combination of one or more of a nanofiltration process, a reverse osmosis process, and a continuous electric desalination process, and an ion exchange process.
当分离处理工序采用反渗透工艺时,可以采用一级或两级反渗透工艺处理,但并不限于此,还可以根据实际情况采用三级反渗透工艺。When the separation treatment process adopts the reverse osmosis process, the first-stage or two-stage reverse osmosis process can be used, but it is not limited thereto, and the three-stage reverse osmosis process can also be adopted according to the actual situation.
作为一个示例,分离处理工序采用一级反渗透工艺,具体地,将放射性废液经过一级反渗透工艺处理,得到一级反渗透净化液和一级反渗透浓缩液分别作为第一净化液和浓缩液。As an example, the separation treatment process adopts a first-stage reverse osmosis process, specifically, the radioactive waste liquid is subjected to a first-stage reverse osmosis process to obtain a first-stage reverse osmosis purification liquid and a first-stage reverse osmosis concentrate as the first purification liquid and Concentrate.
可选地,反渗透工艺可以采用一段或两段以上的反渗透处理,当采用两段以上的反渗透处理时,上一段反渗透处理的中间浓缩液作为下一段反渗透处理的进水,即放射性废液依次经过两段以上的反渗透处理,得到浓缩液,同时从每一段送出该段净化液,所有段送出的净化液汇合为一级反渗透净化液,这样能够提高反渗透的回收率。Alternatively, the reverse osmosis process may employ one or two or more stages of reverse osmosis treatment. When two or more stages of reverse osmosis treatment are used, the upper stage reverse osmosis treatment intermediate concentrate is used as the feed water of the next stage of reverse osmosis treatment, ie The radioactive waste liquid is subjected to reverse osmosis treatment in two or more stages to obtain a concentrated liquid. At the same time, the purified liquid is sent out from each section, and the purified liquid sent from all the sections is combined into a first-stage reverse osmosis purification liquid, which can improve the recovery rate of reverse osmosis. .
作为另一个示例,分离处理工序采用两级反渗透工艺,以进一步提高反渗透净化水平,具体地,先将放射性废液送入第一级反渗透工艺处理,得到第一级反渗透净化液和第一级反渗透浓缩液,再将第一级反渗透净化 液送入第二级反渗透工艺处理,得到第二级反渗透净化液和第二级反渗透浓缩液。其中,第二级反渗透浓缩液返回送入第一级反渗透工艺,第一级反渗透浓缩液即作为上述浓缩液,送入化学沉淀工艺处理;第二级反渗透净化液低于10Bq/L,符合排放标准的要求,作为第一净化液进行排放处理。As another example, the separation treatment process adopts a two-stage reverse osmosis process to further improve the level of reverse osmosis purification. Specifically, the radioactive waste liquid is first sent to the first-stage reverse osmosis process to obtain the first-stage reverse osmosis purification liquid and The first stage reverse osmosis concentrate is sent to the second stage reverse osmosis process to obtain the second stage reverse osmosis purification liquid and the second stage reverse osmosis concentrate. Wherein, the second-stage reverse osmosis concentrate is returned to the first-stage reverse osmosis process, and the first-stage reverse osmosis concentrate is sent to the chemical precipitation process as the concentrated liquid; the second-stage reverse osmosis purification liquid is lower than 10 Bq/ L, in line with the requirements of the discharge standard, as the first purification liquid for discharge treatment.
可选地,第一级反渗透工艺可以采用一段或两段以上的反渗透处理,当采用两段以上的反渗透处理时,上一段反渗透处理产生的段级浓缩液作为下一段反渗透处理的进水,即放射性废液依次经过两段以上的反渗透处理,得到浓缩液,同时从每一段送出该段净化液,所有段送出的净化液汇合为第一级反渗透净化液。Optionally, the first-stage reverse osmosis process may adopt one or two or more stages of reverse osmosis treatment. When two or more stages of reverse osmosis treatment are used, the stage-level concentrate produced by the reverse osmosis treatment of the previous stage is used as the next stage of reverse osmosis treatment. The influent water, that is, the radioactive waste liquid is sequentially subjected to reverse osmosis treatment of two or more stages to obtain a concentrated liquid, and at the same time, the purified liquid is sent out from each section, and the purified liquid sent from all the sections is merged into the first-stage reverse osmosis purification liquid.
可选地,第二级反渗透工艺可以采用一段或两段以上的反渗透处理,同样地,当采用两段以上的反渗透处理时,上一段反渗透处理产生的段级浓缩液作为下一段反渗透处理的进水,即放射性废液依次经过两段以上的反渗透处理,得到第二级反渗透浓缩液,同时从每一段送出该段净化液,所有段送出的净化液汇合为第二级反渗透净化液。Alternatively, the second-stage reverse osmosis process may employ one or two or more stages of reverse osmosis treatment. Similarly, when two or more stages of reverse osmosis treatment are used, the stage-stage concentrate produced by the previous stage of reverse osmosis treatment is used as the next stage. The influent treated by reverse osmosis, that is, the radioactive waste liquid is subjected to reverse osmosis treatment of two or more stages in turn to obtain a second-stage reverse osmosis concentrate, and the purified liquid is sent from each section, and the purified liquid sent from all the sections is merged into the second. Grade reverse osmosis purification solution.
作为一个可选方案,第一级反渗透工艺和第二级反渗透工艺均采用三段反渗透处理,组成“两级三段”反渗透工艺进行放射性废水对的分离处理,具有较高的净化能力和浓缩倍数,减小化学沉淀处理工序的负荷,同时提高回收率。As an alternative, the first-stage reverse osmosis process and the second-stage reverse osmosis process all adopt three-stage reverse osmosis treatment to form a “two-stage three-stage” reverse osmosis process for separation of radioactive wastewater pairs, which has high purification. Capacity and concentration factor reduce the load on the chemical precipitation treatment process while increasing recovery.
当一级反渗透工艺产出的一级反渗透净化液或两级反渗透工艺产出的第二级反渗透净化液,放射性活度大于10Bq/L时,或者,如果追求所排放的第一净化液能够达到更低的放射性活度时,还可以将一级反渗透工艺产出的一级反渗透净化液或两级反渗透工艺产出的第二级反渗透净化液送入连续电除盐工艺(如图2所示)或离子交换工艺(如图3所示)进行进一步地精细处理。When the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis process or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process has a radioactivity of more than 10 Bq/L, or if the first emission is pursued When the purification liquid can achieve lower radioactivity, the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis process or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process can be sent to the continuous electric elimination. The salt process (shown in Figure 2) or the ion exchange process (shown in Figure 3) is further refined.
作为一个示例,将一级反渗透工艺产出的一级反渗透净化液或两级反渗透工艺产出的第二级反渗透净化液经过一级连续电除盐工艺进行精细处理,得到第一净化液,往往已经达到排放标准的要求,甚至达到天然本底水平,几乎不含放射性核素,进行排放处理,产生的一级连续电除盐浓缩 液返回一级反渗透工艺或两级反渗透工艺中的第一级反渗透工艺。As an example, the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis process or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process is subjected to a first-stage continuous electric desalination process for fine treatment to obtain the first Purification liquids often meet the requirements of emission standards, even reach the natural background level, contain almost no radionuclides, and discharge treatment. The first-stage continuous electric desalting concentrate is returned to the first-stage reverse osmosis process or two-stage reverse osmosis. The first stage reverse osmosis process in the process.
