WO2019134436A1 - 浓缩固化放射性废液中核素的方法和系统 - Google Patents

浓缩固化放射性废液中核素的方法和系统 Download PDF

Info

Publication number
WO2019134436A1
WO2019134436A1 PCT/CN2018/114299 CN2018114299W WO2019134436A1 WO 2019134436 A1 WO2019134436 A1 WO 2019134436A1 CN 2018114299 W CN2018114299 W CN 2018114299W WO 2019134436 A1 WO2019134436 A1 WO 2019134436A1
Authority
WO
WIPO (PCT)
Prior art keywords
nuclides
radioactive waste
waste liquid
concentrating
ion exchange
Prior art date
Application number
PCT/CN2018/114299
Other languages
English (en)
French (fr)
Inventor
赵璇
李福志
尉继英
张猛
Original Assignee
清华大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 清华大学 filed Critical 清华大学
Priority to GB2009626.9A priority Critical patent/GB2583276B/en
Publication of WO2019134436A1 publication Critical patent/WO2019134436A1/zh

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • G21F9/125—Processing by absorption; by adsorption; by ion-exchange by solvent extraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/08—Specific process operations in the concentrate stream
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2623—Ion-Exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C02F1/004—Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/008—Sludge treatment by fixation or solidification
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/006—Radioactive compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/40—Liquid flow rate
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • the present invention relates to a method and system for concentrating a nuclides in a solidified radioactive waste liquid.
  • nuclear power is gradually becoming an important part of the world's energy structure.
  • Fukushima nuclear accident in Japan nuclear safety has become a major concern in the development of nuclear energy.
  • a large amount of radioactive waste liquid is usually generated.
  • radionuclides contained in radioactive waste liquids
  • one source is fission products and the other source is activated products and corrosion products.
  • the second source is mainly related to the activation, corrosion, precipitation and release behavior of the metal materials, and the radionuclides include Ag, Co, Cr, Mn, Fe and the like.
  • long-lived fission products 134 Cs/ 137 Cs and 90 Sr with beta radioactivity appear in the radioactive waste liquid.
  • radionuclides with a long half-life they need to be separated from the waste liquid, stored in isolation from the environment for a long period of time until they decay to a harmless level.
  • radioactive waste liquids are generally concentrated and reduced in volume to minimize volume as long as possible for long-term storage.
  • the methods for concentrating radionuclides in radioactive waste liquids are mainly evaporation concentration and ion exchange. Regardless of the treatment method, the radionuclide is concentrated and concentrated in a liquid medium or a solid medium, which is finally solidified and subjected to long-term geological storage.
  • Evaporative concentration is the redistribution of radionuclides in the remnant and condensate to obtain a vapor residue containing most of the radionuclides and a condensate having a lower radionuclide content.
  • Ion exchange is the process of accommodating radionuclides in their own materials.
  • Evaporation concentration and ion exchange have a wide range of applications in the treatment of radioactive waste liquids, with their own advantages and disadvantages.
  • the advantages of the evaporation process are that the technology is mature, the decontamination ability is strong, and the amount of radioactive waste generated is the smallest; the disadvantages are high energy consumption, large equipment, high investment, poor operating conditions, and serious problems such as corrosion and scaling.
  • the ion exchange process is just the opposite. Its advantages are low energy consumption, simple equipment and convenient operation.
  • the disadvantage is that a large amount of radioactive waste ion exchange resin is generated, which is difficult to handle and handle.
  • the evaporation process has gradually withdrawn, and the ion exchange process has become the main process.
  • the existing ion exchange process of nuclear power plants must concentrate the inclusion of radionuclides while ensuring that the liquids they discharge meet environmental emission requirements. This has a high requirement on the resin decontamination coefficient, and thus the adsorption capacity of the resin cannot be fully utilized, resulting in a large amount of radioactive waste resin, which causes a great pressure on the long-term storage in the later stage.
  • Nuclear power plant radioactive waste liquid contains Na-24, Cr-51, Mn-54, Fe-55, Fe-59, Co-58, Co-60, Zn-65, Sr-89, Sr-91, Zr -95, Nb-95, Mo-99, Tc-99m, Ru-103, Ru-106m, Ag-110m, Te-129m, Te-129, Te-131m, Te-131, Te-132, Cs-134 Hundreds of nuclides such as Cs-137, Ba-140, La-140, Ce-141, Ce-143, Ce-144, W-187, and Np-239.
  • each nuclide such as concentration and enrichment properties, presence, concentration, valence, corrosivity, etc.
  • concentration and enrichment properties, presence, concentration, valence, corrosivity, etc. are complex and can be changed under different operating conditions (such as pH, ionic strength, temperature, etc.), concentration of nuclide Enrichment creates a certain degree of difficulty.
  • the mass concentration of radionuclides is extremely low, generally less than 10 -3 ⁇ g / liter; while the concentration of coexisting non-radioactive ions such as K, Na, Ca, Mg is higher, generally in the order of milligrams / liter, and even Up to grams per liter, the presence of these non-radioactive ions severely affects the concentration and solidification of the nuclides in the radioactive waste stream.
  • the present invention relates to a method and system for concentrating a nuclides in a solidified radioactive waste liquid.
  • One aspect of the present invention provides a method of concentrating a nuclides in a solidified radioactive waste liquid, comprising the steps of:
  • Step 1) Pretreatment: extracting the radioactive waste liquid by using the first selective extractant
  • Step 2 Concentration: performing reverse osmosis concentration on the extracted radioactive waste liquid
  • Step 4) Nuclide solidification: The sulfide-rich organic ion exchange resin and/or the second selective extractant obtained in the step 3) and the first selective extractant obtained in the step 1) are further formed into a solidified body.
  • Another aspect of the invention provides a system for concentrating a nuclides in a solidified radioactive waste liquid, comprising:
  • a pretreatment unit comprising a first selective extractant
  • a concentration unit comprising a dope tank provided with a reverse osmosis device such that the retentate of the reverse osmosis device is returned to the dope tank, and the outlet of the pretreatment unit is opposite to the counter Inlet connection of the osmosis device;
  • an extraction unit comprising an organic ion exchange bed and/or a second selective extractant, the water inlet of the extraction unit being connected to the dope tank such that liquid in the dope tank enters the In the extracting unit, the water outlet of the extracting unit is connected to the dope tank such that the liquid passing through the extracting unit is returned to the dope tank;
  • a nuclide curing unit in which a nuclides-rich selective extractant and/or a nuclides-rich organic ion exchange resin form a solidified body.
  • the first selective extractant for pretreatment and the second selective extractant for extraction may or may not be the same.
  • the selective extractants each independently comprise an inorganic oxide support and a nuclides extraction active component, or each independently comprise a molecular sieve or zeolite.
  • the inventors have surprisingly found that by the method and system of the present invention, radionuclides in concentrated radioactive waste liquids can be efficiently extracted for safe storage while minimizing radioactive waste.
  • the method and system of the present invention not only utilizes the adsorption capacity of the resin, but also minimizes the amount of radioactive waste resin produced, and ensures that the discharged liquid meets environmental discharge requirements.
  • the method and system of the present invention exhibits the advantages of low energy consumption, simple equipment, convenient operation, and small amount of nuclide after concentration and solidification.
  • the present invention provides a novel method and system for concentrating the storage of radionuclides in radioactive waste liquids, at least in the following aspects:
  • the inventor repeatedly used the demonstration engineering prototype to repeatedly combine, test, adjust and verify each unit, and finally obtained the most effective organic whole, so that the mutual cooperation between the units is optimal, so that each unit is simple. A feature that cannot be achieved by a combination.
  • Nuclide (Ag and Co) cannot be effectively concentrated by the ion exchange resin, but after oxidation, it is treated with a selective extractant and an ion exchange resin to achieve an enrichment target.
  • Some nuclides, such as Sr, are subject to competition by divalent cations present in the solution when concentrated by the ion exchange resin, thereby shortening the service life of the resin, but can promote the overall radioactive waste after the addition of the selective extractant.
  • Quantify In view of the concentrated nature of various nuclide, the inventors designed the concentrated solidification method and system to subtly achieve concentrated curing of various nuclide.
  • the role of the ion exchange resin is to concentrate and contain the radionuclide, so there is no particularly high requirement for the decontamination coefficient of the resin itself, so that the adsorption capacity of the resin can be fully utilized, and the amount of the radioactive resin can be generated. Greatly reduced.
  • the method and system of the present invention achieves a recovery rate of nuclide in more than 95% of the radioactive waste liquid while ensuring that the discharged liquid meets environmental discharge requirements.
  • One aspect of the present invention provides a method of concentrating a nuclides in a solidified radioactive waste liquid, comprising the steps of: step 1) pretreating: extracting radioactive waste liquid with a first selective extractant; and step 2) concentrating: The extracted radioactive waste liquid is subjected to reverse osmosis concentration; step 3) extraction: using the organic ion exchange resin and/or the second selective extractant to extract the radionuclide enriched in the concentrate to the solid phase; step 4) Curing: The nuclides-rich organic ion exchange resin and/or the first selective extractant obtained in the step 3) and the first selective extractant obtained in the step 1) are further formed into a solidified body.
  • the selective extracting agent in the step 1) is mainly used for extracting a part of the radioactive waste liquid which is not easily trapped by the film, in particular, for extracting a part of the nuclide Cs which is not easily trapped by the film.
  • the inventors found that among the hundreds of species of nuclides, several species of nuclides could not be effectively concentrated by reverse osmosis, and are also referred to herein as "nuclears that are not easily trapped by the membrane.”
  • the selective extractant in step 3) can extract "nuclears that are not easily trapped by the membrane” and nuclei that are prone to competition by divalent cations, thereby promoting the miniaturization of the total radioactive waste.
  • the concentrate in step 3), is treated to remove organics from the liquid prior to the extraction of the nuclide.
  • activated carbon is used.
  • the pretreating further comprises: oxidizing the radionuclide in the radioactive waste liquid to convert it into an ionic state, preferably using ultraviolet light, ozone, hydrogen peroxide, prior to performing the extraction in step 1) Oxidation with and/or sodium hypochlorite.
  • the liquid may be filtered during various stages of the process of the invention (e.g., prior to extraction or oxidation of step 1).
  • filtration is carried out using flocculation, activated carbon, security filters, paper core filters, self-cleaning filters, ultrafiltration devices, or any combination thereof to remove fine suspended solids and colloidal materials.
  • ultraviolet photocatalytic oxidation is preferably employed.
  • H 2 O 2 , ozone and/or sodium hypochlorite may be employed as the oxidizing agent, preferably H 2 O 2 .
  • the amount of oxidizing agent added is controlled to be 2-30 mg/L, preferably 3-25 mg/L, more preferably 5-20 mg/L, such as 10 mg/L or 15 mg/L.
  • a "selective extractant” is a class of materials that are capable of selectively extracting and enriching a nuclides.
  • the selective extractant comprises an inorganic oxide support and a nuclides extraction active component.
  • the inorganic oxide support comprises silica, manganese dioxide, aluminum oxide, titanium oxide, zirconium oxide or any combination thereof.
  • the nuclides extraction active component comprises ferrocyanide, citrate, titanate, tin oxide, tungstate or any combination thereof.
  • the selective extractant comprises silica, alumina, ferrocyanide and citrate.
  • the selective extractant comprises a molecular sieve. It is also possible to use cerium zirconium co-melt, natural or synthetic clinoptilolite, molecular sieve NaY, molecular sieve 13X, molecular sieve ZSM-5, molecular sieve SAPO-34, beta molecular sieve, chitosan adsorbent, montmorillonite, hydrated manganese oxide, titanium A silicon molecular sieve, a metal citrate, a hydrated tin oxide or a sodium titanate or any combination thereof as a selective extractant.
  • the inventors have also found that when the constituent components of the selective extractant include silica, alumina, titania, ferrocyanide and decanoate, the recovery of nuclide in the radioactive waste liquid can be further improved.
  • reverse osmosis concentration is carried out in a concentrate tank.
  • the reverse osmosis concentration may also employ a multi-stage liquid tank such as a dosing tank or a medium dope tank.
  • the liquid can be subjected to one or more stages of reverse osmosis concentration, such as secondary or tertiary reverse osmosis concentration.
  • the multi-stage reverse osmosis concentration the permeate of each stage of reverse osmosis sequentially enters the next stage of reverse osmosis, and the retentate of each stage of reverse osmosis returns to the concentrate tank, and the final permeate leaves the concentrate tank.
