• 专利附录
  • 专利说明
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    • 专利摘要:
    Procedure for solidification of radioactive waste and a solidification product. In the process, the radioactive waste comprising spent intermediate ion exchange resin is mixed into a mixture formed by a hydraulic binder and water, and the mixture obtained is cured into a solidification product containing waste. According to the invention, the hydraulic binder comprises a mixture formed of cement and blast furnace slag and an activator for blast furnace slag and at least a part of the water used for the solidification consists of a boron-containing evaporation-waste solution. The invention also relates to a process for binding the radioactive components of the aqueous evaporation waste. By means of the present solution, the amount of waste can be increased in a package at the same time as the amount of alkaline components to be added can be reduced in the solidification mass recipe. The fact that the surface dose rate does not increase appreciably or not at all, constitutes a considerable advantage.
    公开号:FI20186089A1
    申请号:FI20186089
    申请日:2018-12-16
    公开日:2020-06-17
    发明作者:Kaisa Mäkinen；Ilkka Ropponen；Pasi Kelokaski；Jari Virtanen
    申请人:Fortum Power & Heat Oy；
    IPC主号:
    专利说明:

    The present invention relates to the solidification of radioactive waste.
    In particular, the invention relates to a method according to the preamble of claim 1, wherein the liquid waste is solidified by mixing it with a binder and water to form a mixture to be cured.
    The invention also relates to a solidification product according to the preamble of claim 16 and to a method according to claim 20 for binding the radioactive components of an aqueous evaporative waste.
    Background Intermediate-level liquid waste generated during the operation of a nuclear power plant can be divided into three categories: concentrated evaporative waste from the sewage system, spent ion exchange resins and sewage containing solids. The latter are various precipitates and sludges.
    The resin waste comprises an ion exchange mass which has purified the water of various systems (primary circuit, fuel pools, etc.) and which maintains the chemical balance of the systems. Typically, such waste is generated at a nuclear power plant 5-30 m ”, e.g. about 8-15 m” per year.
    00 The activity of intermediate level waste is usually between 1 MBg / kg and 10 GBg / kg, which is why effective radiation protection arrangements are required for its treatment.
    N © - Concreting is a known method of treating ion exchange resin. In it, the waste is solidified by means of an E 30 binder, in particular a hydraulic binder such as cement, blast furnace slag or mixtures of these 8, and an additive into a hard solidification product (disposal product).
    An example of a known method is the solution disclosed in U.S. Patent No. 9,443,628. According to the publication, the radioactive waste from a nuclear power plant is fed into a lime - containing mixing tank, to which additives are added with stirring. Thereafter, further cement is added to the tank and additional water and mixing is continued until the composition is evenly mixed. The mixture thus obtained is allowed to cure. According to the publication, 100 parts by weight of waste, 170 to 260 parts by weight of cement, 5 to 20 parts by weight of lime, 20 to 60 parts by weight of water and 0.25 to 10 parts by weight of hardener are used for the solidification mixture. In addition, 2 to 20 parts by weight of an additive comprising at least two components selected from the group consisting of sodium hydroxide, lithium carbonate and sodium silicate are added to the mixture. A significant part of the hardener is polycarboxylate. According to the publication, about 40-60% of the volume of the extension package can be solidified as ion exchange resin. The problem with the recipe proposed in U.S. Pat. No. 9,443,628 is that it contains a great variety of additives - in addition to the lithium carbonate and sodium silicate described above, e.g. sodium meta-aluminate and commercial additives that increase the overall cost of the product. A complicated recipe as well as several additions also complicate the operation of the solidification. SUMMARY OF THE INVENTION - The object of the present invention is to eliminate at least some of the problems of the prior art and to provide a completely new solution for solidifying nuclear power plant waste. In particular, it is an object of the invention to provide a method for solidifying radioactive waste. The method solidifies the spent intermediate-activity ion exchange resin, which is mixed with a mixture of a hydraulic binder and water, after which the mixture thus obtained is cured to a solidification product containing waste.
    The invention is based on the idea that at least part of the cement normally used as a hydraulic binder is replaced by blast furnace slag. To such a mixture is added * 30 nuclear power plant radioactive evaporative waste solution. This, in turn, can replace 3 both the part of the water needed for solidification and the alkaline = activator of the blast furnace slag. At the same time, the radioactive part N of the evaporation waste solution is bound to the solidification product.