为了提高连续电除盐工艺的净化水平,还可以在一级反渗透工艺产出的一级反渗透净化液或两级反渗透工艺产出的第二级反渗透净化液中加入活化剂,再送入一级连续电除盐工艺进行深度净化处理。活化剂可以由电阻率大于0.5MΩ·cm的纯水和不同种类的无机盐配制而成,活化剂中含有离子Ca 2+、Na +、Sr 2+、Zn 2+、Mg 2+、Fe 2+和K +,阴离子种类不限,活化剂原液浓度与投加剂量相关,保证在活化剂加入放射性废水中并混合均匀后,放射性废水中含有的离子浓度如下:Ca 2+0.1mg/L~0.2mg/L、Na +0.2mg/L~0.3mg/L、Sr 2+8mg/L~9mg/L、Zn 2+18mg/L~20mg/L、Mg 2+0.2mg/L~0.25mg/L、Fe 2+0.04mg/L~0.05mg/L和K +100mg/L~150mg/L。 In order to improve the purification level of the continuous electric desalination process, the activator may be added to the second-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis process or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process, and then sent. Into the first-stage continuous electric desalination process for deep purification treatment. The activator can be prepared from pure water having a resistivity of more than 0.5 MΩ·cm and different kinds of inorganic salts, and the activator contains ions Ca 2+ , Na + , Sr 2+ , Zn 2+ , Mg 2+ , Fe 2 . + and K + , the type of anion is not limited, the concentration of the activator stock solution is related to the dosage, ensuring that the ion concentration in the radioactive waste water is as follows after the activator is added to the radioactive waste water and mixed uniformly: Ca 2+ 0.1 mg / L ~ 0.2 mg/L, Na + 0.2 mg/L to 0.3 mg/L, Sr 2+ 8 mg/L to 9 mg/L, Zn 2+ 18 mg/L to 20 mg/L, Mg 2+ 0.2 mg/L to 0.25 mg/ L, Fe 2+ 0.04 mg/L to 0.05 mg/L and K + 100 mg/L to 150 mg/L.
作为另一个示例,将一级反渗透工艺产出的一级反渗透净化液或两级反渗透工艺产出的第二级反渗透净化液经过两级连续电除盐工艺进行精细处理,具体地,先将一级反渗透工艺产出的一级反渗透净化液或两级反渗透工艺产出的第二级反渗透净化液送入第一级连续电除盐工艺处理,得到第一级连续电除盐净化液和第一级连续电除盐浓缩液,再将第一级连续电除盐净化液送入第二级连续电除盐工艺处理,得到第二级连续电除盐净化液和第二级连续电除盐浓缩液,其中,第二级连续电除盐净化液即为第一净化液,往往已经达到排放标准的要求,甚至达到天然本底水平,进行排放处理,第一级连续电除盐浓缩液和第二级连续电除盐浓缩液则返回一级反渗透工艺或两级反渗透工艺中的第一级反渗透工艺。As another example, the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis process or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process is subjected to a two-stage continuous electric desalination process for fine treatment, specifically Firstly, the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis process or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process is sent to the first-stage continuous electric desalination process to obtain the first-stage continuous process. The electric demineralization purification liquid and the first-stage continuous electric demineralization concentrate, and then the first-stage continuous electric demineralization purification liquid is sent to the second-stage continuous electric desalination process to obtain the second-stage continuous electric desalting purification liquid and The second-stage continuous electric demineralization concentrate, wherein the second-stage continuous electric desalination purification liquid is the first purification liquid, which has already reached the requirements of the discharge standard, and even reaches the natural background level, and performs the discharge treatment, the first stage The continuous electric desalting concentrate and the second-stage continuous electric desalting concentrate return to the first-stage reverse osmosis process in the first-stage reverse osmosis process or the two-stage reverse osmosis process.
同样地,为了进一步提高连续电除盐工艺的净化水平,还可以在第一级连续电除盐净化液中加入活化剂,再送入第二级连续电除盐工艺进行净化处理。活化剂可以选用如前文所述的活化剂。Similarly, in order to further improve the purification level of the continuous electric desalination process, an activator may be added to the first-stage continuous electric desalination purification liquid, and then sent to a second-stage continuous electric desalination process for purification treatment. The activator may be selected from an activator as described above.
精细处理还可以是采用一级以上的离子交换工艺。将一级或两级反渗透工艺处理得到的净化液,依次经过一级以上离子交换工艺处理,得到第一净化液。The fine treatment may also be an ion exchange process using one or more stages. The purified liquid obtained by the first-stage or two-stage reverse osmosis process is sequentially subjected to one or more ion exchange processes to obtain a first purified liquid.
可以理解的是,分离处理工序并不限于采用上述工艺,如还可以是一级以上的连续电除盐工艺;纳滤一反渗透组合工艺;纳滤一连续电除盐组合工艺;纳滤一反渗透一连续电除盐组合工艺;纳滤一反渗透一离子交换 组合工艺等,本领域技术人员可以根据实际情况进行确定。It can be understood that the separation treatment process is not limited to adopting the above process, for example, it may be a continuous electric desalination process of more than one level; a nanofiltration-reverse osmosis combination process; a nanofiltration-continuous electric desalination combination process; Reverse osmosis-continuous electric desalination combined process; nanofiltration-reverse osmosis-ion exchange combination process, etc., can be determined by those skilled in the art according to actual conditions.
在放射性废水进行分离处理之前,可选择地对放射性废水进行预处理,但这并不是必须的工序。The radioactive waste water is optionally pretreated before the radioactive waste water is separated, but this is not an essential process.
放射性废水中除放射性核素和无机盐之外,还可能存在油类、胶体、颗粒物等杂质,这些杂质大部分是非放射性的,但会对反渗透、化学沉淀、无机吸附等工艺产生影响,预处理去除这些杂质,能够延长反渗透膜、无机吸附剂的使用周期,减少反渗透膜、无机吸附剂的更换,提高化学沉淀剂的效率,进一步减少放射性废无机吸附剂的产生量和放射性化学沉淀物的产生量。In addition to radionuclides and inorganic salts, radioactive waste water may also contain impurities such as oils, colloids, and particulate matter. Most of these impurities are non-radioactive, but they may affect processes such as reverse osmosis, chemical precipitation, and inorganic adsorption. The removal of these impurities can prolong the life cycle of the reverse osmosis membrane and the inorganic adsorbent, reduce the replacement of the reverse osmosis membrane and the inorganic adsorbent, improve the efficiency of the chemical precipitant, and further reduce the amount of radioactive waste inorganic adsorbent and radioactive chemical precipitation. The amount of matter produced.
还可以预先对放射性废水调节pH值至6~8,可以使反渗透工艺的处理效果更好,并使反渗透膜具有较长的使用寿命。It is also possible to adjust the pH value of the radioactive waste water to 6-8 in advance, which can make the reverse osmosis process better, and the reverse osmosis membrane has a longer service life.
为了实现上述放射性废液处理方法,本申请实施例进一步提供了一种放射性废液处理装置,以下结合图4至图7进行详细说明。In order to achieve the above method for treating a radioactive waste liquid, the embodiment of the present application further provides a radioactive waste liquid processing apparatus, which will be described in detail below with reference to FIGS. 4 to 7.