  • the ratio of fresh water to concentrated water produced by reverse osmosis of each stage is independently controlled, preferably from 1:1 to 8:1, such as 3:1 or 5:1.
  • the fresh water produced by the primary reverse osmosis has a conductivity of less than or equal to 50 ⁇ S/cm, for example, 40 ⁇ S/cm, 35 ⁇ S/cm, 30 ⁇ S/cm, and 25 ⁇ S/cm.
  • the fresh water produced by the second or more stages of reverse osmosis has a conductivity of less than or equal to 25 [mu]S/cm, such as 20 [mu]S/cm, 15 [mu]S/cm, 11 [mu]S/cm, 10 [mu]S/cm.
  • the total number of microbial indicator colonies of the permeate is ⁇ 200 CFU/mL, preferably ⁇ 100 CFU/mL.
  • the liquid produced during the reverse osmosis concentration process (ie, the final permeate) is subjected to desalting purification.
  • the liquid purified concentrated water can be returned to the concentration step.
  • the method of the present invention further comprises the step of 5) liquid purification: desalting the reverse osmosis permeate produced in step 2), and purifying the liquid-purified concentrated water rich in radionuclides Go back to step 2).
  • continuous electric desalination purification is employed.
  • the anode is a pure titanium plate electrode and the cathode is a stainless steel plate.
  • the ratio of fresh water to concentrated water in the continuous electric desalination unit is from 0.5:1 to 10:1, preferably from 1:1 to 5:1, for example 3:1. Fresh water that has been demineralized to meet environmental emissions.
  • the reverse osmosis concentrated concentrate is extracted using an organic ion exchange resin and/or a selective extractant.
  • the organic matter in the concentrate is removed with activated carbon before extraction to avoid enrichment of the organic matter in the concentrate, further improving the stability of the system.
  • the ion exchange resin bed and optional selective extractant are divided into one, two or more stages. When two or more stages of ion exchange resin bed and optional selective extractant are used, the liquid sequentially passes through each stage of the ion exchange resin bed and the selective extractant of each stage, and the ion exchange bed is filled with the mixed cation exchange resin.
  • the cation exchange resin is of the hydrogen type and the anion exchange resin is of the hydrogen oxygen type. Based on the present specification, those skilled in the art can reasonably determine the specifically used ion exchange resin.
  • the reverse osmosis concentrated concentrate is pumped into an organic ion exchange bed and a selective extractant bed.
  • the selective extractant described above can be employed.
  • the first selective extractant for pretreatment and the second selective extractant for extraction may be the same or may not be the same.
  • the various levels of selective extractants used for extraction may or may not be the same.
  • the pH of the final effluent is controlled at 6-8 and returned to the concentrate tank.
  • the flow of liquid into the pretreatment is not critical and can be determined based on actual needs and can be any value.
  • the liquid flow entering the pretreatment is in the range of 0.05 m3/h to 10 m3/h, such as 0.1 m3/h to 5 m3/h, for example, 0.2 m3/h and 1 m3/h.
  • the nuclides-rich selective extractant and/or the nuclides-rich ion exchange resin are stirred with the cement or dehydrated and dried to form a solidified body.
  • the present invention provides a method of concentrating a nuclides in a solidified radioactive waste liquid, comprising the steps of:
  • Step 2 Concentration: at least two stages of reverse osmosis concentration in the concentrated liquid tank, the permeate of each stage of reverse osmosis sequentially enters the next stage, and the retentate of each stage of reverse osmosis returns to the concentrated liquid tank;
  • Step 3) Extraction: The liquid in the concentrated tank in step 2) is extracted using two or more organic ion exchange resins and/or a second selective extractant, and the liquid passes through the ion exchange resins and/or in sequence. Or a second selective extractant, the final effluent is returned to the concentrate tank;
  • Step 4) Nuclide solidification: curing the first selective extractant obtained in step 1) and/or the organic ion exchange resin obtained in step 3) and/or the second selective extractant to form a solidified body;
  • the selective extractant comprises an inorganic oxide support comprising a silica, alumina, titania or any combination thereof, and a nuclides extraction active component comprising a sub Ferricyanide and / or citrate.
  • the present invention provides a method for concentrating a nuclides in a solidified radioactive waste liquid comprising the steps of: 3) extracting: first extracting organic matter in the concentrated liquid by using activated carbon, and then using two or more organic ions.
  • the exchange resin and/or the second selective extractant extracts the liquid in the dope tank in the step 2), and the liquid sequentially passes through the ion exchange resin and/or the second selective extractant, and finally returns to the concentrated liquid tank.
  • Step 1) Pretreatment: the waste liquid enters an oxidizing device, the device is provided with a dosing device and an online pH control measuring and controlling device, and H 2 O 2 is added, and the effluent from the device passes through a selective extracting agent and a selective extracting agent.
  • the composition includes: i) any combination of silica, alumina, titania, zirconia; and, ii) any combination of ferrocyanide, citrate, titanate, tin oxide, tungstate, The effluent from the selective extractant enters the concentrated tank of step 2);
  • Step 2 Concentration: multi-stage reverse osmosis concentration is carried out in the concentrated liquid tank, and the permeate of each stage of reverse osmosis sequentially enters the next stage, and the retentate of each stage of reverse osmosis returns to the concentrated liquid tank;
  • Step 3) Extraction: firstly, the liquid in the concentrated liquid tank in the step 2) is treated with activated carbon to remove the organic matter in the liquid, and then the treated liquid is pumped into the organic ion exchange bed, and the ion exchange resin bed is divided into two stages or more. In multiple stages, the liquid passes through the ion exchange resin beds in each stage, and finally the water returns to the concentrated liquid tank;
  • Step 4) Nuclide curing: The selective extractant produced in the step 1) and/or the ion exchange resin produced in the step 3) are cured to form a solidified body.
  • the effluent conductivity of the extraction step is greater than or equal to the concentrate conductivity in the concentration step, or step 2) the final permeate conductivity is above 50 ⁇ S/cm
  • the first stage in the extraction step The ion exchange resin (nuclear-rich ion exchange resin) and/or the selective extractant in the bed are subjected to step 4) nuclide curing.
  • fresh ion exchange resin and/or fresh selective extractant are loaded as the last stage ion exchange resin and/or selective extractant, and other levels of ion exchange resin and/or selective extractant are sequentially advanced .
  • the controlling step 5) discharges the liquid and the proportion of liquid entering the step 3), preferably from 1 to 10:1, more preferably from 3 to 10:1, for example 3:1, 5: 1 or 8:1.
  • the ratio of the liquid it is possible to further achieve higher nuclides recovery, obtain a smaller volume of concentrated solidified nuclides, further improve the concentration efficiency of the method and system of the present invention, and at the same time, the purified effluent meets the environment. Emission requirements.
  • the present invention provides a novel method for concentrating nuclides in a solidified radioactive waste liquid, the specific process steps of which are as follows:
  • Step 1) Pretreatment: The radioactive waste liquid is first stored in the original liquid tank, and the fine suspension in the liquid can be removed by using flocculation, activated carbon, security filter, paper core filter, self-cleaning filter, ultrafiltration, etc.
  • the device is provided with a dosing device and an online pH control measuring and controlling device to control the addition of a certain amount of H 2 O 2 .
  • the effluent passes through the selective extractant at a flow rate and then proceeds to the concentrate tank of step 2).
  • the composition of the selective extractant comprises: i) any combination of silica, alumina, titania, zirconia; and, ii) ferrocyanide, citrate, titanate, tin oxide, tungstic acid Any combination of salts.
  • Step 2 Concentration: Set high and low working level switches in the concentrated tank.
  • the concentrated liquid tank is provided with multi-stage reverse osmosis concentration, and the permeate of each stage of reverse osmosis sequentially enters the next stage, and finally proceeds to step 5), and the retentate of each stage of reverse osmosis returns to the concentrated liquid tank.
  • Step 3) Extraction: The liquid in the concentrate tank in step 2) is pumped into the organic ion exchange bed.
  • the bed is filled with an yin-yang mixed ion exchange resin.
  • the cation exchange resin is a hydrogen type
  • the anion exchange resin is a hydrogen oxygen type.
  • the ion exchange resin bed is divided into two or more stages, and the liquid sequentially passes through the ion exchange resin beds of each stage, and the final effluent pH is controlled at 6-8, and returns to the concentrated liquid tank.
  • the ion exchange bed effluent conductivity is not lower than the concentration tank conductivity, or step 2) the final permeate conductivity is higher than 50 ⁇ S/cm
  • the ion exchange resin in the first stage bed is fed into the step 4) through the feed pump. After loading the new resin, it is placed in the final stage, and the other levels are moved forward.
  • Step 4) Nuclide solidification: the selective extractant produced in step 1) and the ion exchange resin produced in step 3) are fed into a standard barrel of a predetermined amount of cement through a feed pump, and the cement is stirred to form a solidified body, or After dehydration and drying, it is sent to a standard barrel for storage.
  • Step 5) Liquid purification: the reverse osmosis permeate produced in step 2) enters continuous electric desalting, and the residual radionuclide is enriched in the concentrated electric desalted concentrated water, and returns to the concentrated tank of step 2), and the remaining liquid satisfies Environmental emission requirements.
  • Step 5) The ratio of the liquid discharged into the concentrated liquid tank to the step 3) is controlled at 1-10:1.
  • the present invention provides a novel method for concentrating a nuclides in a solidified radioactive waste liquid comprising the steps of 3) extracting: pumping the liquid in the concentrating tank of step 2) into the activated carbon bed, and then Pumped into an organic ion exchange bed.
  • Another aspect of the invention provides a system for concentrating a nuclides in a solidified radioactive waste liquid, comprising:
  • a pretreatment unit comprising a first selective extractant
  • a concentration unit comprising a dope tank provided with a reverse osmosis device such that the retentate of the reverse osmosis device is returned to the dope tank, and the outlet of the pretreatment unit is opposite to the counter Inlet connection of the osmosis device;
  • an extraction unit comprising an organic ion exchange bed and/or a second selective extractant, the water inlet of the extraction unit being connected to the dope tank such that liquid in the dope tank enters the In the extracting unit, the water outlet of the extracting unit is connected to the dope tank such that the liquid passing through the extracting unit is returned to the dope tank;
  • a nuclides curing unit in which a nuclides-rich selective extractant and/or a nuclides-rich ion exchange resin form a solidified body.
  • the system further comprises an oxidizing device upstream of the first selective extractant.
  • the oxidizing device is preferably equipped with an ultraviolet light source or an ozone oxidizing device.
  • the oxidizing device is provided with a dosing device and an on-line pH control measuring device.
  • the system of nuclides in the concentrated solidified radioactive waste liquid of the present invention comprises:
  • a pretreatment unit comprising a stock solution tank and an oxidation unit, the pretreatment unit further comprising a selective extractant at the effluent;
  • a concentration unit comprising a concentrate tank provided with at least two stages of reverse osmosis means, the outlet of the pretreatment unit being connected to the concentrate tank, and each stage of the reverse osmosis unit is The dosing tank is connected such that the retentate of each stage of the reverse osmosis device is returned to the dope tank;
  • an extracting unit comprising an organic ion exchange bed, wherein the organic ion exchange bed is filled with an anion-mixed ion exchange resin, and a water inlet of the extraction unit is connected to the dope tank such that the concentration unit is The liquid enters the extraction unit, and the water outlet of the extraction unit is connected to the concentrated liquid tank so that the liquid passing through the extraction unit is returned to the concentrated liquid tank;
  • a nuclide curing unit in which a nuclides-rich selective extractant and/or a nuclides-rich ion exchange resin form a solidified body.
  • a filtration device can be included in each unit.
  • the pretreatment unit further comprises a filtering device. More preferably, the filtration device is located upstream of the oxidizing device or selective extractant.
  • the filtration device has a flocculation device, activated carbon, a security filter, a paper core filter, a self-cleaning filter, an ultrafiltration device, or any combination thereof. Filtration is carried out using flocculation, activated carbon, security filters, paper core filters, self-cleaning filters, ultrafiltration devices, or any combination thereof to remove fine suspended solids and colloidal materials.
  • a high working level switch, a low working level switch, or a combination of both is provided in the dope tank.
  • the extraction unit comprises an activated carbon bed prior to the organic ion exchange bed and/or the second selective extractant.
  • the stability of the system can be further improved by removing the organic matter in the concentrate by using activated carbon in the extraction unit to avoid enrichment of the organic matter in the concentrate.
  • the system of the invention further comprises e) a liquid purification unit.
  • the liquid purification unit may comprise or consist of a desalination unit.
  • the water inlet of the liquid purification unit is connected to the concentration unit, so that the permeate passing through the reverse osmosis device enters the liquid purification unit, and the concentrated water outlet of the liquid purification unit is connected to the concentration unit, so that the concentrated water obtained from the desalination unit is returned to the concentrated liquid tank. in.
  • the desalination unit is a continuous electric desalination unit.
  • the anode is a pure titanium plate electrode and the cathode is a stainless steel plate.
  • the inventors of the present invention have surprisingly found that with the method and system of the present invention, an optimum concentration effect and a highly simplified process can be obtained, and the recovery rate of radionuclides in radioactive waste liquid is as high as 95% or more, even as high as 99.9%, and each The unit forms the most efficient organic whole.
  • the resin decontamination coefficient is not required, so that the adsorption capacity of the resin can be fully utilized, and the amount of the radioactive resin produced can be greatly reduced.
  • the method and system of the present invention are capable of recovering radionuclides in radioactive waste liquids at very high recovery rates while the discharged liquids meet environmental emission requirements.
  • the invention also specifically provides some non-limiting embodiments as follows:
  • Embodiment 1 A method for concentrating a nuclides in a solidified radioactive waste liquid, comprising the steps of:
  • Step 1) Pretreatment: extracting the radioactive waste liquid by using the first selective extractant
  • Step 2 Concentration: performing reverse osmosis concentration on the extracted radioactive waste liquid
  • Step 3) extraction extracting the radionuclide enriched in the concentrate into a solid phase by using an organic ion exchange resin and/or a second selective extractant;
  • Step 4) Nuclide solidification: The sulfide-rich organic ion exchange resin and/or the second selective extractant obtained in the step 3) and the first selective extractant obtained in the step 1) are further formed into a solidified body.
  • Embodiment 2 The method of concentrating a nuclides in a solidified radioactive waste liquid according to Embodiment 1, wherein the pretreatment further comprises: in performing the extraction in the step 1), in the radioactive waste liquid
  • the nuclides are oxidized to convert them to an ionic state, preferably by ultraviolet light, ozone, hydrogen peroxide and/or sodium hypochlorite.
  • Embodiment 3 The method for concentrating a nuclides in a solidified radioactive waste liquid according to Embodiment 1, characterized in that the method further comprises, in step 3), preferably using activated carbon to remove the liquid prior to performing the nuclides extraction. Organic matter in the middle.
  • Embodiment 4 The method for concentrating a nuclides in a solidified radioactive waste liquid according to Embodiment 1, characterized in that the method further comprises the step of: 5) purifying the liquid: removing the reverse osmosis permeate produced in the step 2) The salt is purified, preferably continuously demineralized, and the liquid-purified concentrated water enriched in radionuclides is returned to step 2).
  • the inorganic oxide carrier comprises silica, manganese dioxide, aluminum oxide, titanium oxide, zirconium oxide or Any combination thereof
  • the nuclide extraction active component comprises ferrocyanide, citrate, titanate, tin oxide, tungstate or any combination thereof.
  • the organic ion exchange resin comprises a hydrogen type cation exchange resin and a hydroxide type anion exchange resin.
  • the selective extractants each independently comprise a molecular sieve, preferably comprising a molecular sieve NaY, Molecular sieve 13X, molecular sieve ZSM-5, molecular sieve SAPO-34, beta molecular sieve or any combination thereof.
  • Embodiment 9 The method of concentrating a nuclides in a solidified radioactive waste liquid according to any of the preceding embodiments, comprising the steps of:
  • Step 2 Concentration: at least two stages of reverse osmosis concentration in the concentrated liquid tank, the permeate of each stage of reverse osmosis sequentially enters the next stage, and the retentate of each stage of reverse osmosis returns to the concentrated liquid tank;
  • Step 3) Extraction: The liquid in the concentrated tank in step 2) is extracted using two or more organic ion exchange resins and/or a second selective extractant, and the liquid passes through the ion exchange resins and/or in sequence. Or a second selective extractant, the final effluent is returned to the concentrate tank;
  • Step 4) Nuclide solidification: curing the first selective extractant obtained in step 1) and/or the organic ion exchange resin obtained in step 3) and/or the second selective extractant to form a solidified body;
  • the selective extracting agents each independently comprise an inorganic oxide carrier comprising a silica, alumina, titania or any combination thereof, the nuclide extraction activity, and a nuclide extraction active component
  • the component comprises ferrocyanide and/or citrate.
  • step 3 The method of concentrating a nuclides in a solidified radioactive waste liquid according to any one of the preceding embodiments, wherein the conductivity of the effluent in step 3) is greater than or equal to the conductivity of the concentrate in step 2) Or step 2) when the final permeate conductivity is higher than 50 ⁇ S/cm, the first stage ion exchange resin and/or the selective extractant in step 3) is subjected to step 4) nuclide curing, and optionally, loading Fresh ion exchange resin and/or fresh selective extractant are used as the last stage ion exchange resin and/or selective extractant, and other levels of ion exchange resin and/or selective extractant are sequentially advanced.
  • the method of concentrating a nuclides in a solidified radioactive waste liquid characterized in that before the step 1), the flocculation, activated carbon, security filter,
  • the waste liquid is treated by a paper core filter, a self-cleaning filter, ultrafiltration or any combination thereof.
  • the method of concentrating a nuclides in a solidified radioactive waste liquid according to any one of embodiments 4-11, wherein the volume ratio of the fresh water discharged in step 5) to the liquid entering step 3) is controlled at In the range of 1-10:1, preferably in the range of 3-10:1.
  • Embodiment 13 A system for concentrating a nuclides in a solidified radioactive waste liquid, comprising:
  • a pretreatment unit comprising a first selective extractant
  • a concentration unit comprising a dope tank provided with a reverse osmosis device such that the retentate of the reverse osmosis device is returned to the dope tank, and the outlet of the pretreatment unit is opposite to the counter Inlet connection of the osmosis device;
  • an extraction unit comprising an organic ion exchange bed and/or a second selective extractant, the water inlet of the extraction unit being connected to the dope tank such that liquid in the dope tank enters the In the extracting unit, the water outlet of the extracting unit is connected to the dope tank such that the liquid passing through the extracting unit is returned to the dope tank;
  • a nuclide curing unit in which a nuclides-rich selective extractant and/or a nuclides-rich organic ion exchange resin form a solidified body.
  • Embodiment 14 The system for concentrating a nuclides in a solidified radioactive waste liquid according to embodiment 13, wherein in the pretreatment unit, the system further comprises an oxidizing device upstream of the first selective extractant
  • the oxidizing device is preferably equipped with an ultraviolet light source or an ozone device.
  • Embodiment 15 The system for concentrating a nuclides in a solidified radioactive waste liquid according to embodiment 13, wherein the extraction unit comprises a bed of activated carbon prior to the organic ion exchange bed and/or the second selective extraction agent.
  • Embodiment 16 The system for concentrating a nuclides in a solidified radioactive waste liquid according to embodiment 13, wherein the system further comprises e) a liquid purification unit, wherein the liquid purification unit is provided with a desalting unit, the liquid purification a water inlet of the unit is connected to the concentration unit such that permeate passing through the reverse osmosis device enters the liquid purification unit, and a concentrated water outlet of the liquid purification unit is connected to the concentration unit such that the removal is performed The concentrated water obtained by the salt unit is returned to the dope tank.
  • a liquid purification unit wherein the liquid purification unit is provided with a desalting unit, the liquid purification a water inlet of the unit is connected to the concentration unit such that permeate passing through the reverse osmosis device enters the liquid purification unit, and a concentrated water outlet of the liquid purification unit is connected to the concentration unit such that the removal is performed
  • the concentrated water obtained by the salt unit is returned to the dope tank.
  • a system for nucleating a nucleus in a solidified radioactive waste liquid according to any one of the preceding claims 13 to 16, wherein the selective extractant each independently comprises an inorganic oxide carrier and a nuclides extraction Active ingredient.
  • Embodiment 18 The system for concentrating a nuclides in a solidified radioactive waste liquid according to embodiment 17, wherein the inorganic oxide supports each independently comprise silica, manganese dioxide, aluminum oxide, titanium oxide, Zirconia or any combination thereof, and the nuclides extraction active component comprises ferrocyanide, citrate, titanate, tin oxide, tungstate or any combination thereof.
  • the organic ion exchange resin comprises a hydrogen type cation exchange resin and a hydroxide type anion exchange Resin.
  • the selective extractants each independently comprise a molecular sieve, preferably comprising a molecular sieve NaY, Molecular sieve 13X, molecular sieve ZSM-5, molecular sieve SAPO-34, P molecular sieve or any combination thereof.
  • the pretreatment unit further comprises a filtering device having a flocculation device, activated carbon, security Filter, paper core filter, self-cleaning filter, ultrafiltration device or any combination thereof.
  • the concentrating unit comprises a concentrating tank provided with at least two stages of reverse osmosis means, and each The retentate outlet of the stage reverse osmosis unit is connected to the dope tank such that the retentate of each stage of the reverse osmosis unit is returned to the dope tank.
  • the conductivity of the radioactive waste liquid enters the original liquid tank, and the flow rate is controlled at 1 m3/h.
  • the self-cleaning filter and ultrafiltration are used to remove the fine suspended matter in the liquid, and then enter the ultraviolet photocatalytic oxidation device.
  • the device is provided with a dosing device and an online pH control measuring and controlling device, and controls to add a certain amount of H 2 O 2 (adding The amount is controlled at 5 mg/L), and the effluent passes through the selective extractant at a certain flow rate.
  • the components of the selective extractant include: silica, titanium oxide, ferrocyanide and citrate, and the effluent enters the concentrate tank.
  • High and low working level switches are set in the concentrated tank.
  • the concentrated liquid tank is provided with two-stage reverse osmosis concentration, and the permeate of each stage of reverse osmosis sequentially enters the next stage, and finally enters the continuous electric desalting unit, and the retentate of each stage of reverse osmosis returns to the concentrated liquid tank.
  • the membrane module When the system is turned on, the membrane module is automatically flushed and enters the normal working procedure.
  • the radioactive waste liquid first passes through the security filter, and the effluent enters the first-stage reverse osmosis.
  • the ratio of fresh water to concentrated water produced by the first-stage reverse osmosis is controlled at 5:1, the conductivity of fresh water is 40 ⁇ S/cm, and the secondary reverse osmosis enters, and the concentrated water enters the ion exchange resin.
  • the volume ratio of the two-stage reverse osmosis fresh water to the concentrated water is controlled at 5:1, the concentrated water is returned to the concentration tank, the conductivity of the fresh water effluent is 11 ⁇ S/cm, and the total number of microbial indicator colonies is ⁇ 100 CFU/mL, and the continuous electric desalting unit is entered.
  • the anode of the continuous electric desalination unit is a pure titanium plate electrode, and the cathode is made of a stainless steel plate.
  • the ratio of fresh water to concentrated water in the continuous electric desalination unit is 5:1. The fresh water satisfies the environmental discharge, and the concentrated water is returned to the concentration tank through the booster pump.
  • the liquid in the medium concentration tank is first pumped into the activated carbon bed, and then pumped into the ion exchange resin bed, and the flow rate is controlled at 100 L/h.
  • the ion exchange resin bed is divided into two stages, each stage of resin is filled with 10L, the first stage is filled with cation exchange resin, and the second stage is filled with a mixture of positive and negative ion exchange resins.
  • the cation exchange resin is a hydrogen type, and the anion exchange resin is a hydrogen oxygen type.
  • the liquid passes through the ion exchange resin beds in sequence, and the final effluent pH is controlled at 6-8, returning to the concentrate tank.
  • the ion exchange resin in the first stage bed is fed into a standard barrel of a predetermined amount of cement through a feed pump, and the cement is stirred to form a solidified body, or Dehydrated, dried and sent to a standard barrel for storage.
  • the recovery rate of nuclides (except hydrazine) in the radioactive waste liquid is over 99%, and all of them are stored in the selective extractant and the ion exchange material.