图4示出了本申请一个实施例提供的放射性废液处理装置工艺流程示意图。该装置包括分离单元200、化学沉淀单元310和排水单元400,其中,分离单元200的浓缩液出口与化学沉淀单元310的进口相连;分离单元200的净化液出口与化学沉淀单元310的净化液出口分别连接至排水单元400。FIG. 4 is a schematic diagram showing the process flow of a radioactive waste liquid processing apparatus provided by an embodiment of the present application. The apparatus includes a separation unit 200, a chemical precipitation unit 310, and a drainage unit 400, wherein the concentrate outlet of the separation unit 200 is connected to the inlet of the chemical precipitation unit 310; the purification liquid outlet of the separation unit 200 and the purification liquid outlet of the chemical precipitation unit 310 Connected to the drain unit 400, respectively.
作为一个示例,排水单元400包括第一排水子单元和第二排水子单元(图中未示出),分离单元200的净化液出口连接至第一排水子单元,化学沉淀单元310的净化液出口连接至第二排水子单元,第一排水子单元和第二排水子单元之间可以是连通的。这样,经检测第二净化液的放射性活度符合排放标准的要求时,可以根据不同需求将第一净化液和第二净化液分别直接排放,也可以是将两者混合后排放;经检测第二净化液与第一净化液混合后符合排放标准的要求时,则将第二净化液与第一净化液混合后进行排放。As an example, the drainage unit 400 includes a first drainage subunit and a second drainage subunit (not shown), the purification liquid outlet of the separation unit 200 is connected to the first drainage subunit, and the purification liquid outlet of the chemical precipitation unit 310 Connected to the second drainage subunit, the first drainage subunit and the second drainage subunit may be in communication. In this way, when the activity of the second purification liquid is determined to meet the requirements of the emission standard, the first purification liquid and the second purification liquid may be directly discharged according to different requirements, or may be discharged after mixing the two; When the second purification liquid is mixed with the first purification liquid and meets the requirements of the discharge standard, the second purification liquid is mixed with the first purification liquid and discharged.
可以理解的是,排水单元400可以仅仅是排水管道,也可以是在排水管道上连接监测排放罐410(如图6和图7所示),以监测排水的放射性活度,或者其他将净化液排出的形式,本申请不作限制。It can be understood that the drainage unit 400 may be only a drainage pipe, or may be connected to the drainage discharge tank 410 (as shown in FIG. 6 and FIG. 7) on the drainage pipe to monitor the drainage activity, or other purification liquid. The form of discharge is not limited in this application.
如果追求更高的去污因子,该装置还包括无机吸附单元320;化学沉淀单元310的净化液出口经无机吸附单元320连接至排水单元400。If a higher decontamination factor is pursued, the apparatus further includes an inorganic adsorption unit 320; the purification liquid outlet of the chemical precipitation unit 310 is connected to the drainage unit 400 via the inorganic adsorption unit 320.
根据本申请的一些实施例,请参照图6和图7,化学沉淀单元310采用化学沉淀反应器311,其可以为一体化沉淀设备,能够完成加药、化学沉淀反应和分离,化学沉淀剂可以采用碳酸盐、磷酸盐、硫化物、硫酸盐、氢氧化物、金属氧化物、草酸、草酸盐中的一种或几种,但并不限于此,只要能实现将放射性核素转化成难溶物质并沉淀出来即可。According to some embodiments of the present application, referring to FIG. 6 and FIG. 7, the chemical precipitation unit 310 employs a chemical precipitation reactor 311, which may be an integrated precipitation device capable of performing dosing, chemical precipitation reaction, and separation, and the chemical precipitant may be Using one or more of carbonate, phosphate, sulfide, sulfate, hydroxide, metal oxide, oxalic acid, oxalate, but not limited thereto, as long as the radionuclide can be converted into Insoluble matter can be precipitated.
根据本申请的一些实施例,请参照图6和图7,无机吸附单元320采用无机吸附柱321,可以采用针对锶的无机吸附柱、针对铯的无机吸附柱、针对锶和铯的无机吸附柱中的一种以上。According to some embodiments of the present application, referring to FIG. 6 and FIG. 7 , the inorganic adsorption unit 320 adopts an inorganic adsorption column 321 , and may adopt an inorganic adsorption column for ruthenium, an inorganic adsorption column for ruthenium, and an inorganic adsorption column for ruthenium and osmium. More than one of them.
根据本申请的一些实施例,分离单元200包括纳滤子单元、反渗透子单元、连续电除盐子单元中的一种或两种以上的组合。根据本申请的另一些实施例,分离单元200包括纳滤子单元、反渗透子单元、连续电除盐子单元中的一种或两种以上与离子交换子单元的组合。According to some embodiments of the present application, the separation unit 200 includes one or a combination of two or more of a nanofiltration unit, a reverse osmosis subunit, a continuous electric desalting subunit. According to further embodiments of the present application, the separation unit 200 includes one or more of a nanofiltration unit, a reverse osmosis subunit, a continuous electric desalting subunit, and a combination of ion exchange subunits.
作为一个示例,请参照图5至图7,分离单元200包括反渗透子单元210,反渗透子单元210中采用一级或两级反渗透设备,但并不限于此,还可以根据实际情况采用三级反渗透设备。As an example, referring to FIG. 5 to FIG. 7 , the separation unit 200 includes a reverse osmosis subunit 210, and the reverse osmosis subunit 210 adopts a first- or two-stage reverse osmosis device, but is not limited thereto, and may be adopted according to actual conditions. Three-stage reverse osmosis equipment.
在一些实施例中,请参照图6,反渗透子单元210中采用一级反渗透设备,反渗透设备213的浓缩液出口与化学沉淀单元310的进口相连。从反渗透设备213送出的净化液已经低于10Bq/L,符合排放标准的要求,可以进行排放处理,此时,反渗透设备213的净化液出口连接至排水单元400。In some embodiments, referring to FIG. 6, a reverse osmosis unit 210 employs a primary reverse osmosis device, and a concentrate outlet of the reverse osmosis device 213 is coupled to the inlet of the chemical precipitation unit 310. The purification liquid sent from the reverse osmosis apparatus 213 has been lower than 10 Bq/L, which meets the requirements of the discharge standard, and can be discharged. At this time, the purification liquid outlet of the reverse osmosis apparatus 213 is connected to the drainage unit 400.
为了提高反渗透的回收率,反渗透设备213的浓缩液出口经管道分为两个支路,一个支路与反渗透设备213的进口相连,另一个支路与化学沉淀单元310的进口相连。这样还减少了浓缩液的排出量,降低化学沉淀单元310的负荷,进一步提高化学沉淀剂的利用率,以及避免了能量浪费,节约能耗。In order to increase the recovery rate of reverse osmosis, the concentrate outlet of the reverse osmosis apparatus 213 is divided into two branches via a pipe, one branch is connected to the inlet of the reverse osmosis device 213, and the other branch is connected to the inlet of the chemical precipitation unit 310. This also reduces the discharge amount of the concentrate, reduces the load of the chemical precipitation unit 310, further improves the utilization rate of the chemical precipitant, and avoids energy waste and saves energy.
进一步地,反渗透设备213可以采用一个反渗透膜组件或两个以上的反渗透膜组件串联,当采用两个以上的反渗透膜组件时,上一个反渗透膜 组件的浓缩液出口与下一个反渗透膜组件的进口相连,即将上一个反渗透膜组件产生的段级浓缩液作为下一个反渗透膜组件的进水,所有反渗透膜组件送出的段级净化液汇合为反渗透设备213的净化液。Further, the reverse osmosis device 213 may employ one reverse osmosis membrane module or two or more reverse osmosis membrane modules in series. When two or more reverse osmosis membrane modules are used, the concentrate outlet of the previous reverse osmosis membrane module is next to the next The inlet of the reverse osmosis membrane module is connected, that is, the stage-level concentrate produced by the previous reverse osmosis membrane module is used as the inlet water of the next reverse osmosis membrane module, and the stage-level purification liquids sent from all the reverse osmosis membrane modules are merged into the reverse osmosis apparatus 213. Purification fluid.
在一些实施例中,请参照图7示出的本申请一个实施例提供的放射性废液处理装置工艺流程图,反渗透子单元210采用两级反渗透设备,其中第一级反渗透设备211和第二反渗透设备212串联为两级,具体地,第一级反渗透设备211的净化液出口与第二级反渗透设备212的进口相连,第二级反渗透设备212的浓缩液出口与第一级反渗透设备211的进口相连,第一级反渗透设备211的浓缩液出口与化学沉淀单元310的进口相连。从第二级反渗透设备212送出的净化液低于10Bq/L,符合排放标准的要求,可以进行排放处理,此时,第一级反渗透设备212的净化液出口连接至排水单元400。In some embodiments, referring to the process flow diagram of the radioactive waste liquid processing apparatus provided by one embodiment of the present application shown in FIG. 7, the reverse osmosis subunit 210 employs a two-stage reverse osmosis apparatus, wherein the first stage reverse osmosis apparatus 211 and The second reverse osmosis device 212 is connected in two stages. Specifically, the purified liquid outlet of the first-stage reverse osmosis device 211 is connected to the inlet of the second-stage reverse osmosis device 212, and the concentrated liquid outlet of the second-stage reverse osmosis device 212 is The inlet of the primary reverse osmosis apparatus 211 is connected, and the concentrate outlet of the first stage reverse osmosis apparatus 211 is connected to the inlet of the chemical precipitation unit 310. The purification liquid sent from the second-stage reverse osmosis apparatus 212 is lower than 10 Bq/L, and meets the requirements of the discharge standard, and the discharge treatment can be performed. At this time, the purification liquid outlet of the first-stage reverse osmosis apparatus 212 is connected to the drainage unit 400.
为了提高反渗透的回收率,第一级反渗透设备211的浓缩液出口经管道分为两个支路,一个支路与第一级反渗透设备211的进口相连,另一个支路与化学沉淀单元310的进口相连。这样还减少了浓缩液的排出量,降低化学沉淀单元310的负荷,进一步提高化学沉淀剂的利用率,以及避免了能量浪费,节约能耗。In order to increase the recovery rate of reverse osmosis, the concentrate outlet of the first-stage reverse osmosis apparatus 211 is divided into two branches via a pipeline, one branch is connected to the inlet of the first-stage reverse osmosis apparatus 211, and the other branch is chemically precipitated. The inlets of unit 310 are connected. This also reduces the discharge amount of the concentrate, reduces the load of the chemical precipitation unit 310, further improves the utilization rate of the chemical precipitant, and avoids energy waste and saves energy.
进一步地,第一级反渗透设备211可以采用一个反渗透膜组件或两个以上的反渗透膜组件串联,当采用两个以上的反渗透膜组件时,上一个反渗透膜组件的浓缩液出口与下一个反渗透膜组件的进口相连,即将上一个反渗透膜组件产生的段级浓缩液作为下一个反渗透膜组件的进水,所有反渗透膜组件送出的段级净化液汇合为第一级反渗透设备211的净化液。Further, the first-stage reverse osmosis device 211 may adopt a reverse osmosis membrane module or two or more reverse osmosis membrane modules connected in series, and when more than two reverse osmosis membrane modules are used, the concentrate outlet of the previous reverse osmosis membrane module Connected to the inlet of the next reverse osmosis membrane module, that is, the stage-level concentrate produced by the previous reverse osmosis membrane module is used as the inlet water of the next reverse osmosis membrane module, and the stage-level purification liquids sent from all the reverse osmosis membrane modules are merged into the first The purification liquid of the reverse osmosis apparatus 211.
第二级反渗透设备212也可以是采用可以一个反渗透膜组件或两个以上的反渗透膜组件串联,同样地,当采用两个以上的反渗透膜组件时,上一个反渗透膜组件的浓缩液出口与下一个反渗透膜组件的进口相连,即将上一个反渗透膜组件产生的段级浓缩液作为下一个反渗透膜组件的进水,所有反渗透膜组件送出的段级净化液汇合为第二级反渗透设备212的净化液。The second stage reverse osmosis apparatus 212 may also be in series with one reverse osmosis membrane module or two or more reverse osmosis membrane modules, and similarly, when two or more reverse osmosis membrane modules are used, the last reverse osmosis membrane module The concentrate outlet is connected to the inlet of the next reverse osmosis membrane module, that is, the stage-level concentrate produced by the previous reverse osmosis membrane module is used as the inlet water of the next reverse osmosis membrane module, and the stage-level purification liquids sent from all the reverse osmosis membrane modules are combined. It is a purification liquid of the second-stage reverse osmosis device 212.
作为一个可选方案,第一级反渗透设备211和第二级反渗透设备212 均采用三段反渗透膜组件串联,组成“两级三段”反渗透子单元210进行放射性废水的分离处理,具有较高的净化能力和浓缩倍数,减小化学沉淀单元310的负荷,同时提高反渗透的回收率。As an alternative, the first-stage reverse osmosis device 211 and the second-stage reverse osmosis device 212 are all connected in series by a three-stage reverse osmosis membrane module to form a "two-stage three-stage" reverse osmosis subunit 210 for separating and treating radioactive waste water. It has a higher purification capacity and concentration factor, reduces the load of the chemical precipitation unit 310, and increases the recovery rate of reverse osmosis.
当一级反渗透设备产出的一级反渗透净化液或两级反渗透设备产出的第二级反渗透净化液,放射性活度大于10Bq/L时,或者,当追求所排放的净化液能够达到更低的放射性活度时,还可以在反渗透子单元的下游设置连续电除盐子单元(如图6和图7所示)或离子交换子单元230(如图5所示),将一级反渗透设备产出的一级反渗透净化液或两级反渗透工艺产出的第二级反渗透净化液送入连续电除盐子单元或离子交换子单元230进行进一步地精细处理。When the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis equipment or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis equipment has a radioactivity of more than 10 Bq/L, or when pursuing the discharged purification liquid When a lower activity can be achieved, a continuous electric desalting subunit (as shown in Figures 6 and 7) or an ion exchange subunit 230 (shown in Figure 5) can be disposed downstream of the reverse osmosis subunit. The first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis apparatus or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis process is sent to the continuous electric desalination unit or the ion exchange subunit 230 for further fine processing. .
在一些实施例中,请参照图6,连续电除盐子单元采用一级连续电除盐设备,反渗透子单元210的净化液出口与连续电除盐设备223的进口相连,连续电除盐设备223的净化液出口连接至排水单元400,连续电除盐设备223的浓缩液出口与反渗透子单元210的进口相连。当反渗透子单元210采用一级反渗透设备时,请参照图6,反渗透子单元210的进口指的是反渗透设备213的进口;当反渗透子单元210采用两级反渗透设备时,请参照图7,反渗透子单元210的进口指的是第一级反渗透设备211的进口。In some embodiments, referring to FIG. 6, the continuous electric desalination unit uses a first-stage continuous electric desalination apparatus, and the purification liquid outlet of the reverse osmosis subunit 210 is connected to the inlet of the continuous electric desalination apparatus 223 for continuous electric desalination. The purge liquid outlet of the apparatus 223 is connected to the drain unit 400, and the concentrate outlet of the continuous electric desalination apparatus 223 is connected to the inlet of the reverse osmosis subunit 210. When the reverse osmosis subunit 210 employs a primary reverse osmosis apparatus, please refer to FIG. 6. The inlet of the reverse osmosis subunit 210 refers to the inlet of the reverse osmosis apparatus 213; when the reverse osmosis subunit 210 employs a two-stage reverse osmosis apparatus, Referring to FIG. 7, the inlet of the reverse osmosis subunit 210 refers to the inlet of the first stage reverse osmosis apparatus 211.