  • the conductivity of the radioactive waste liquid enters the original liquid tank, and the flow rate is controlled at 1 m3/h.
  • the self-cleaning filter and ultrafiltration are used to remove the fine suspended matter in the liquid, and then enter the ultraviolet photocatalytic oxidation device.
  • the device is provided with a dosing device and an online pH control measuring and controlling device, and controls to add a certain amount of H 2 O 2 (adding The amount is controlled at 10 mg/L), and the effluent passes through the selective extractant at a certain flow rate.
  • the components of the selective extractant include: alumina, titania, ferrocyanide and citrate, and the effluent enters the concentrate tank.
  • High and low working level switches are set in the concentrated tank.
  • the concentrated liquid tank is provided with three-stage reverse osmosis concentration, and the permeate of each stage of reverse osmosis sequentially enters the next stage, and finally enters the continuous electric desalting unit, and the retentate of each stage of reverse osmosis returns to the concentrated liquid tank.
  • the membrane module When the system is turned on, the membrane module is automatically flushed and enters the normal working procedure.
  • the radioactive waste liquid first passes through the security filter, and the effluent enters the first-stage reverse osmosis.
  • the ratio of fresh water to concentrated water produced by the first-stage reverse osmosis is controlled at 5:1, the conductivity of fresh water is 40 ⁇ S/cm, and the secondary and tertiary reverse osmosis enters, and the concentrated water enters the ion exchange resin.
  • the volume ratio of reverse osmosis fresh water to concentrated water is controlled at 5:1, and the concentrated water returns to the concentration tank.
  • the conductivity of fresh water effluent is 10 ⁇ S/cm, and the total number of microbial indicator colonies is ⁇ 100 CFU/mL, which enters the continuous electric desalting unit.
  • the anode of the continuous electric desalination unit is a pure titanium plate electrode, and the cathode is made of a stainless steel plate.
  • the ratio of fresh water to concentrated water in the continuous electric desalination unit is 3:1. The fresh water satisfies the environmental discharge, and the concentrated water is returned to the concentration tank through the booster pump.
  • the liquid in the medium concentration tank is pumped into the activated carbon bed, and the water is pumped into the adsorption bed.
  • the flow rate of the adsorption bed is controlled at 100 L/h, and the selective extractant filled in the bed comprises: alumina, titanium oxide, ferrocyanide And citrate, a total of 10L.
  • the water is pumped into the organic ion exchange bed and the flow rate is controlled at 100 L/h.
  • the bed is filled with yin and yang mixed ion exchange resin for a total of 20L.
  • the cation exchange resin is a hydrogen type
  • the anion exchange resin is a hydrogen oxygen type.
  • the ion exchange resin bed is divided into two stages, and the liquid passes through the ion exchange resin beds in each stage in turn, and the final effluent pH is controlled at 6-8, and returns to the concentrated liquid tank.
  • the ion exchange resin in the first stage bed is fed into a standard barrel of a predetermined amount of cement through a feed pump, and the cement is stirred to form a solidified body, or Dehydrated, dried and sent to a standard barrel for storage. After the resin bed is filled with new resin, it is placed in the final stage, and the other levels are moved forward.
  • the recovery rate of nuclides (except hydrazine) in the radioactive waste liquid is over 99.9%, and all of them are stored in the selective extractant and the ion exchange material.
  • the conductivity of the radioactive waste liquid enters the original liquid tank, and the flow rate is controlled at 0.2 m3/h.
  • the self-cleaning filter and ultrafiltration are used to remove the fine suspended matter in the liquid, and then enter the ultraviolet photocatalytic oxidation device.
  • the device is provided with a dosing device and an online pH control measuring and controlling device, and controls to add a certain amount of H 2 O 2 (adding The amount is controlled at 10 mg/L), and the effluent passes through the selective extractant at a certain flow rate.
  • the components of the selective extractant include: silica, alumina, titania, ferrocyanide, tin oxide and citrate, effluent Enter the concentrate tank.
  • High and low working level switches are set in the concentrated tank.
  • the concentrated liquid tank is provided with two-stage reverse osmosis concentration, and the permeate of each stage of reverse osmosis sequentially enters the next stage, and finally enters the continuous electric desalting unit, and the retentate of each stage of reverse osmosis returns to the concentrated liquid tank.
  • the membrane module When the system is turned on, the membrane module is automatically flushed and enters the normal working procedure.
  • the radioactive waste liquid first passes through the security filter, and the effluent enters the first-stage reverse osmosis.
  • the volume ratio of fresh water to concentrated water produced by the first-stage reverse osmosis is controlled at 1:1, the conductivity of fresh water is 50 ⁇ S/cm, and the secondary reverse osmosis enters, and the concentrated water enters the ion exchange resin.
  • the volume ratio of the two-stage reverse osmosis fresh water to the concentrated water is controlled at 1:1, and the concentrated water is returned to the concentration tank.
  • the conductivity of the fresh water effluent is 20 ⁇ S/cm, and the total number of microbial indicator colonies is ⁇ 100 CFU/mL, and the continuous electric desalting unit is entered.
  • the anode of the continuous electric desalination unit is a pure titanium plate electrode, and the cathode is made of a stainless steel plate.
  • the ratio of fresh water to concentrated water in the continuous electric desalination unit is 1:1. The fresh water satisfies the environmental discharge, and the concentrated water is returned to the concentration tank through the booster pump.
  • the liquid in the medium concentration tank is pumped into the activated carbon bed, and then pumped into the adsorption bed, and the components of the selective extractant filled in the adsorption bed include: silica, alumina, titania, ferrocyanide, tin oxide And citrate, pumped into the organic ion exchange bed, flow control at 50L / h.
  • the bed is filled with yin and yang mixed ion exchange resin for a total of 10L.
  • the cation exchange resin is a hydrogen type
  • the anion exchange resin is a hydrogen oxygen type.
  • the ion exchange resin bed is divided into two stages, and the liquid passes through the ion exchange resin beds in each stage in turn, and the final effluent pH is controlled at 6-8, and returns to the concentrated liquid tank.
  • the ion exchange resin in the first stage bed is fed into a standard barrel of a predetermined amount of cement through a feed pump, and the cement is stirred to form a solidified body, or Dehydrated, dried and sent to a standard barrel for storage. After the resin bed is filled with new resin, it is placed in the final stage, and the other levels are moved forward.
  • the recovery rate of nuclides (except hydrazine) in the radioactive waste liquid is over 99.9%, and all of them are stored in the selective extractant and the ion exchange material.
  • the conductivity of the radioactive waste liquid enters the original liquid tank, and the flow rate is controlled at 0.2 m3/h. After removing the fine suspension in the liquid by self-cleaning filter and ultrafiltration, the liquid passes through the selective extractant at a certain flow rate, and the components of the selective extracting agent include: alumina, zirconia, ferrocyanide, tin oxide and Tungstate, the effluent enters the concentrate tank.
  • High and low working level switches are set in the concentrated tank.
  • the concentrated liquid tank is provided with two-stage reverse osmosis concentration, and the permeate of each stage of reverse osmosis sequentially enters the next stage, and finally enters the continuous electric desalting unit, and the retentate of each stage of reverse osmosis returns to the concentrated liquid tank.
  • the membrane module When the system is turned on, the membrane module is automatically flushed and enters the normal working procedure.
  • the radioactive waste liquid first passes through the security filter, and the effluent enters the first-stage reverse osmosis.
  • the ratio of fresh water to concentrated water produced by the first-stage reverse osmosis is controlled at 3:1, the conductivity of fresh water is 35 ⁇ S/cm, and the secondary reverse osmosis enters, and the concentrated water enters the ion exchange resin.
  • the volume ratio of the two-stage reverse osmosis fresh water to the concentrated water is controlled at 5:1, the concentrated water is returned to the concentration tank, the conductivity of the fresh water effluent is 10 ⁇ S/cm, and the total number of microbial indicator colonies is ⁇ 100 CFU/mL, and the continuous electric desalting unit is entered.
  • the anode of the continuous electric desalination unit is a pure titanium plate electrode, and the cathode is made of a stainless steel plate.
  • the ratio of fresh water to concentrated water in the continuous electric desalination unit is 5:1. The fresh water satisfies the environmental discharge, and the concentrated water is returned to the concentration tank through the booster pump.
  • the liquid in the medium concentration tank is pumped into the activated carbon bed and then pumped into the adsorption bed.
  • the components of the selective extractant filled in the adsorption bed include: alumina, zirconia, ferrocyanide, tin oxide and tungstate.
  • the water is pumped into the organic ion exchange bed and the flow rate is controlled at 200L/h.
  • the bed is filled with yin and yang mixed ion exchange resin for a total of 10L.
  • the cation exchange resin is a hydrogen type, and the anion exchange resin is a hydrogen oxygen type.
  • the ion exchange resin bed is divided into two stages, and the liquid passes through the ion exchange resin beds in each stage in turn, and the final effluent pH is controlled at 6-8, and returns to the concentrated liquid tank.
  • the ion exchange resin in the first stage bed is fed into a standard barrel of a predetermined amount of cement through a feed pump, and the cement is stirred to form a solidified body, or Dehydrated, dried and sent to a standard barrel for storage. After the resin bed is filled with new resin, it is placed in the final stage, and the other levels are moved forward.
  • the recovery rate of nuclides (except hydrazine) in the radioactive waste liquid is over 95%, and all of them are stored in the selective extractant and the ion exchange material.
  • the conductivity of the radioactive waste liquid enters the original liquid tank, and the flow rate is controlled at 1 m3/h.
  • the self-cleaning filter and ultrafiltration are used to remove the fine suspended matter in the liquid, and then enter the ultraviolet photocatalytic oxidation device.
  • the device is provided with a dosing device and an online pH control measuring and controlling device, and controls to add a certain amount of H 2 O 2 (adding The amount is controlled at 5 mg/L), and the effluent passes through the selective extractant at a certain flow rate.
  • the components of the selective extractant include: silica, zirconia, ferrocyanide and tin oxide, and the effluent enters the concentrate tank.
  • High and low working level switches are set in the concentrated tank.
  • the concentrated liquid tank is provided with two-stage reverse osmosis concentration, and the permeate of each stage of reverse osmosis sequentially enters the next stage, and finally enters the continuous electric desalting unit, and the retentate of each stage of reverse osmosis returns to the concentrated liquid tank.
  • the membrane module When the system is turned on, the membrane module is automatically flushed and enters the normal working procedure.
  • the radioactive waste liquid first passes through the security filter, and the effluent enters the first-stage reverse osmosis.
  • the ratio of the volume of fresh water to concentrated water produced by the first-stage reverse osmosis is controlled at 5:1, the conductivity of fresh water is 40 ⁇ S/cm, and the secondary reverse osmosis enters, and the concentrated water enters the ion exchange resin.
  • the volume ratio of the secondary reverse osmosis fresh water to the concentrated water is controlled at 5:1, the concentrated water is returned to the concentration tank, the conductivity of the fresh water effluent is 11 ⁇ S/cm, and the total number of microbial indicator colonies is ⁇ 100 CFU/mL, and the continuous electric desalting unit is entered.
  • the anode of the continuous electric desalination unit is a pure titanium plate electrode, and the cathode is made of a stainless steel plate.
  • the ratio of fresh water to concentrated water in the continuous electric desalination unit is 5:1. The fresh water satisfies the environmental discharge, and the concentrated water is returned to the concentration tank through the booster pump.
  • the liquid in the medium concentration tank is pumped into the adsorption bed, and the components of the selective extractant filled in the bed include: silica, zirconia, ferrocyanide and tin oxide, and then pumped into the organic ion exchange bed, the flow rate Controlled at 100L/h.
  • the organic ion exchange bed is filled with yin and yang mixed ion exchange resin for a total of 5L.
  • the cation exchange resin is a hydrogen type, and the anion exchange resin is a hydrogen oxygen type.
  • the ion exchange resin bed is divided into two stages, and the liquid passes through the ion exchange resin beds in each stage in turn, and the final effluent pH is controlled at 6-8, and returns to the concentrated liquid tank.
  • the ion exchange resin in the first stage bed is fed into a standard barrel of a predetermined amount of cement through a feed pump, and the cement is stirred to form a solidified body, or Dehydrated, dried and sent to a standard barrel for storage. After the resin bed is filled with new resin, it is placed in the final stage, and the other levels are moved forward.
  • the recovery rate of nuclides (except hydrazine) in the radioactive waste liquid is over 95%, and all are stored in the selective extractant ion exchange material.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Physical Water Treatments (AREA)