在一些实施例中,请参照图7,连续电除盐子单元采用两级连续电除盐设备,其中第一级连续电除盐设备221与第二级连续电除盐设备222串联,具体地,反渗透子单元210的净化液出口与第一级连续电除盐设备221的进口相连,第一级连续电除盐设备221的净化液出口与第二级连续电除盐设备222的进口相连,第二级连续电除盐设备222的净化液出口连接至排水单元400,第一级连续电除盐设备221的浓缩液出口和第二级连续电除盐设备222的浓缩液出口分别与反渗透子单元210的进口相连。In some embodiments, referring to FIG. 7, the continuous electric desalination unit uses a two-stage continuous electric desalination apparatus, wherein the first-stage continuous electric desalination apparatus 221 is connected in series with the second-stage continuous electric desalination apparatus 222, specifically The purification liquid outlet of the reverse osmosis subunit 210 is connected to the inlet of the first stage continuous electric desalination apparatus 221, and the purification liquid outlet of the first stage continuous electric desalination apparatus 221 is connected to the inlet of the second stage continuous electric desalination apparatus 222. The purification liquid outlet of the second-stage continuous electric desalination apparatus 222 is connected to the drainage unit 400, and the concentrated liquid outlet of the first-stage continuous electric desalination apparatus 221 and the concentrated liquid outlet of the second-stage continuous electric desalination apparatus 222 are respectively reversed The inlets of the permeation subunits 210 are connected.
为了提高连续电除盐子单元的净化水平,当连续电除盐子单元采用一级连续电除盐设备时,可以在反渗透子单元与连续电除盐子单元之间连接一中间水箱,该中间水箱与活化剂箱相连。这样,在反渗透子单元送出的净化液中,如一级反渗透设备产出的一级反渗透净化液或两级反渗透设备 产出的第二级反渗透净化液中,加入活化剂,再送入一级连续电除盐设备进行深度净化处理。当连续电除盐子单元采用两级连续电除盐设备串联时,请参照图7,可以在第一级连续电除盐设备221与第二级连续电除盐设备222之间连接一中间水箱224,该中间水箱224与活化剂箱225相连,并设置加药泵以控制活化剂的加入量,使经连续电除盐子单元处理后产出的净化液达到天然本底水平。In order to improve the purification level of the continuous electric desalination unit, when the continuous electric desalination unit adopts the first-stage continuous electric desalination device, an intermediate water tank may be connected between the reverse osmosis subunit and the continuous electric desalination unit. The intermediate tank is connected to the activator tank. In this way, in the purification liquid sent by the reverse osmosis subunit, such as the first-stage reverse osmosis purification liquid produced by the first-stage reverse osmosis apparatus or the second-stage reverse osmosis purification liquid produced by the two-stage reverse osmosis apparatus, the activator is added, and then sent Into a first-class continuous electric desalination equipment for deep purification treatment. When the continuous electric desalination unit is connected in series by two-stage continuous electric desalination equipment, referring to FIG. 7, an intermediate water tank can be connected between the first-stage continuous electric desalination device 221 and the second-stage continuous electric desalination device 222. 224, the intermediate water tank 224 is connected to the activator tank 225, and a dosing pump is provided to control the amount of the activator to be added, so that the purified liquid produced by the continuous electric desalination unit can reach the natural background level.
离子交换子单元230进行精细处理可以是采用一级以上的离子交换器串联,可以根据实际情况采用一级、两级、三级、四级或更多级离子交换器。The fine treatment of the ion exchange subunit 230 may be performed by using one or more ion exchangers in series, and the first, two, three, four or more ion exchangers may be used according to actual conditions.
如图4所示,在分离单元200的上游还可以设置预处理单元100,但并不是必须的。如需设置,预处理单元100可以是除油过滤器、活性炭过滤器、无机膜过滤器、保安过滤器、纸芯过滤器、自清洗过滤器、超滤器中的一种或几种的组合。As shown in FIG. 4, the pre-processing unit 100 may be provided upstream of the separation unit 200, but is not essential. If necessary, the pre-processing unit 100 may be one or a combination of a degreasing filter, an activated carbon filter, an inorganic membrane filter, a security filter, a paper core filter, a self-cleaning filter, and an ultrafilter. .
放射性废水中除放射性核素和无机盐之外,还可能存在的油类、胶体、颗粒物等杂质,这些杂质大部分是非放射性的,但会对后续工艺产生影响,预处理去除这些杂质,能够延长反渗透膜、无机吸附剂的使用周期,减少无机吸附剂和反渗透膜的更换,提高化学沉淀剂的利用效率,进一步减少放射性废无机吸附剂的产生量和放射性化学沉淀污泥的产生量。除油过滤器101能够长期稳定地去除放射性废水中的油类,无机膜过滤器102能够进一步去除放射性废水中的油类,还能够有效去除放射性废水中的胶体、颗粒物,如图5至图7所示,采用除油过滤器101和无机膜过滤器102依次连接,对放射性废水进行预处理,去浊能力强,且简化预处理工艺设备和流程。In addition to radionuclides and inorganic salts, radioactive waste water may also contain impurities such as oils, colloids, and particulate matter. Most of these impurities are non-radioactive, but they will affect subsequent processes. Pretreatment to remove these impurities can extend The use period of the reverse osmosis membrane and the inorganic adsorbent reduces the replacement of the inorganic adsorbent and the reverse osmosis membrane, improves the utilization efficiency of the chemical precipitant, and further reduces the amount of radioactive waste inorganic adsorbent generated and the amount of radioactive chemical precipitated sludge. The degreasing filter 101 can stably remove oil in the radioactive waste water for a long period of time, and the inorganic membrane filter 102 can further remove oil in the radioactive waste water, and can effectively remove colloids and particulate matter in the radioactive waste water, as shown in FIG. 5 to FIG. 7 . As shown, the degreasing filter 101 and the inorganic membrane filter 102 are sequentially connected to pretreat the radioactive waste water, and the turbidity is strong, and the pretreatment process equipment and the flow are simplified.
分离单元200还包括缓冲水箱201,以缓存来自预处理单元100的放射性废水。在缓冲水箱201与反渗透子单元210之间进一步连接保安过滤器202,用于保护后续工艺的反渗透设备。分离单元200还可以包括缓冲水箱204,以缓存从反渗透子单元210送出的净化液。The separation unit 200 also includes a buffer tank 201 to buffer the radioactive wastewater from the pretreatment unit 100. A security filter 202 is further coupled between the buffer tank 201 and the reverse osmosis subunit 210 for protecting the reverse osmosis apparatus of the subsequent process. The separation unit 200 may further include a buffer tank 204 to buffer the purge liquid sent from the reverse osmosis subunit 210.