Abstract

本发明涉及浓缩固化放射性废液中核素的方法和系统。本发明的浓缩固化放射性废液中核素的方法包括如下步骤：步骤1)预处理：利用第一选择性提取剂对放射性废液进行提取；步骤2)浓缩：对经提取的放射性废液进行反渗透浓缩；步骤3)提取：利用有机离子交换树脂和/或第二选择性提取剂将浓缩液中富集的放射性核素提取至固相；步骤4)核素固化：再使步骤3)获得的富含核素的有机离子交换树脂和/或第二选择性提取剂和步骤1)获得的第一选择性提取剂形成固化体。通过本发明的方法和系统，可以有效提取浓缩放射性废液中的放射性核素，进行安全贮存，同时实现放射性废物的贮存体积最小化。

Description

浓缩固化放射性废液中核素的方法和系统
相关申请的交叉引用
本申请要求获得2018年1月3日提交的名称为“浓缩固化放射性废液中核素的方法和系统”的中国专利申请201810006458.6的优先权。
技术领域
本发明涉及浓缩固化放射性废液中核素的方法和系统。
背景技术
核电作为一种重要的清洁能源，正在逐渐成为世界能源结构中的重要组成部分。日本福岛核事故后，核安全已经成为核能发展中需要重点关注的问题。在核电厂的日常运行及事故工况中，通常产生大量放射性废液。
放射性废液中包含的放射性核素主要有两个来源，一个来源为裂变产物，另一个来源为活化产物和腐蚀产物。第二来源主要与金属材料的活化、腐蚀、沉淀以及释放行为有关，该部分放射性核素包括Ag、Co、Cr、Mn、Fe等核素。在发生燃料破损时，放射性废液中出现具有β放射性的长寿命裂变产物 134Cs/ 137Cs和 90Sr等。对于半衰期长的放射性核素，需要从废液中分离，与环境隔离后长期储存，直至其衰变至无害的水平。
由于放射性核素长期地质储存处置的费用较高，暂存库或处置场容量有限，放射性废液一般要经过浓缩减容，尽可能实现体积最小化，才可以进行长期储存。目前核电厂中，浓缩放射性废液中核素的方法主要是蒸发浓缩和离子交换。无论采取哪种处理方法，实质上是将放射性核素浓缩富集到液体介质或者固体介质中，这些物质最终经固化后进行长期地质储存。蒸发浓缩是将放射性核素在蒸残液和冷凝液中进行重新分配，获得包含绝大多数放射性核素的蒸残液和放射性核素含量较低的冷凝液。离子交换则是将放射性核素容纳在自身的材料中。
蒸发浓缩和离子交换在放射性废液处理中都有广泛的应用，具有各自的优缺点。蒸发工艺优点在于技术成熟，去污能力强，放射性废物产生量最小；缺点在于能耗高，设备庞大，投资高，操作条件差，腐蚀结垢等问题严重。而离子交换工艺则恰好相反，其优点在于能耗低，设备简单，操作方便；缺点在于产生大量的放射性废离子交换树脂，后续处理处置困难。
在三代核电的设计中，蒸发工艺已经逐渐退出，离子交换工艺成为了主体工艺。但是核电厂现有的离子交换工艺在浓缩包容放射性核素的同时，必须确保其排出的液体满足环境排放要求。这对树脂去污系数有较高的要求，并因此使得树脂的吸附容量不可能得到充分利用，导致放射性废树脂的产生量较大，对后期的长期储存产生了较大的压力。
放射性废液本身的处理难度较大，主要表现在以下几个方面：
1)核电厂放射性废液中含有Na-24、Cr-51、Mn-54、Fe-55、Fe-59、Co-58、Co-60、Zn-65、Sr-89、Sr-91、Zr-95、Nb-95、Mo-99、Tc-99m、Ru-103、Ru-106m、Ag-110m、Te-129m、Te-129、Te-131m、Te-131、Te-132、Cs-134、Cs-137、Ba-140、La-140、Ce-141、Ce-143、Ce-144、W-187、Np-239等上百种核素。各核素的性质(例如浓缩富集性质，存在形态，浓度，化合价，腐蚀性等)复杂且可在不同操作条件(例如pH值、离子强度、温度等)下发生变化，对核素的浓缩富集造成一定的难度。
2)放射性核素的质量浓度极低，一般为10 -3微克/升以下；而共存的非放射性离子如K、Na、Ca、Mg的浓度较高，一般为毫克/升的量级，甚至高达克/升量级，这些非放射性离子的存在严重影响放射性废液中核素的浓缩和固化。
3)需要尽可能降低放射性废物的量(尤其是体积)，以较高的回收率浓缩放射性废液中的核素。
4)避免产生放射性的二次废液。
5)需要同时考虑放射性条件下的设备可操作性与可维护维修性、燃料动力消耗、各核素的存在状态和浓缩性质差异等因素。
6)在尽可能简化工艺的情况下，难于使各处理方式间相互协调配合，难以高效地浓缩放射性废液中核素。
目前，本领域中浓缩固化放射性废液中核素的方法或系统，距离全面解决上述问题尚有一定的距离。
发明内容
本发明涉及浓缩固化放射性废液中核素的方法和系统。
本发明的一个方面提供一种浓缩固化放射性废液中核素的方法，其包括如下步骤：
步骤1)预处理：利用第一选择性提取剂对放射性废液进行提取；
步骤2)浓缩：对经提取的放射性废液进行反渗透浓缩；
步骤3)提取：利用第一离子交换树脂和/或第二选择性提取剂将浓缩液中富集的放射性核素提取至固相；
步骤4)核素固化：再使步骤3)获得的富含核素的有机离子交换树脂和/或第二选择性提取剂和步骤1)获得的第一选择性提取剂形成固化体。
本发明的另一个方面提供一种浓缩固化放射性废液中核素的系统，其包含：
a)预处理单元，所述预处理单元包含第一选择性提取剂；
b)浓缩单元，所述浓缩单元包含设有反渗透装置的浓液槽，使得所述反渗透装置的截留液返回所述浓液槽中，并且所述预处理单元的出水口与所述反渗透装置的入口连接；
c)提取单元，所述提取单元包含有机离子交换床和/或第二选择性提取剂，所述提取单元的进水口与所述浓液槽连接使得所述浓液槽中的液体进入所述提取单元中，所述提取单元的出水口与所述浓液槽连接使得经过所述提取单元的液体返回所述浓液槽中；
d)核素固化单元，在所述核素固化单元中富含核素的选择性提取剂和/或富含核素的有机离子交换树脂形成固化体。
在本发明的方法和系统中，用于预处理的第一选择性提取剂和用于提取的第二选择性提取剂可以相同或者可以不相同。选择性提取剂各自独立地包含无机氧化物载体和核素提取活性组分，或者各自独立地包含分子筛或沸石。
发明人惊奇地发现，通过本发明的方法和系统，可以有效提取浓缩放射性废液中的放射性核素，进行安全贮存，同时实现放射性废物最小化。本发明的方法和系统不仅充分利用树脂的吸附容量，使放射性废树脂的产生量最低，而且能够确保排出的液体满足环境排放要求。本发明的方法和系统表现出能耗低、设备简单、操作方便且浓缩固化后核素的量小等优点。
与现有的浓缩方法和系统相比，本发明提供一种浓缩储存放射性废液中核素的新方法和系统的创新性至少表现在以下几个方面：
1)工艺的合理优化组合方式。在本领域，放射性废液极具特殊性。一些技术路线在非放射性料液条件下和放射性料液条件下表现出迥然不同的行为，不通过放射性实验的实际操作与测试，所确定的工艺组合往往与实际情况差异较大。而且在实验室规模和真实的工业规模之间存在较大的差异，不具有可比性。在本发明的方法和系统中，各步骤或单元能够有机地协调配合，形成了集成的方法和系统，其成果被评为示范工程。该示范工程是我国目前唯一在核电厂核岛厂房内、利用真实的放射性料液、完成的工程规模的示范工程。发明人在放射性条件下、利用示范工程样机，对各单元进行反复组合、测试、调整、验证，最终获得了最有效的有机整体，使各单元之间的相互配合最佳，从而实现各个单元简单组合所无法实现的功能。
2)核电厂放射性废液中含有上百种核素。通过开展各单元对单组分核素与多组分核素的浓缩富集规律研究，包括实验室模拟放射性废液中核素浓缩固化实验和在核电厂的示范工程中放射性真实料液验证，发明人首次发现，在上百种核素中，有几种核素、尤其是Cs无法有效被反渗透浓缩，但在加入选择性提取剂后，可以实现富集目标；还发现，有2种核素(Ag和Co)无法有效被离子交换树脂浓缩，但经过氧化后再经过选择性提取剂和离子交换树脂处理，可以实现富集目标。有些核素，例如Sr，在被离子交换树脂浓缩时，会面临溶液中存在的二价阳离子的竞争，从而缩短树脂的使用寿命，但在加入选择性提取剂后，可以促进总体放射性废物的小量化。针对各种核素的浓缩性质，发明人对浓缩固化的方法和系统进行设计，巧妙地实现对各种核素的浓缩固化。
3)由于本发明的方法不需要利用蒸发来实现放射性废液的浓缩，因此系统高度简化，所采用的设备在尺寸、可操作性、可维护维修性、燃料动力消耗上等与其他方法相比都具有明显的优势。
4)通过工艺的合理设置，使得离子交换树脂的作用是浓缩包容放射性核素，因而对树脂本身的去污系数没有特别高的要求，这样可以充分利用树脂的吸附容量，放射性树脂的产生量可以得到大幅度的降低。
5)本发明的方法和系统实现95％以上的放射性废液中核素回收率，同时确保排出的液体满足环境排放要求。
6)本发明的方法和系统在国内外均未见报道，所采用的特定组合方式为放射性液体的核素回收提供了一种开创性设计构思。
具体实施方式
下面对本发明的浓缩固化放射性废液中核素的方法和系统作进一步说明。
本发明的一个方面提供一种浓缩固化放射性废液中核素的方法，其包括如下步骤：步骤1)预处理：利用第一选择性提取剂对放射性废液进行提取；步骤2)浓缩：对经提取的放射性废液进行反渗透浓缩；步骤3)提取：利用有机离子交换树脂和/或第二选择性提取剂将浓缩液中富集的放射性核素提取至固相；步骤4)核素固化：再使步骤3)获得的富含核素的有机离子交换树脂和/或第一选择性提取剂和步骤1)获得的第一选择性提取剂形成固化体。
在本发明的方法中，步骤1)中的选择性提取剂主要用于对放射性废液中部分不易被膜截留的核素进行提取，尤其是用于对部分不易被膜截留的核素Cs进行提取。发明人首次发现，在上百种核素中，有若干种核素无法有效被反渗透浓缩，在本文中也被称为“不易被膜截留的核素”。根据本发明，通过在反渗透处理之前采用选择性提取剂处理，可以有效地实现Cs等部分不易被膜截留的核素的富集。步骤3)中的选择性提取剂可以提取“不易被膜截留的核素”以及易于二价阳离子竞争的核素，从而促进总体放射性废物的小量化。
在一些优选的实施方式中，在步骤3)中，在进行核素提取前，对浓缩液进行处理，以去除液体中的有机物。优选地，使用活性炭。发明人惊奇地发现，通过去除浓缩液中的有机物，避免有机物在浓缩液中富集，能够进一步提高系统的稳定性。
在一种优选的实施方式中，预处理还包括：在进行步骤1)中的提取之前，对放射性废液中核素进行氧化，使其转化为离子态，优选地采用紫外光、臭氧、双氧水和/或次氯酸钠进行氧化。
在本发明的方法的各个阶段中(例如，在步骤1)的提取或氧化前)，可以对液体进行过滤。优选地，采用絮凝、活性炭、保安过滤器、纸芯过滤器、自清洗过滤器、超滤装置或其任意组合，进行过滤，以去除细微悬浮物和胶体物质。
在氧化中，优选地采用紫外光催化氧化。可以采用H 2O 2、臭氧和/或次氯酸钠为氧化剂，优选地采用H 2O 2。在一些实施方式中，氧化剂的加入量控制在2-30mg/L，优选地3-25mg/L，更优选地5-20mg/L，例如10mg/L或15mg/L。
在本文中使用时，“选择性提取剂”是一类能够对核素进行选择性地提取、富集的物质。
在本发明的一些实施方式中，选择性提取剂包含无机氧化物载体和核素提取活性组分。优选地，无机氧化物载体包含二氧化硅、二氧化锰、氧化铝、氧化钛、氧化锆或其任意组合。优选地，核素提取活性组分包含亚铁氰化物、锑酸盐、钛酸盐、氧化锡、钨酸盐或其任意组合。最优选地，选择性提取剂包含二氧化硅、氧化铝、亚铁氰化物和锑酸盐。
在另一些实施方式中，选择性提取剂包含分子筛。也可以使用铈锆共熔体、天然或合成斜发沸石、分子筛NaY、分子筛13X、分子筛ZSM-5、分子筛SAPO-34、β分子筛、壳聚糖吸附剂、蒙脱石、水合氧化锰、钛硅分子筛、金属锑酸盐、水合氧化锡或钛酸钠或其任意组合作为选择性提取剂。
发明人还发现，当选择性提取剂的组成成分包括：二氧化硅、氧化铝、氧化钛、亚铁氰化物和锑酸盐时，能够进一步提高放射性废液中核素的回 收率。
在本文中，反渗透浓缩在浓液槽中进行。在优选的实施方式中，反渗透浓缩也可以采用浓液槽和中浓液槽等多级液槽。在浓液槽中，液体可以进行一级或多级反渗透浓缩，例如进行二级或三级反渗透浓缩。在采用多级反渗透浓缩时，每一级反渗透的透过液依次进入下一级反渗透，每一级反渗透的截留液均返回浓液槽，最终的透过液离开浓液槽。在一些实施方式中，独立地控制各级反渗透产生的淡水与浓水体积比例，优选地1:1至8:1，例如3:1或5:1。一级反渗透产生的淡水的电导率为小于或等于50μS/cm，例如40μS/cm、35μS/cm、30μS/cm、25μS/cm。二级或更多级反渗透产生的淡水的电导率为小于或等于25μS/cm，例如20μS/cm、15μS/cm、11μS/cm、10μS/cm。在反渗透浓缩过程中，最终的透过液的微生物指标菌落总数<200CFU/mL，优选地<100CFU/mL。
在一些实施方式中，对反渗透浓缩过程中产生的液体(即，最终的透过液)进行除盐净化。可以将经液体净化的浓水返回到浓缩步骤中。在一些优选的实施方式中，本发明的方法还包括步骤5)液体净化：对步骤2)产生的反渗透透过液进行除盐净化，并且将富含放射性核素的经液体净化的浓水返回步骤2)。优选地，采用连续电除盐净化。在优选的实施方式中，在连续电除盐中，阳极采用纯钛板电极，阴极采用不锈钢板。连续电除盐单元的淡水与浓水体积比例为0.5:1至10:1，优选地1:1至5:1，例如3:1。经过除盐净化的淡水满足环境排放。
在本文中，利用有机离子交换树脂和/或选择性提取剂对反渗透浓缩的浓缩液进行提取。优选地，在提取前，用活性炭去除浓缩液中的有机物，以避免有机物在浓缩液中富集，进一步提高系统的稳定性。离子交换树脂床和任选的选择性提取剂分为一级、两级或更多级。采用两级或更多级离子交换树脂床和任选的选择性提取剂时，液体依次穿过各级离子交换树脂床和各级选择性提取剂，离子交换床内填装阴阳混合离子交换树脂。优选地，阳离子交换树脂为氢型，阴离子交换树脂为氢氧型。在本说明书的基础上，本领域技术人员能够合理地确定具体采用的离子交换树脂。
在一些实施方式中，将反渗透浓缩的浓缩液泵入有机离子交换床和选 择性提取剂床中。当采用选择性提取剂进行提取步骤时，可以采用上文所述的选择性提取剂。用于预处理的第一选择性提取剂和用于提取的第二选择性提取剂可以相同或者可以不相同。用于提取的各级选择性提取剂可以相同或者可以不相同。经过提取步骤后，最终出水的pH值控制在6-8，并且返回浓液槽。
进入预处理的液体流量并不是关键的，可以根据实际需要来确定，并且可以是任何值。在本发明的一些示例性实施方式中，进入预处理的液体流量在0.05m3/h-10m3/h范围内，例如0.1m3/h-5m3/h，例如，0.2m3/h和1m3/h。
在一些优选的实施方式中，富含核素的选择性提取剂和/或富含核素的离子交换树脂与水泥经搅拌，或者经过脱水、烘干，以形成固化体。
在尤其优选的实施方式中，本发明提供一种浓缩固化放射性废液中核素的方法，包括如下步骤：
步骤1)预处理：在紫外光下用H 2O 2对所述放射性废液进行催化氧化，然后利用第一选择性提取剂进行提取；
步骤2)浓缩：在浓液槽中进行至少两级反渗透浓缩，每一级反渗透的透过液依次进入下一级，每一级反渗透的截留液均返回浓液槽；
步骤3)提取：使用两级或更多级有机离子交换树脂和/或第二选择性提取剂对步骤2)中浓液槽中的液体进行提取，液体依次穿过各级离子交换树脂和/或第二选择性提取剂，最终出水返回浓液槽；
步骤4)核素固化：使步骤1)获得的第一选择性提取剂和/或步骤3)获得的有机离子交换树脂和/或第二选择性提取剂固化形成固化体；
所述选择性提取剂包含无机氧化物载体和核素提取活性组分，所述无机氧化物载体包含二氧化硅、氧化铝、氧化钛或其任意组合，所述核素提取活性组分包含亚铁氰化物和/或锑酸盐。
在甚至更优选的实施方式中，本发明提供一种浓缩固化放射性废液中核素的方法包括步骤3)提取：先利用活性炭提取浓缩液中的有机物，再使用两级或更多级有机离子交换树脂和/或第二选择性提取剂对步骤2)中浓液槽中的液体进行提取，液体依次穿过各级离子交换树脂和/或第二选择 性提取剂，最终出水返回浓液槽。
在本发明的另一个方面还提供一种浓缩固化放射性废液中核素的方法，包括如下步骤：
步骤1)预处理：使废液进入氧化装置，所述装置设有加药装置和在线pH控制测控装置，加入H 2O 2，来自所述装置的出水经过选择性提取剂，选择性提取剂的组成成分包括：i)二氧化硅、氧化铝、氧化钛、氧化锆的任意组合；和，ii)亚铁氰化物、锑酸盐、钛酸盐、氧化锡、钨酸盐的任意组合，经过选择性提取剂的出水进入步骤2)的浓液槽；
步骤2)浓缩：在浓液槽中进行多级反渗透浓缩，每一级反渗透的透过液依次进入下一级，每一级反渗透的截留液均返回浓液槽；
步骤3)提取：先将步骤2)中浓液槽中的液体用活性炭处理，以去除液体中的有机物，再将经处理的液体泵入有机离子交换床，离子交换树脂床分两级或更多级，液体依次穿过各级离子交换树脂床，最终出水返回浓液槽；
步骤4)核素固化：使步骤1)产生的选择性提取剂和/或步骤3)产生的离子交换树脂固化形成固化体。
在一些优选的实施方式中，当提取步骤的出水电导率大于或等于浓缩步骤中浓缩液电导率，或者步骤2)最终透过液电导率高于50μS/cm时，提取步骤中的第一级床内的离子交换树脂(富含核素的离子交换树脂)和/或选择性提取剂进行步骤4)核素固化。任选地，装填新鲜的离子交换树脂和/或新鲜的选择性提取剂作为最后一级离子交换树脂和/或选择性提取剂，其它各级离子交换树脂和/或选择性提取剂依次前移。
在一些优选的实施方式中，控制步骤5)排出液体与进入步骤3)的液体比例，优选地1-10:1，更优选地在3-10:1范围内，例如3:1、5:1或8:1。通过控制该液体比例，能够进一步实现更高的核素回收率，获得更小的经浓缩固化的核素的体积，进一步提高本发明的方法和系统的浓缩效率，同时使经过净化的出水满足环境排放要求。
在一个尤其优选的示例中，本发明提供一种浓缩固化放射性废液中核素的新方法，其具体工艺步骤如下：
步骤1)预处理：放射性废液首先存入原液槽，可以利用絮凝、活性炭、保安过滤器、纸芯过滤器、自清洗过滤器、超滤等方法，去除液体中细微悬浮物后，进入氧化装置，该装置设有加药装置和在线pH控制测控装置，控制加入一定量的H 2O 2。出水以一定流速经过选择性提取剂，然后进入步骤2)的浓液槽。该选择性提取剂的组成成分包括：i)二氧化硅、氧化铝、氧化钛、氧化锆的任意组合；和，ii)亚铁氰化物、锑酸盐、钛酸盐、氧化锡、钨酸盐的任意组合。
步骤2)浓缩：浓液槽内设置高、低工作液位开关。浓液槽设多级反渗透浓缩，每一级反渗透的透过液依次进入下一级，最终进入步骤5)，每一级反渗透的截留液均返回浓液槽。
步骤3)提取：将步骤2)中浓液槽中的液体泵入有机离子交换床。床内填装阴阳混合离子交换树脂。阳离子交换树脂为氢型，阴离子交换树脂为氢氧型。离子交换树脂床分两级或多级，液体依次穿过各级离子交换树脂床，最终出水pH值控制在6-8，返回浓液槽。当离子交换床出水电导率不低于浓缩槽电导率，或者步骤2)最终透过液电导率高于50μS/cm，第一级床内的离子交换树脂经供料泵输进入步骤4)，装填新树脂后置为最后一级，其它各级依次前移。
步骤4)核素固化：步骤1)产生的选择性提取剂和步骤3)产生的离子交换树脂经供料泵输送入预先置有一定量水泥的标准桶，与水泥经搅拌后形成固化体，或者经过脱水、烘干后送入标准桶储存。
步骤5)液体净化：步骤2)产生的反渗透透过液进入连续电除盐，残留的放射性核素富集在连续电除盐的浓水中，返回步骤2)的浓液槽，剩余液体满足环境排放要求。步骤5)排出液体与浓液槽中进入步骤3)的液体比例控制在1-10:1。
在甚至更优选的示例中，本发明提供一种浓缩固化放射性废液中核素的新方法，其包括步骤3)提取：将步骤2)中浓液槽中的液体先泵入活性炭床，再泵入有机离子交换床。
本发明的另一个方面提供一种浓缩固化放射性废液中核素的系统，其包括：
a)预处理单元，所述预处理单元包含第一选择性提取剂；
b)浓缩单元，所述浓缩单元包含设有反渗透装置的浓液槽，使得所述反渗透装置的截留液返回所述浓液槽中，并且所述预处理单元的出水口与所述反渗透装置的入口连接；
c)提取单元，所述提取单元包含有机离子交换床和/或第二选择性提取剂，所述提取单元的进水口与所述浓液槽连接使得所述浓液槽中的液体进入所述提取单元中，所述提取单元的出水口与所述浓液槽连接使得经过所述提取单元的液体返回所述浓液槽中；
d)核素固化单元，在所述核素固化单元中富含核素的选择性提取剂和/或富含核素的有离子交换树脂形成固化体。
在一些优选的实施方式中，在预处理单元中，系统还包含位于第一选择性提取剂的上游的氧化装置。氧化装置优选地配备有紫外光源或臭氧氧化装置。优选地，氧化装置设有加药装置和在线pH控制测控装置。
在一些优选的实施方式中，本发明的浓缩固化放射性废液中核素的系统包括：
a)预处理单元，所述预处理单元包含原液槽和氧化装置，所述预处理单元在出水处还包含选择性提取剂；
b)浓缩单元，所述浓缩单元包含设有至少两级反渗透装置的浓液槽，所述预处理单元的出水口与所述浓液槽连接，并且每一级反渗透装置均与所述浓液槽连接使得每一级反渗透装置的截留液均返回所述浓液槽中；
c)提取单元，所述提取单元包含有机离子交换床，所述有机离子交换床内填装阴阳混合离子交换树脂，所述提取单元的进水口与所述浓液槽连接使得所述浓缩单元中的液体进入所述提取单元中，所述提取单元的出水口与所述浓液槽连接使得经过所述提取单元的液体返回所述浓液槽中；
d)核素固化单元，在所述核素固化单元中富含核素的选择性提取剂和/或富含核素的离子交换树脂形成固化体。
在一些优选的实施方式中，在各个单元中可以包含过滤装置。优选地，预处理单元还包含过滤装置。更优选地，过滤装置位于氧化装置或选择性提取剂的上游位置。在一些实施方式中，过滤装置具有絮凝装置、活性炭、 保安过滤器、纸芯过滤器、自清洗过滤器、超滤装置或其任意组合。采用絮凝、活性炭、保安过滤器、纸芯过滤器、自清洗过滤器、超滤装置或其任意组合，进行过滤，以去除细微悬浮物和胶体物质。
在本发明的系统中，在浓液槽内设置高工作液位开关、低工作液位开关或二者的组合。
在一些优选的实施方式中，在本发明的浓缩固化放射性废液中核素的系统中，提取单元包含在有机离子交换床和/或第二选择性提取剂之前的活性炭床。如上文所讨论，通过在提取单元中优选地使用活性炭去除浓缩液中的有机物，避免有机物在浓缩液中富集，能够进一步提高系统的稳定性。
在优选的实施方式中，本发明的系统还包含e)液体净化单元。液体净化单元可以包含除盐单元或由除盐单元组成。液体净化单元的进水口与浓缩单元连接，使得经过反渗透装置的透过液进入液体净化单元，并且液体净化单元的浓水出口与浓缩单元连接使得从除盐单元获得的浓水返回浓液槽中。
在优选的实施方式中，除盐单元是连续电除盐单元。优选地，在连续电除盐单元中，阳极采用纯钛板电极，阴极采用不锈钢板。
本发明的发明人惊讶地发现，采用本发明的方法和系统，能够获得最佳浓缩效果且高度简化的工艺，放射性废液中核素的回收率高达95％以上，甚至高达99.9％，并且各单元形成了最高效的有机整体。在本发明的方法和系统中，不对树脂去污系数有要求，从而可以充分利用树脂的吸附容量，使放射性树脂的产生量可以得到大幅度的降低。本发明的方法和系统能够以非常高的回收率回收放射性废液中核素，同时排出的液体满足环境排放要求。
为了进一步举例说明本发明的某些方面，本发明还具体地提供了如下的一些非限制性实施方式：
实施方式1.一种浓缩固化放射性废液中核素的方法，其包括如下步骤：
步骤1)预处理：利用第一选择性提取剂对放射性废液进行提取；
步骤2)浓缩：对经提取的放射性废液进行反渗透浓缩；
步骤3)提取：利用有机离子交换树脂和/或第二选择性提取剂将浓缩 液中富集的放射性核素提取至固相；
步骤4)核素固化：再使步骤3)获得的富含核素的有机离子交换树脂和/或第二选择性提取剂和步骤1)获得的第一选择性提取剂形成固化体。
实施方式2.如实施方式1所述的浓缩固化放射性废液中核素的方法，其特征在于，所述预处理还包括：在进行步骤1)中的所述提取之前，对放射性废液中核素进行氧化，使其转化为离子态，优选地采用紫外光、臭氧、双氧水和/或次氯酸钠进行氧化。
实施方式3.如实施方式1所述的浓缩固化放射性废液中核素的方法，其特征在于，所述方法还包括步骤3)中，在进行核素提取前，优选地使用活性炭，去除液体中的有机物。
实施方式4.如实施方式1所述的浓缩固化放射性废液中核素的方法，其特征在于，所述方法还包括步骤5)液体净化：对步骤2)产生的反渗透透过液进行除盐净化、优选地连续电除盐，并且将富含放射性核素的经液体净化的浓水返回步骤2)。
实施方式5.如实施方式1-4中任意一项所述的浓缩固化放射性废液中核素的方法，其特征在于，所述选择性提取剂各自独立地包含无机氧化物载体和核素提取活性组分。
实施方式6.如实施方式5所述的浓缩固化放射性废液中核素的方法，其特征在于，所述无机氧化物载体包含二氧化硅、二氧化锰、氧化铝、氧化钛、氧化锆或其任意组合，并且所述核素提取活性组分包含亚铁氰化物、锑酸盐、钛酸盐、氧化锡、钨酸盐或其任意组合。
实施方式7.如前面实施方式中任意一项所述的浓缩固化放射性废液中核素的方法，其特征在于，所述有机离子交换树脂包含氢型阳离子交换树脂和氢氧型阴离子交换树脂。
实施方式8.如实施方式1-4中任意一项所述的浓缩固化放射性废液中核素的方法，其特征在于，所述选择性提取剂各自独立地包含分子筛，优选地包含分子筛NaY、分子筛13X、分子筛ZSM-5、分子筛SAPO-34、β分子筛或其任意组合。
实施方式9.如前面实施方式中任意一项所述的浓缩固化放射性废液中 核素的方法，其包括如下步骤：
步骤1)预处理：在紫外光下用H 2O 2对所述放射性废液进行催化氧化，然后利用第一选择性提取剂进行提取；
步骤2)浓缩：在浓液槽中进行至少两级反渗透浓缩，每一级反渗透的透过液依次进入下一级，每一级反渗透的截留液均返回浓液槽；
步骤3)提取：使用两级或更多级有机离子交换树脂和/或第二选择性提取剂对步骤2)中浓液槽中的液体进行提取，液体依次穿过各级离子交换树脂和/或第二选择性提取剂，最终出水返回浓液槽；
步骤4)核素固化：使步骤1)获得的第一选择性提取剂和/或步骤3)获得的有机离子交换树脂和/或第二选择性提取剂固化形成固化体；
其中所述选择性提取剂各自独立地包含无机氧化物载体和核素提取活性组分，所述无机氧化物载体包含二氧化硅、氧化铝、氧化钛或其任意组合，所述核素提取活性组分包含亚铁氰化物和/或锑酸盐。
实施方式10.如前面实施方式中任意一项所述的浓缩固化放射性废液中核素的方法，其特征在于，当步骤3)中出水的电导率大于或等于步骤2)中浓缩液电导率，或者步骤2)最终透过液电导率高于50μS/cm时，步骤3)中的第一级离子交换树脂和/或选择性提取剂进行步骤4)核素固化，并且任选地，装填新鲜的离子交换树脂和/或选新鲜的择性提取剂作为最后一级离子交换树脂和/或选择性提取剂，其它各级离子交换树脂和/或选择性提取剂依次前移。
实施方式11.如前面实施方式中任意一项所述的浓缩固化放射性废液中核素的方法，其特征在于，在所述步骤1)预处理步骤前，利用絮凝、活性炭、保安过滤器、纸芯过滤器、自清洗过滤器、超滤或其任意组合对废液进行处理。