该装置还包括适当的供水泵20、高压泵203和循环泵205,可以是本领域常用的各种泵,例如柱塞泵、离心泵等。该装置还可以包括进水缓冲 罐10,以缓存放射性废水。The apparatus also includes a suitable water supply pump 20, a high pressure pump 203, and a circulation pump 205, which may be various pumps commonly used in the art, such as a plunger pump, a centrifugal pump, and the like. The apparatus may also include a water inlet buffer tank 10 to buffer the radioactive waste water.
采用本申请实施例提供的放射性废水装置,能够实施上述放射性废水方法,以实现高的放射性废液净化水平,同时能够显著降低放射性废物的产生量,实现放射性废物的小量化。By adopting the radioactive waste water device provided in the embodiment of the present application, the above-mentioned radioactive waste water method can be implemented to achieve a high level of radioactive waste liquid purification, and at the same time, the amount of radioactive waste generated can be significantly reduced, and the radioactive waste can be quantified.
下面借助实施例来举例说明本申请,但这些实施例绝不构成对本申请的限制。The present application is exemplified by the following examples, but these examples are in no way intended to limit the application.
以下实施例中离子浓度采用电感耦合等离子体-质谱ICP-MS仪进行测定,油类的浓度采用总有机碳TOC分析仪进行表征。The ion concentrations in the following examples were determined by inductively coupled plasma-mass spectrometry (ICP-MS), and the concentrations of the oils were characterized using a total organic carbon TOC analyzer.
实施例1Example 1
本实施例所用放射性废水处理装置与如图6所示的装置不同的是,没有设置连续电除盐设备223,即反渗透设备213的净化液出口直接连接至监测排放罐410,其他部分与图6所示的装置相同。其中,反渗透设备213为三个反渗透膜组件串联形成的三段式反渗透设备,化学沉淀反应器311采用一体化沉淀设备,无机膜过滤器102采用陶瓷膜。The radioactive waste water treatment device used in this embodiment is different from the device shown in FIG. 6 in that no continuous electric desalination device 223 is provided, that is, the purification liquid outlet of the reverse osmosis device 213 is directly connected to the monitoring discharge tank 410, and other parts and figures are shown. The device shown in 6 is the same. The reverse osmosis device 213 is a three-stage reverse osmosis device formed by connecting three reverse osmosis membrane modules in series, the chemical precipitation reactor 311 adopts an integrated precipitation device, and the inorganic membrane filter 102 uses a ceramic membrane.
本实施例处理的模拟放射性废水中含有Cs +10mg/L,Sr 2+10mg/L,NaCl 10g/L,含油量为100ppm。 The simulated radioactive waste water treated in this example contained Cs + 10 mg/L, Sr 2+ 10 mg/L, NaCl 10 g/L, and the oil content was 100 ppm.
放射性废水处理装置的设计处理量为1m 3/h。 The designed treatment capacity of the radioactive waste water treatment device is 1 m 3 /h.
模拟放射性废水通过除油过滤器101后,将油含量从100ppm降低至5ppm,进一步通过无机膜过滤器102后,油含量降低至1ppm,满足后续的进水条件。After the simulated radioactive waste water passed through the degreasing filter 101, the oil content was reduced from 100 ppm to 5 ppm. After further passing through the inorganic membrane filter 102, the oil content was lowered to 1 ppm to satisfy the subsequent influent conditions.
反渗透操作压力为5MPa,模拟放射性废水经过一级反渗透工艺高度浓缩,反渗透的回收率设置为80%,浓缩倍数为5倍,浓缩液中放射性核素浓度提高5倍,其中Cs +浓度为49mg/L、Sr 2+的浓度为50mg/L,NaCl浓度为49.5g/L。根据化学沉淀的原理,在一定的溶度积Ksp条件下,当阳离子浓度提高5倍时,所需要的阴离子药剂浓度可以减少5倍,同时由于浓缩液水量降低为原水量的1/5,化学沉淀剂的使用量降低为原需要量的1/25,可以大幅度提高化学沉淀工艺对放射性核素的去污因子,大幅度降低放射性固体废物产生量。 The reverse osmosis operating pressure is 5 MPa, and the simulated radioactive wastewater is highly concentrated by the first-stage reverse osmosis process. The recovery rate of reverse osmosis is set to 80%, the concentration multiple is 5 times, and the concentration of radionuclide in the concentrate is increased by 5 times, of which Cs + concentration The concentration was 49 mg/L, Sr 2+ was 50 mg/L, and the NaCl concentration was 49.5 g/L. According to the principle of chemical precipitation, under a certain solubility product Ksp, when the concentration of cation is increased by 5 times, the required concentration of anionic agent can be reduced by 5 times, and at the same time, since the amount of concentrated water is reduced to 1/5 of the amount of raw water, chemistry The amount of precipitant used is reduced to 1/25 of the original requirement, which can greatly improve the decontamination factor of the radionuclide by the chemical precipitation process and greatly reduce the amount of radioactive solid waste generated.
由于处理水量降低,化学沉淀反应可在一体化沉淀设备中进行,化学 沉淀剂可以采用氢氧化亚铁、碳酸钙、二氧化锰、硫酸钡等中的一种或两种以上的组合,在本实施例中化学沉淀剂采用碳酸钙。经化学沉淀后Sr 2+的浓度降低至0.5mg/L,而化学沉淀工艺对NaCl没有去除效果,经化学沉淀后NaCl浓度保持为49.5g/L,因此NaCl不会存在于固体废物中,从而降低了固体废物含量。 Since the amount of treated water is reduced, the chemical precipitation reaction can be carried out in an integrated precipitation apparatus, and the chemical precipitating agent can be one or a combination of two or more of ferrous hydroxide, calcium carbonate, manganese dioxide, barium sulfate, and the like. In the examples, the chemical precipitant used calcium carbonate. After chemical precipitation, the concentration of Sr 2+ is reduced to 0.5 mg/L, while the chemical precipitation process has no removal effect on NaCl. After chemical precipitation, the NaCl concentration is kept at 49.5 g/L, so NaCl is not present in the solid waste. Reduced solid waste content.
由于化学沉淀工艺对Cs +的去污作用较低,化学沉淀工艺产水进一步送入铯吸附床进行无机吸附去除铯,去污因子达到10 3,无机吸附工艺产水(即第二净化液)中Cs +浓度降为49μg/L,Sr 2+的浓度为0.5mg/L,NaCl的浓度为49.5g/L,产水量为0.2m 3/h。 Since the chemical precipitation process has a low decontamination effect on Cs + , the chemical precipitation process produces water further into the 铯 adsorption bed for inorganic adsorption to remove 铯, the decontamination factor reaches 10 3 , and the inorganic adsorption process produces water (ie, the second purification liquid). The concentration of Cs + was decreased to 49 μg / L, the concentration of Sr 2+ was 0.5 mg / L, the concentration of NaCl was 49.5 g / L, and the water yield was 0.2 m 3 / h.
反渗透工艺产水(即第一净化液)中Cs +浓度为100μg/L,Sr 2+的浓度为10μg/L,NaCl的浓度为0.125g/L,产水量为0.8m 3/h。第一净化液与第二净化液混合后排放,监测Cs +浓度为89.8μg/L,Sr 2+的浓度为108μg/L,NaCl的浓度为10g/L,整套装置对铯和锶的去污因子约为100。 The concentration of Cs + in the reverse osmosis process water production (ie, the first purification liquid) was 100 μg/L, the concentration of Sr 2+ was 10 μg/L, the concentration of NaCl was 0.125 g/L, and the water production was 0.8 m 3 /h. The first purification liquid is mixed with the second purification liquid and discharged, and the concentration of Cs + is 89.8 μg/L, the concentration of Sr 2+ is 108 μg/L, the concentration of NaCl is 10 g/L, and the whole device is decontaminated against sputum and sputum. The factor is approximately 100.