实施方式12.如实施方式4-11中任意一项所述的浓缩固化放射性废液中核素的方法，其特征在于，步骤5)排出的淡水与进入步骤3)的液体的体积比例控制在1-10:1范围内，优选地在3-10:1范围内。
实施方式13.一种浓缩固化放射性废液中核素的系统，其包含：
a)预处理单元，所述预处理单元包含第一选择性提取剂；
b)浓缩单元，所述浓缩单元包含设有反渗透装置的浓液槽，使得所述反渗透装置的截留液返回所述浓液槽中，并且所述预处理单元的出水口与所述反渗透装置的入口连接；
c)提取单元，所述提取单元包含有机离子交换床和/或第二选择性提取剂，所述提取单元的进水口与所述浓液槽连接使得所述浓液槽中的液体进入所述提取单元中，所述提取单元的出水口与所述浓液槽连接使得经过所述提取单元的液体返回所述浓液槽中；
d)核素固化单元，在所述核素固化单元中富含核素的选择性提取剂和/或富含核素的有机离子交换树脂形成固化体。
实施方式14.如实施方式13所述的浓缩固化放射性废液中核素的系统，其中在所述预处理单元中，所述系统还包含位于所述第一选择性提取剂的上游的氧化装置，所述氧化装置优选地配备有紫外光源或臭氧装置。
实施方式15.如实施方式13所述的浓缩固化放射性废液中核素的系统，其中所述提取单元包含在所述有机离子交换床和/或第二选择性提取剂之前的活性炭床。
实施方式16.如实施方式13所述的浓缩固化放射性废液中核素的系统，其中所述系统还包含e)液体净化单元，所述液体净化单元中设有除盐单元，所述液体净化单元的进水口与所述浓缩单元连接，使得经过所述反渗透装置的透过液进入所述液体净化单元，并且所述液体净化单元的浓水出口与所述浓缩单元连接使得从所述除盐单元获得的浓水返回所述浓液槽中。
实施方式17.如实施方式13-16中任意一项所述的浓缩固化放射性废液中核素的系统，其特征在于，所述选择性提取剂各自独立地包含无机氧化物载体和核素提取活性组分。
实施方式18.如实施方式17所述的浓缩固化放射性废液中核素的系统，其特征在于，所述无机氧化物载体各自独立地包含二氧化硅、二氧化锰、氧化铝、氧化钛、氧化锆或其任意组合，并且所述核素提取活性组分包含亚铁氰化物、锑酸盐、钛酸盐、氧化锡、钨酸盐或其任意组合。
实施方式19.如实施方式13-16中任意一项所述的浓缩固化放射性废液中核素的系统，其特征在于，所述有机离子交换树脂包含氢型阳离子交换 树脂和氢氧型阴离子交换树脂。
实施方式20.如实施方式13-16中任意一项所述的浓缩固化放射性废液中核素的系统，其特征在于，所述选择性提取剂各自独立地包含分子筛，优选地包含分子筛NaY、分子筛13X、分子筛ZSM-5、分子筛SAPO-34、P分子筛或其任意组合。
实施方式21.根据实施方式13-16中任意一项所述的浓缩固化放射性废液中核素的系统，其中所述预处理单元还包含过滤装置，所述过滤装置具有絮凝装置、活性炭、保安过滤器、纸芯过滤器、自清洗过滤器、超滤装置或其任意组合。
实施方式22.根据实施方式13-16中任意一项所述的浓缩固化放射性废液中核素的系统，其中所述浓缩单元包含设有至少两级反渗透装置的浓液槽，并且每一级反渗透装置的截留液出口均与所述浓液槽连接使得每一级反渗透装置的截留液均返回所述浓液槽中。
通过下文的实施例对本发明的技术方案进行示例性地说明。
实施例
实施例1：
放射性废液电导率进入原液槽，流量控制在1m3/h。利用自清洗过滤器、超滤，去除液体中细微悬浮物后，进入紫外光催化氧化装置，该装置设有加药装置和在线pH控制测控装置，控制加入一定量的H 2O 2(投加量控制在5mg/L)，出水以一定流速经过选择性提取剂，选择性提取剂的组成成分包括：二氧化硅、氧化钛、亚铁氰化物和锑酸盐，出水进入浓液槽。
浓液槽内设置高、低工作液位开关。浓液槽设两级反渗透浓缩，每一级反渗透的透过液依次进入下一级，最终进入连续电除盐单元，每一级反渗透的截留液均返回浓液槽。系统开机时对膜组件自动冲洗，进入正常工作程序。系统停运时，用非放射性水或者系统产生的淡水进行在线冲洗。放射性废液首先经过保安过滤器，出水进入一级反渗透。一级反渗透产生的淡水与浓水体积比例控制在5:1，淡水的电导率为40μS/cm，进入二级反渗透，浓水进入离子交换树脂。二级反渗透淡水与浓水体积比例控制在5:1， 浓水返回浓缩槽，淡水出水电导率为11μS/cm，微生物指标菌落总数<100CFU/mL，进入连续电除盐单元。连续电除盐单元阳极采用的是纯钛板电极，阴极采用不锈钢板。连续电除盐单元的淡水与浓水体积比例为5:1。淡水满足环境排放，浓水经增压泵返回浓缩槽。
将中浓液槽中的液体先泵入活性炭床，再泵入离子交换树脂床，流量控制在100L/h。离子交换树脂床分两级，每级树脂装填10L，第一级装填阳离子交换树脂，第二级装填阳阴混合离子交换树脂。阳离子交换树脂为氢型，阴离子交换树脂为氢氧型。液体依次穿过各级离子交换树脂床，最终出水pH值控制在6-8，返回浓液槽。当离子交换床出水电导率不低于浓缩槽电导率，第一级床内的离子交换树脂经供料泵输送入预先置有一定量水泥的标准桶，与水泥经搅拌后形成固化体，或者经过脱水、烘干后送入标准桶储存。
利用此工艺，放射性废液中核素(除氚外)回收率达到99％以上，全部存贮在选择性提取剂和离子交换材料中。
实施例2：
放射性废液电导率进入原液槽，流量控制在1m3/h。利用自清洗过滤器、超滤，去除液体中细微悬浮物后，进入紫外光催化氧化装置，该装置设有加药装置和在线pH控制测控装置，控制加入一定量的H 2O 2(投加量控制在10mg/L)，出水以一定流速经过选择性提取剂，选择性提取剂的组成成分包括：氧化铝、氧化钛、亚铁氰化物和锑酸盐，出水进入浓液槽。
浓液槽内设置高、低工作液位开关。浓液槽设三级反渗透浓缩，每一级反渗透的透过液依次进入下一级，最终进入连续电除盐单元，每一级反渗透的截留液均返回浓液槽。系统开机时对膜组件自动冲洗，进入正常工作程序。系统停运时，用非放射性水或者系统产生的淡水进行在线冲洗。放射性废液首先经过保安过滤器，出水进入一级反渗透。一级反渗透产生的淡水与浓水体积比例控制在5:1，淡水的电导率为40μS/cm，进入二级和三级反渗透，浓水进入离子交换树脂。反渗透淡水与浓水体积比例控制在 5:1，浓水返回浓缩槽，淡水出水电导率为10μS/cm，微生物指标菌落总数<100CFU/mL，进入连续电除盐单元。连续电除盐单元阳极采用的是纯钛板电极，阴极采用不锈钢板。连续电除盐单元的淡水与浓水体积比例为3:1。淡水满足环境排放，浓水经增压泵返回浓缩槽。
将中浓液槽中的液体泵入活性炭床，出水泵入吸附床，吸附床流量控制在100L/h，床内填充的选择性提取剂组成成分包括：氧化铝、氧化钛、亚铁氰化物和锑酸盐，共计10L。出水泵入有机离子交换床，流量控制在100L/h。床内填装阴阳混合离子交换树脂，共计20L。阳离子交换树脂为氢型，阴离子交换树脂为氢氧型。离子交换树脂床分两级，液体依次穿过各级离子交换树脂床，最终出水pH值控制在6-8，返回浓液槽。当离子交换床出水电导率不低于浓缩槽电导率，第一级床内的离子交换树脂经供料泵输送入预先置有一定量水泥的标准桶，与水泥经搅拌后形成固化体，或者经过脱水、烘干后送入标准桶储存。树脂床装填新树脂后置为最后一级，其它各级依次前移。
利用此工艺，放射性废液中核素(除氚外)回收率达到99.9％以上，全部存贮在选择性提取剂和离子交换材料中。
实施例3：
放射性废液电导率进入原液槽，流量控制在0.2m3/h。利用自清洗过滤器、超滤，去除液体中细微悬浮物后，进入紫外光催化氧化装置，该装置设有加药装置和在线pH控制测控装置，控制加入一定量的H 2O 2(投加量控制在10mg/L)，出水以一定流速经过选择性提取剂，选择性提取剂的组成成分包括：二氧化硅、氧化铝、氧化钛、亚铁氰化物、氧化锡和锑酸盐，出水进入浓液槽。
浓液槽内设置高、低工作液位开关。浓液槽设两级反渗透浓缩，每一级反渗透的透过液依次进入下一级，最终进入连续电除盐单元，每一级反渗透的截留液均返回浓液槽。系统开机时对膜组件自动冲洗，进入正常工作程序。系统停运时，用非放射性水或者系统产生的淡水进行在线冲洗。放射性废液首先经过保安过滤器，出水进入一级反渗透。一级反渗透产生 的淡水与浓水体积比例控制在1:1，淡水的电导率为50μS/cm，进入二级反渗透，浓水进入离子交换树脂。二级反渗透淡水与浓水体积比例控制在1:1，浓水返回浓缩槽，淡水出水电导率为20μS/cm，微生物指标菌落总数<100CFU/mL，进入连续电除盐单元。连续电除盐单元阳极采用的是纯钛板电极，阴极采用不锈钢板。连续电除盐单元的淡水与浓水体积比例为1:1。淡水满足环境排放，浓水经增压泵返回浓缩槽。
将中浓液槽中的液体泵入活性炭床，再泵入吸附床，吸附床内填充的选择性提取剂的组成成分包括：二氧化硅、氧化铝、氧化钛、亚铁氰化物、氧化锡和锑酸盐，出水泵入有机离子交换床，流量控制在50L/h。床内填装阴阳混合离子交换树脂，共计10L。阳离子交换树脂为氢型，阴离子交换树脂为氢氧型。离子交换树脂床分两级，液体依次穿过各级离子交换树脂床，最终出水pH值控制在6-8，返回浓液槽。当离子交换床出水电导率不低于浓缩槽电导率，第一级床内的离子交换树脂经供料泵输送入预先置有一定量水泥的标准桶，与水泥经搅拌后形成固化体，或者经过脱水、烘干后送入标准桶储存。树脂床装填新树脂后置为最后一级，其它各级依次前移。
利用此工艺，放射性废液中核素(除氚外)回收率达到99.9％以上，全部存贮在选择性提取剂和离子交换材料中。
实施例4：
放射性废液电导率进入原液槽，流量控制在0.2m3/h。利用自清洗过滤器、超滤，去除液体中细微悬浮物后，液体以一定流速经过选择性提取剂，选择性提取剂的组成成分包括：氧化铝、氧化锆、亚铁氰化物、氧化锡和钨酸盐，出水进入浓液槽。
浓液槽内设置高、低工作液位开关。浓液槽设两级反渗透浓缩，每一级反渗透的透过液依次进入下一级，最终进入连续电除盐单元，每一级反渗透的截留液均返回浓液槽。系统开机时对膜组件自动冲洗，进入正常工作程序。系统停运时，用非放射性水或者系统产生的淡水进行在线冲洗。放射性废液首先经过保安过滤器，出水进入一级反渗透。一级反渗透产生 的淡水与浓水体积比例控制在3:1，淡水的电导率为35μS/cm，进入二级反渗透，浓水进入离子交换树脂。二级反渗透淡水与浓水体积比例控制在5:1，浓水返回浓缩槽，淡水出水电导率为10μS/cm，微生物指标菌落总数<100CFU/mL，进入连续电除盐单元。连续电除盐单元阳极采用的是纯钛板电极，阴极采用不锈钢板。连续电除盐单元的淡水与浓水体积比例为5:1。淡水满足环境排放，浓水经增压泵返回浓缩槽。
将中浓液槽中的液体泵入活性炭床，再泵入吸附床，吸附床内填充的选择性提取剂的组成成分包括：氧化铝、氧化锆、亚铁氰化物、氧化锡和钨酸盐，出水泵入有机离子交换床，流量控制在200L/h。床内填装阴阳混合离子交换树脂，共计10L。阳离子交换树脂为氢型，阴离子交换树脂为氢氧型。离子交换树脂床分两级，液体依次穿过各级离子交换树脂床，最终出水pH值控制在6-8，返回浓液槽。当离子交换床出水电导率不低于浓缩槽电导率，第一级床内的离子交换树脂经供料泵输送入预先置有一定量水泥的标准桶，与水泥经搅拌后形成固化体，或者经过脱水、烘干后送入标准桶储存。树脂床装填新树脂后置为最后一级，其它各级依次前移。
利用此工艺，放射性废液中核素(除氚外)回收率达到95％以上，全部存贮在选择性提取剂和离子交换材料中。
实施例5：
放射性废液电导率进入原液槽，流量控制在1m3/h。利用自清洗过滤器、超滤，去除液体中细微悬浮物后，进入紫外光催化氧化装置，该装置设有加药装置和在线pH控制测控装置，控制加入一定量的H 2O 2(投加量控制在5mg/L)，出水以一定流速经过选择性提取剂，选择性提取剂的组成成分包括：二氧化硅、氧化锆、亚铁氰化物和氧化锡，出水进入浓液槽。
浓液槽内设置高、低工作液位开关。浓液槽设两级反渗透浓缩，每一级反渗透的透过液依次进入下一级，最终进入连续电除盐单元，每一级反渗透的截留液均返回浓液槽。系统开机时对膜组件自动冲洗，进入正常工作程序。系统停运时，用非放射性水或者系统产生的淡水进行在线冲洗。放射性废液首先经过保安过滤器，出水进入一级反渗透。一级反渗透产生 的淡水与浓水体积比例控制在5:1，淡水的电导率为40μS/cm，进入二级反渗透，浓水进入离子交换树脂。二级反渗透淡水与浓水体积比例控制在5:1，浓水返回浓缩槽，淡水出水电导率为11μS/cm，微生物指标菌落总数<100CFU/mL，进入连续电除盐单元。连续电除盐单元阳极采用的是纯钛板电极，阴极采用不锈钢板。连续电除盐单元的淡水与浓水体积比例为5:1。淡水满足环境排放，浓水经增压泵返回浓缩槽。
将中浓液槽中的液体泵入吸附床，床内填充的选择性提取剂的组成成分包括：二氧化硅、氧化锆、亚铁氰化物和氧化锡，然后泵入有机离子交换床，流量控制在100L/h。有机离子交换床内填装阴阳混合离子交换树脂，共计5L。阳离子交换树脂为氢型，阴离子交换树脂为氢氧型。离子交换树脂床分两级，液体依次穿过各级离子交换树脂床，最终出水pH值控制在6-8，返回浓液槽。当离子交换床出水电导率不低于浓缩槽电导率，第一级床内的离子交换树脂经供料泵输送入预先置有一定量水泥的标准桶，与水泥经搅拌后形成固化体，或者经过脱水、烘干后送入标准桶储存。树脂床装填新树脂后置为最后一级，其它各级依次前移。
利用此工艺，放射性废液中核素(除氚外)回收率达到95％以上，全部存贮在选择性提取剂离子交换材料中。
上面通过具体实施例的方式对本发明的各个方面进行了解释，但是本领域技术人员可以理解：本发明并不仅限于上面所描述的具体实施方式，本领域技术人员对本文所公开的各种具体技术手段、原料、装置、工艺步骤等所做的等效替换和以及各种技术手段、原料、装置、工艺步骤等的组合都在本发明的范围之内。

Claims (22)

  1. 一种浓缩固化放射性废液中核素的方法，其包括如下步骤：
    步骤1)预处理：利用第一选择性提取剂对放射性废液进行提取；
    步骤2)浓缩：对经提取的放射性废液进行反渗透浓缩；
    步骤3)提取：利用有机离子交换树脂和/或第二选择性提取剂将浓缩液中富集的放射性核素提取至固相；
    步骤4)核素固化：再使步骤3)获得的富含核素的有机离子交换树脂和/或第二选择性提取剂和步骤1)获得的第一选择性提取剂形成固化体。
  2. 如权利要求1所述的浓缩固化放射性废液中核素的方法，其特征在于，所述预处理还包括：在进行步骤1)中的所述提取之前，对放射性废液中核素进行氧化，使其转化为离子态，优选地采用紫外光、臭氧、双氧水和/或次氯酸钠进行氧化。
  3. 如权利要求1所述的浓缩固化放射性废液中核素的方法，其特征在于，所述方法还包括步骤3)中，在进行核素提取前，优选地使用活性炭，去除液体中的有机物。
  4. 如权利要求1所述的浓缩固化放射性废液中核素的方法，其特征在于，所述方法还包括步骤5)液体净化：对步骤2)产生的反渗透透过液进行除盐净化、优选地连续电除盐，并且将富含放射性核素的经液体净化的浓水返回步骤2)。
  5. 如权利要求1-4中任意一项所述的浓缩固化放射性废液中核素的方法，其特征在于，所述选择性提取剂各自独立地包含无机氧化物载体和核素提取活性组分。
  6. 如权利要求5所述的浓缩固化放射性废液中核素的方法，其特征在于，所述无机氧化物载体包含二氧化硅、二氧化锰、氧化铝、氧化钛、氧化锆或其任意组合，并且所述核素提取活性组分包含亚铁氰化物、锑酸盐、钛酸盐、氧化锡、钨酸盐或其任意组合。
  7. 如前面权利要求中任意一项所述的浓缩固化放射性废液中核素的方法，其特征在于，所述有机离子交换树脂包含氢型阳离子交换树脂和氢氧 型阴离子交换树脂。
  8. 如权利要求1-4中任意一项所述的浓缩固化放射性废液中核素的方法，其特征在于，所述选择性提取剂各自独立地包含分子筛，优选地包含分子筛NaY、分子筛13X、分子筛ZSM-5、分子筛SAPO-34、β分子筛或其任意组合。
  9. 如前面权利要求中任意一项所述的浓缩固化放射性废液中核素的方法，其包括如下步骤：
    步骤1)预处理：在紫外光下用H 2O 2对所述放射性废液进行催化氧化，然后利用第一选择性提取剂进行提取；
    步骤2)浓缩：在浓液槽中进行至少两级反渗透浓缩，每一级反渗透的透过液依次进入下一级，每一级反渗透的截留液均返回浓液槽；
    步骤3)提取：使用两级或更多级有机离子交换树脂和/或第二选择性提取剂对步骤2)中浓液槽中的液体进行提取，液体依次穿过各级离子交换树脂和/或第二选择性提取剂，最终出水返回浓液槽；
    步骤4)核素固化：使步骤1)获得的第一选择性提取剂和/或步骤3)获得的有机离子交换树脂和/或第二选择性提取剂固化形成固化体；
    其中所述选择性提取剂各自独立地包含无机氧化物载体和核素提取活性组分，所述无机氧化物载体包含二氧化硅、氧化铝、氧化钛或其任意组合，所述核素提取活性组分包含亚铁氰化物和/或锑酸盐。
  10. 如前面权利要求中任意一项所述的浓缩固化放射性废液中核素的方法，其特征在于，当步骤3)中出水的电导率大于或等于步骤2)中浓缩液电导率，或者步骤2)最终透过液电导率高于50μS/cm时，步骤3)中的第一级离子交换树脂和/或选择性提取剂进行步骤4)核素固化，并且任选地，装填新鲜的离子交换树脂和/或选新鲜的择性提取剂作为最后一级离子交换树脂和/或选择性提取剂，其它各级离子交换树脂和/或选择性提取剂依次前移。
  11. 如前面权利要求中任意一项所述的浓缩固化放射性废液中核素的方法，其特征在于，在所述步骤1)预处理步骤前，利用絮凝、活性炭、保安过滤器、纸芯过滤器、自清洗过滤器、超滤或其任意组合对废液进行 处理。
  12. 如权利要求4-11中任意一项所述的浓缩固化放射性废液中核素的方法，其特征在于，步骤5)排出的淡水与进入步骤3)的液体的体积比例控制在1-10:1范围内，优选地在3-10:1范围内。
  13. 一种浓缩固化放射性废液中核素的系统，其包含：
    a)预处理单元，所述预处理单元包含第一选择性提取剂；
    b)浓缩单元，所述浓缩单元包含设有反渗透装置的浓液槽，使得所述反渗透装置的截留液返回所述浓液槽中，并且所述预处理单元的出水口与所述反渗透装置的入口连接；
    c)提取单元，所述提取单元包含有机离子交换床和/或第二选择性提取剂，所述提取单元的进水口与所述浓液槽连接使得所述浓液槽中的液体进入所述提取单元中，所述提取单元的出水口与所述浓液槽连接使得经过所述提取单元的液体返回所述浓液槽中；
    d)核素固化单元，在所述核素固化单元中富含核素的选择性提取剂和/或富含核素的有机离子交换树脂形成固化体。
  14. 如权利要求13所述的浓缩固化放射性废液中核素的系统，其中在所述预处理单元中，所述系统还包含位于所述第一选择性提取剂的上游的氧化装置，所述氧化装置优选地配备有紫外光源或臭氧装置。
  15. 如权利要求13所述的浓缩固化放射性废液中核素的系统，其中所述提取单元包含在所述有机离子交换床和/或第二选择性提取剂之前的活性炭床。
  16. 如权利要求13所述的浓缩固化放射性废液中核素的系统，其中所述系统还包含e)液体净化单元，所述液体净化单元中设有除盐单元，所述液体净化单元的进水口与所述浓缩单元连接，使得经过所述反渗透装置的透过液进入所述液体净化单元，并且所述液体净化单元的浓水出口与所述浓缩单元连接使得从所述除盐单元获得的浓水返回所述浓液槽中。
  17. 如权利要求13-16中任意一项所述的浓缩固化放射性废液中核素的系统，其特征在于，所述选择性提取剂各自独立地包含无机氧化物载体和核素提取活性组分。
  18. 如权利要求17所述的浓缩固化放射性废液中核素的系统，其特征在于，所述无机氧化物载体各自独立地包含二氧化硅、二氧化锰、氧化铝、氧化钛、氧化锆或其任意组合，并且所述核素提取活性组分包含亚铁氰化物、锑酸盐、钛酸盐、氧化锡、钨酸盐或其任意组合。
  19. 如权利要求13-16中任意一项所述的浓缩固化放射性废液中核素的系统，其特征在于，所述有机离子交换树脂包含氢型阳离子交换树脂和氢氧型阴离子交换树脂。
  20. 如权利要求13-16中任意一项所述的浓缩固化放射性废液中核素的系统，其特征在于，所述选择性提取剂各自独立地包含分子筛，优选地包含分子筛NaY、分子筛13X、分子筛ZSM-5、分子筛SAPO-34、P分子筛或其任意组合。
  21. 根据权利要求13-16中任意一项所述的浓缩固化放射性废液中核素的系统，其中所述预处理单元还包含过滤装置，所述过滤装置具有絮凝装置、活性炭、保安过滤器、纸芯过滤器、自清洗过滤器、超滤装置或其任意组合。
  22. 根据权利要求13-16中任意一项所述的浓缩固化放射性废液中核素的系统，其中所述浓缩单元包含设有至少两级反渗透装置的浓液槽，并且每一级反渗透装置的截留液出口均与所述浓液槽连接使得每一级反渗透装置的截留液均返回所述浓液槽中。
PCT/CN2018/114299 2018-01-03 2018-11-07 浓缩固化放射性废液中核素的方法和系统 WO2019134436A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB2009626.9A GB2583276B (en) 2018-01-03 2018-11-07 Method and system for concentrating and solidifying radionuclides in radioactive waste liquid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810006458.6 2018-01-03
CN201810006458.6A CN109994238B (zh) 2018-01-03 2018-01-03 浓缩固化放射性废液中核素的方法和系统

Publications (1)

Publication Number Publication Date
WO2019134436A1 true WO2019134436A1 (zh) 2019-07-11

Family

ID=67128532

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/114299 WO2019134436A1 (zh) 2018-01-03 2018-11-07 浓缩固化放射性废液中核素的方法和系统

Country Status (3)

Country Link
CN (1) CN109994238B (zh)
GB (1) GB2583276B (zh)
WO (1) WO2019134436A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112485273A (zh) * 2020-11-11 2021-03-12 苏州热工研究院有限公司 水体中放射性铁的收集装置以及检测方法
CN115779867A (zh) * 2022-11-22 2023-03-14 兰州大学 一种可选择性富集分离Th(IV)的树脂及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111768885B (zh) * 2020-06-10 2022-07-26 清华大学 放射性废液处理系统及方法
CN111863302A (zh) * 2020-07-27 2020-10-30 上海核工程研究设计院有限公司 一种用于放射性废液深度净化处理装置和使用方法
CN112340917B (zh) * 2020-11-04 2023-12-22 江汉大学 一种放射性废水的处理方法和系统
CN113466002A (zh) * 2021-06-21 2021-10-01 中国原子能科学研究院 模拟放射性废液的配制方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1090490A (ja) * 1996-09-20 1998-04-10 Jgc Corp 放射性廃液の固化処理方法および濃縮混練装置
CN101567227A (zh) * 2009-06-02 2009-10-28 武汉工程大学 核废水的处理方法及装置
CN103177784A (zh) * 2013-03-28 2013-06-26 清华大学 一种处理放射性废水的方法
CN103762004A (zh) * 2014-01-22 2014-04-30 清华大学 一种浓缩放射性废水的方法和系统

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2118945C1 (ru) * 1996-03-12 1998-09-20 Пензин Роман Андреевич Способ комплексной переработки жидких радиоактивных отходов
RU2112289C1 (ru) * 1996-03-12 1998-05-27 Пензин Роман Андреевич Способ переработки жидких радиоактивных отходов
US5972216A (en) * 1997-10-24 1999-10-26 Terra Group, Inc. Portable multi-functional modular water filtration unit
JP2004028903A (ja) * 2002-06-27 2004-01-29 Mitsubishi Heavy Ind Ltd 放射性廃液分離装置、およびそれを備えた放射性イオン交換樹脂の処理システム
DE10255064A1 (de) * 2002-11-25 2004-06-17 Rwe Nukem Gmbh Verfahren zum Behandeln von radioaktivem Abwasser
US20060283787A1 (en) * 2005-06-20 2006-12-21 Pedee Vincent J C Integrated Advanced Simultaneous Oxidation Process (ASOP) to Defeat Chemical, Biological, and Radiological Agents in Aqueous and/or other Fluid Solutions
CN101229949B (zh) * 2007-12-19 2011-09-07 核工业理化工程研究院华核新技术开发公司 移动式放射性废水处理设备
US20140094975A1 (en) * 2012-09-28 2014-04-03 Elo Nielsen Control system for a mobile water filtration unit, and related devices, components, systems and methods
CA3148050A1 (en) * 2014-06-24 2015-12-30 Veolia Nuclear Solutions, Inc. Mobile processing system for hazardous and radioactive isotope removal
CN105617982B (zh) * 2016-02-24 2019-08-06 清华大学 一种去除放射性水中110mAg的无机吸附剂及其制备方法
CN105719718B (zh) * 2016-02-24 2018-01-02 清华大学 一种去除放射性水中胶体态核素110mAg和60Co/58Co的方法
CN105702310B (zh) * 2016-02-24 2018-04-06 清华大学 一种去除放射性水中络合态核素110mAg和60Co/58Co的方法
KR101741232B1 (ko) * 2016-04-08 2017-05-30 한국수력원자력 주식회사 밸브의 개폐조작에 의한 방사성 액체 폐기물 다 공정 처리 유닛

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1090490A (ja) * 1996-09-20 1998-04-10 Jgc Corp 放射性廃液の固化処理方法および濃縮混練装置
CN101567227A (zh) * 2009-06-02 2009-10-28 武汉工程大学 核废水的处理方法及装置
CN103177784A (zh) * 2013-03-28 2013-06-26 清华大学 一种处理放射性废水的方法
CN103762004A (zh) * 2014-01-22 2014-04-30 清华大学 一种浓缩放射性废水的方法和系统

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112485273A (zh) * 2020-11-11 2021-03-12 苏州热工研究院有限公司 水体中放射性铁的收集装置以及检测方法
CN115779867A (zh) * 2022-11-22 2023-03-14 兰州大学 一种可选择性富集分离Th(IV)的树脂及其制备方法

Also Published As

Publication number Publication date
CN109994238A (zh) 2019-07-09
GB2583276B (en) 2023-03-29
GB2583276A (en) 2020-10-21
CN109994238B (zh) 2023-05-26
GB202009626D0 (en) 2020-08-05

Similar Documents

Publication Publication Date Title
WO2019134436A1 (zh) 浓缩固化放射性废液中核素的方法和系统
CN103177784B (zh) 一种处理放射性废水的方法
WO2016187915A1 (zh) 将放射性废水处理至天然本底放射性水平的系统及应用
CN105702310B (zh) 一种去除放射性水中络合态核素110mAg和60Co/58Co的方法
CN110349689B (zh) 核电站放射性废液处理装置
CN105719718B (zh) 一种去除放射性水中胶体态核素110mAg和60Co/58Co的方法
CN104108813A (zh) 炼化污水脱盐一体化处理工艺及装置
RU2297055C1 (ru) Способ переработки кубового остатка жидких радиоактивных отходов
RU2467419C1 (ru) Способ очистки кубовых остатков жидких радиоактивных отходов от радиоактивного кобальта и цезия
CN105321589A (zh) 一种采用全膜法处理放射性废水的方法
WO2018096700A1 (ja) 超純水製造システム及び超純水製造方法
JPH0638953B2 (ja) 高純度水の製造装置
CN110379532B (zh) 放射性废液处理方法及装置
JPH0240220A (ja) 純水製造装置
CN212954669U (zh) 一种多级过滤净水系统及净水器
RU2817393C9 (ru) Способ переработки жидких радиоактивных отходов
RU2817393C1 (ru) Способ переработки жидких радиоактивных отходов
US9133047B2 (en) Decontamination system with insoluble additives
CN109809593B (zh) 适用于不同含盐量低水平放射性废水处理的设备及方法
JP2018086657A (ja) 純水製造装置、超純水製造システム及び純水製造方法
RU2112289C1 (ru) Способ переработки жидких радиоактивных отходов
CN217535693U (zh) 一种一体化纯水处理系统
Zakrzewska-Trznadel et al. Liquid low-level radioactive waste treatment by membrane processes
Vinnitskii et al. Radioactive waste management in PWR technology: some technical solutions for liquid radioactive media processing systems of the “nuclear island”
JP3674368B2 (ja) 純水製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18898890

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 202009626

Country of ref document: GB

Kind code of ref document: A

Free format text: PCT FILING DATE = 20181107

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18898890

Country of ref document: EP

Kind code of ref document: A1