还可以在反渗透设备213之后设置连续电除盐设备,能够达到更高的去污因子。It is also possible to provide a continuous electric desalination device after the reverse osmosis device 213 to achieve a higher decontamination factor.
以上所述,仅为本申请的具体实施方式,应当理解的是,本申请的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本申请揭露的技术范围内,可轻易想到各种等效的修改或替换,这些修改或替换都应涵盖在本申请的保护范围之内。The foregoing is only a specific embodiment of the present application, and it should be understood that the scope of protection of the present application is not limited thereto, and any person skilled in the art can easily think of each within the technical scope disclosed in the present application. Equivalent modifications or substitutions are intended to be included within the scope of the present application.

Claims (22)

  1. 一种放射性废液处理方法,其中,所述方法包括:A method of treating a radioactive waste liquid, wherein the method comprises:
    将放射性废液进行分离处理,得到第一净化液和浓缩液;Separating the radioactive waste liquid to obtain a first purification liquid and a concentrated liquid;
    对所述浓缩液进行去除放射性核素处理,得到第二净化液;其中,所述对所述浓缩液进行去除放射性核素处理包括所述浓缩液经过化学沉淀工艺处理;Performing the removal of the radionuclide treatment to obtain a second purification liquid; wherein the removing the radioactive nuclides on the concentrated liquid comprises treating the concentrated liquid through a chemical precipitation process;
    将所述第一净化液与所述第二净化液排放处理。The first purification liquid and the second purification liquid are discharged.
  2. 根据权利要求1所述的方法,其中,所述对所述浓缩液进行去除放射性核素处理还包括无机吸附工艺处理;The method according to claim 1, wherein said removing the radionuclide treatment of said concentrate further comprises an inorganic adsorption process;
    其中,所述浓缩液经过所述化学沉淀工艺处理之后,再经过无机吸附工艺处理,得到所述第二净化液。Wherein, the concentrated liquid is treated by the chemical precipitation process, and then subjected to an inorganic adsorption process to obtain the second purified liquid.
  3. 根据权利要求1所述的方法,其中,所述分离处理采用纳滤工艺、反渗透工艺、连续电除盐工艺中的一种或两种以上的组合工艺,或者,采用纳滤工艺、反渗透工艺、连续电除盐工艺中的一种或两种以上与离子交换工艺的组合工艺。The method according to claim 1, wherein the separation treatment employs one or a combination of one of a nanofiltration process, a reverse osmosis process, a continuous electric desalination process, or a nanofiltration process, reverse osmosis A combination process of one or more of a process, a continuous electric desalination process, and an ion exchange process.
  4. 根据权利要求1所述的方法,其中,所述将放射性废液分离处理得到第一净化液和浓缩液包括:将放射性废液经过一级或两级反渗透工艺处理。The method according to claim 1, wherein said separating the radioactive waste liquid to obtain the first purified liquid and the concentrated liquid comprises: treating the radioactive waste liquid by a one-stage or two-stage reverse osmosis process.
  5. 根据权利要求4所述的方法,其中,所述反渗透工艺采用一段或两段以上的反渗透处理,当采用两段以上的反渗透处理时,上一段反渗透处理的中间浓缩液作为下一段反渗透处理的进水,从各段送出净化液汇合为所述反渗透工艺的净化液。The method according to claim 4, wherein said reverse osmosis process employs one or two or more stages of reverse osmosis treatment, and when two or more stages of reverse osmosis treatment are employed, the intermediate stage of the previous stage of reverse osmosis treatment is used as the next stage. The infiltration water of the reverse osmosis treatment, the purified liquid sent from each section is merged into the purification liquid of the reverse osmosis process.
  6. 根据权利要求4所述的方法,其中,所述两级反渗透工艺处理包括:The method of claim 4 wherein said two-stage reverse osmosis process comprises:
    将放射性废液依次经过第一级反渗透工艺和第二级反渗透工艺处理,将所述第二级反渗透工艺送出的第二级反渗透浓缩液返回所述第一级反渗透工艺,从所述第一级反渗透工艺送出所述浓缩液。The radioactive waste liquid is sequentially processed through the first-stage reverse osmosis process and the second-stage reverse osmosis process, and the second-stage reverse osmosis concentrate sent from the second-stage reverse osmosis process is returned to the first-stage reverse osmosis process. The first stage reverse osmosis process delivers the concentrate.
  7. 根据权利要求4所述的方法,其中,所述将放射性废液经过一级 或两级反渗透工艺处理之后,还包括:The method of claim 4, wherein after the treating the radioactive waste liquid through the one-stage or two-stage reverse osmosis process, the method further comprises:
    将所述一级或两级反渗透工艺处理得到的净化液经过一级或两级连续电除盐工艺处理;或者,Treating the purified liquid obtained by the first-stage or two-stage reverse osmosis process through a first-stage or two-stage continuous electric desalination process; or
    将所述一级或两级反渗透工艺处理得到的净化液经过一级以上离子交换工艺处理。The purified liquid obtained by the first-stage or two-stage reverse osmosis process is treated by one or more ion exchange processes.
  8. 根据权利要求7所述的方法,其中,所述两级连续电除盐工艺处理包括:The method of claim 7 wherein said two-stage continuous electrical desalination process comprises:
    将所述一级或两级反渗透工艺处理得到的净化液依次经过第一级连续电除盐工艺和第二级连续电除盐工艺处理,得到所述第一净化液;将所述第一级连续电除盐工艺送出的第一级连续电除盐浓缩液和所述第二级连续电除盐工艺送出的第二级连续电除盐浓缩液均返回所述一级或两级反渗透工艺。Purifying the liquid obtained by the first-stage or two-stage reverse osmosis process through a first-stage continuous electric desalination process and a second-stage continuous electric desalination process to obtain the first purification liquid; The first-stage continuous electric desalting concentrate sent by the continuous electric desalination process and the second-stage continuous electric desalting concentrate sent by the second-stage continuous electric desalination process return to the first- or two-stage reverse osmosis Process.
  9. 根据权利要求8所述的方法,其中,在所述第一级连续电除盐工艺送出的中间净化液中加入活化剂,再送入所述第二级连续电除盐工艺。The method according to claim 8, wherein an activator is added to the intermediate cleaning liquid sent from the first-stage continuous electric desalination process, and then sent to the second-stage continuous electric desalination process.
  10. 根据权利要求1所述的方法,其中,所述放射性废液的体积为所述浓缩液的体积的2倍以上,所述浓缩液中放射性核素的浓度为所述放射性废液中放射性核素的浓度的2倍以上。The method according to claim 1, wherein the volume of the radioactive waste liquid is more than twice the volume of the concentrated liquid, and the concentration of the radionuclide in the concentrated liquid is a radionuclide in the radioactive waste liquid. The concentration is more than 2 times.
  11. 根据权利要求1所述的方法,其中,所述放射性废液进行所述分离处理之前,经过预处理,以去除油类、胶体、颗粒物中的一种以上,和/或,调节pH值。The method according to claim 1, wherein the radioactive waste liquid is subjected to pretreatment to remove one or more of oils, colloids, particles, and/or pH values before the separation treatment.
  12. 一种放射性废液处理装置,其中,该装置包括分离单元、化学沉淀单元和排水单元,其中,A radioactive waste liquid processing apparatus, wherein the apparatus comprises a separation unit, a chemical precipitation unit, and a drainage unit, wherein
    所述分离单元的浓缩液出口与所述化学沉淀单元的进口相连;a concentrated liquid outlet of the separation unit is connected to an inlet of the chemical precipitation unit;
    所述分离单元的净化液出口与所述化学沉淀单元的净化液出口分别连接至所述排水单元。The purification liquid outlet of the separation unit and the purification liquid outlet of the chemical precipitation unit are respectively connected to the drainage unit.
  13. 根据权利要求12所述的装置,其中,该装置还包括无机吸附单元;所述化学沉淀单元的净化液出口经所述无机吸附单元连接至所述排水单元。The apparatus according to claim 12, wherein the apparatus further comprises an inorganic adsorption unit; the purification liquid outlet of the chemical precipitation unit is connected to the drainage unit via the inorganic adsorption unit.
  14. 根据权利要求12所述的装置,其中,所述分离单元包括纳滤子 单元、反渗透子单元、连续电除盐子单元中的一种或两种以上的组合;或者,所述分离单元包括纳滤子单元、反渗透子单元、连续电除盐子单元中的一种或两种以上与离子交换子单元的组合。The apparatus according to claim 12, wherein said separation unit comprises one of a nanofiltration unit, a reverse osmosis subunit, a continuous electric desalting subunit, or a combination of two or more; or, said separation unit comprises A combination of one or more of a nanofiltration unit, a reverse osmosis subunit, and a continuous electric desalting subunit with an ion exchange subunit.
  15. 根据权利要求14所述的装置,其中,所述分离单元包括反渗透子单元,其中,所述反渗透子单元包括一级或两级反渗透设备。The apparatus of claim 14 wherein said separation unit comprises a reverse osmosis subunit, and wherein said reverse osmosis subunit comprises a one or two stage reverse osmosis apparatus.
  16. 根据权利要求15所述的装置,其中,所述分离单元进一步包括连续电除盐子单元,所述反渗透子单元和所述连续电除盐子单元依次连接,其中,所述连续电除盐子单元包括一级或两级连续电除盐设备;或者,The apparatus according to claim 15, wherein said separation unit further comprises a continuous electric desalting subunit, said reverse osmosis subunit and said continuous electric desalting subunit being sequentially connected, wherein said continuous electric desalination The subunit includes one or two stages of continuous electric desalination equipment; or
    所述分离单元进一步包括离子交换子单元,所述反渗透子单元和所述离子交换子单元依次连接,其中,所述离子交换子单元包括一级以上离子交换器。The separation unit further includes an ion exchange subunit, and the reverse osmosis subunit and the ion exchange subunit are sequentially connected, wherein the ion exchange subunit includes one or more ion exchangers.
  17. 根据权利要求15或16所述的装置,其中,所述反渗透设备采用一个反渗透膜组件或两个以上的反渗透膜组件串联,当采用两个以上的反渗透膜组件时,上一个反渗透膜组件的浓缩液出口与下一个反渗透膜组件的进口相连。The apparatus according to claim 15 or 16, wherein said reverse osmosis apparatus employs a reverse osmosis membrane module or two or more reverse osmosis membrane modules in series, and when two or more reverse osmosis membrane modules are used, the upper one is reversed. The concentrate outlet of the permeable membrane module is connected to the inlet of the next reverse osmosis membrane module.
  18. 根据权利要求15或16所述的装置,其中,所述反渗透子单元包括一级反渗透设备,所述反渗透设备的浓缩液出口经管道分为两个支路,一个支路与所述反渗透设备的进口相连,另一个支路与所述化学沉淀单元的进口相连;或者,The apparatus according to claim 15 or 16, wherein said reverse osmosis subunit comprises a primary reverse osmosis device, and said concentrate outlet of said reverse osmosis device is divided into two branches via a pipe, a branch and said The inlet of the reverse osmosis device is connected, and the other branch is connected to the inlet of the chemical precipitation unit; or
    所述反渗透子单元包括两级反渗透设备,其中第一级反渗透设备的浓缩液出口经管道分为两个支路,一个支路与第一级反渗透设备的进口相连,另一个支路与所述化学沉淀单元的进口相连。The reverse osmosis subunit comprises a two-stage reverse osmosis device, wherein the concentrate outlet of the first stage reverse osmosis device is divided into two branches via a pipeline, one branch is connected to the inlet of the first stage reverse osmosis device, and the other branch is connected The road is connected to the inlet of the chemical precipitation unit.
  19. 根据权利要求15或16所述的装置,其中,所述反渗透子单元包括两级反渗透设备,其中,第一级反渗透设备的净化液出口与第二级反渗透设备的进口相连,第二级反渗透设备的浓缩液出口与所述第一级反渗透设备的进口相连,第一级反渗透设备的浓缩液出口与所述化学沉淀单元的进口相连。The apparatus according to claim 15 or 16, wherein said reverse osmosis subunit comprises a two-stage reverse osmosis apparatus, wherein a purge liquid outlet of the first stage reverse osmosis apparatus is connected to an inlet of the second stage reverse osmosis apparatus, The concentrate outlet of the secondary reverse osmosis apparatus is connected to the inlet of the first stage reverse osmosis apparatus, and the concentrate outlet of the first stage reverse osmosis apparatus is connected to the inlet of the chemical precipitation unit.
  20. 根据权利要求16所述的装置,其中,所述连续电除盐子单元包 括两级连续电除盐设备,其中,所述反渗透子单元的净化液出口与所述第一级连续电除盐设备的进口相连,所述第一级连续电除盐设备的净化液出口与所述第二级连续电除盐设备的进口相连,所述第二级连续电除盐设备的净化液出口与所述排水单元相连,所述第一级连续电除盐设备的浓缩液出口和所述第二级连续电除盐设备的浓缩液出口分别与所述反渗透子单元的进口相连。The apparatus according to claim 16, wherein said continuous electric desalination subunit comprises a two-stage continuous electric desalination apparatus, wherein said purification liquid outlet of said reverse osmosis subunit is continuously deionized with said first stage The inlet of the device is connected, the outlet of the purification liquid of the first-stage continuous electric desalination device is connected with the inlet of the second-stage continuous electric desalination device, and the purification liquid outlet of the second-stage continuous electric desalination device The drain unit is connected, and the concentrate outlet of the first stage continuous electric desalination apparatus and the concentrate outlet of the second stage continuous electric desalination apparatus are respectively connected to the inlet of the reverse osmosis subunit.
  21. 根据权利要求20所述的装置,其中,所述第一级连续电除盐设备的净化液出口经中间水箱与所述第二级连续电除盐设备的进口相连,所述中间水箱与活化剂箱相连。The apparatus according to claim 20, wherein said purification liquid outlet of said first-stage continuous electric desalination apparatus is connected to an inlet of said second-stage continuous electric desalination apparatus via an intermediate water tank, said intermediate water tank and activator The boxes are connected.
  22. 根据权利要求12所述的装置,其中,该装置还包括预处理单元,所述预处理单元与所述分离单元的进口相连,用于去除放射性废液中的油类、胶体、颗粒物中的一种以上,和/或,调节pH值。The apparatus according to claim 12, wherein the apparatus further comprises a pre-processing unit connected to the inlet of the separation unit for removing one of oil, colloid, and particulate matter in the radioactive waste liquid. Above and/or, adjust the pH.
PCT/CN2018/085069 2018-04-13 2018-04-28 Radioactive waste liquid treatment method and apparatus WO2019196143A1 (en)

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