    Based on the above, a method is thus obtained in which by-products or by-products of other processes, such as blast furnace slag and evaporative waste solution, can replace at least some of the corresponding pure raw materials, while the added components provide effective curing of the concrete and a significant increase in the binding radioactive amount. The product to be produced by the process, “solidification product”, comprises radioactive waste solidified in a concrete mass, wherein the binder of the solidification product comprises a mixture of cement, blast furnace slag and alkali metal carbonate, and the waste comprises more than 50% by weight of the solidification product. At least about 10% by weight of the waste in question is then waste which does not bind to the ion exchange resin. In another application, there is provided a method of bonding the radioactive components of a nuclear power plant's aqueous evaporative waste, the method comprising: - feeding the aqueous evaporative waste to a curable mixture comprising radioactive ion exchange waste and a hydraulic binder. More specifically, the solution according to the invention is mainly characterized by what is set out in the independent claims.
    The invention achieves considerable advantages. With the developed solution, a solidified ion exchange resin is obtained in the waste package by using concentrated evaporative waste from the sewage treatment system of the control area as an additional water for solidification. This increases the amount of waste in the solidification product and © 25 - the result is still a safe and durable solidification product.
    S A The solution can therefore increase the amount of waste in the package, while reducing the amount of alkaline components to be added separately in the solidification mass recipe. = The fact that the surface dose rate does not increase significantly or at all, and the amount of material to be eluted> 30, does not represent a significant advantage. 3 = The recipe used to make the firming product is exceptionally effective; More than 50% of the solidification product is waste, while with other solutions the proportion of waste in the solidification product is typically about 10-20%. If the waste package is solidified - only ion exchange resin, the solidification product contains more than 40% ion exchange resin waste.
    By using evaporative waste as additional water for concrete solidification, the amount of waste in the package can be increased to more than 50%, preferably to more than 55%, up to 58-64%. Another advantage of the solution is that the treatment of evaporative waste is simplified and the amount of separately treated waste is reduced. As a result, e.g. the need for storage of liquid waste is reduced. In the following, a few preferred applications will be examined in more detail by means of a detailed explanation.
    Figure 1 shows a simplified process diagram of a method according to one embodiment, Figure 2 shows a perspective view of the structure of five concrete pieces after immersion in water to support the assessment of water retention, and Figure 3 shows graphically the elution test results of Co-60, Cs-134 and Cs-137 as a function of time, always 365 until the day. Embodiments In the present context, “solidification product” means a solidified body containing radioactive waste and a hydraulic binder, which encloses that waste and which is suitable for the final disposal of that radioactive waste. Typically, the mixture is fed from its upper end into an open shell, such as a metal shell © or a reinforced concrete vessel, where the mixture is allowed to cure to form a solidification product N, after which a concrete lid is cast on the open end of the metal shell. The product is also called = “waste packaging”. E: 30> The waste package is particularly suitable for solidifying intermediate level waste for disposal 3. In the present context, “intermediate level waste” means> waste generated by the operation of a nuclear power plant with a radioactivity of between 1 MBg / kg and 10 GBg / kg. This group includes the above: concentrated evaporative wastes from the sewage system, ion exchange resins used for the separation of radionuclides, and sewage containing solids, including sludges and sludges. Examples of ion exchange resins include e.g. ion exchange resins for use in the control of primary circuit water chemistry, decontamination solutions and, for example, pool water treatment. These resins end up in a liquid waste storage facility and are solidified into a concrete mix. “Evaporative waste solution” is an alkaline solution containing boron compounds, salts and very - small amounts of solids. In one application, the evaporation waste solution is the evaporation residue obtained after the removal of radioactivity-free liquid from the clarified mother liquor, sludge and sludge solution of a nuclear power plant by evaporation. “Hydraulic binder” is a substance, especially a mineral substance, which, due to the addition of water, is able to harden and bind together, for example, solid particles and bodies with which it has been mixed. Particularly in the present context is meant a substance which, on hydration, forms the hydrates of the silicates and aluminates which it contains, which over time harden into a uniform cementitious adhesive.
    - 'Cement' means an inorganic hydraulic binder based on limestone or calcium silicate. Typical examples are Portland and rapid cement. “Blast furnace slag” is a binder obtained from a blast furnace when calcium oxide from limestone binds side metal non-metallic compounds such as silicates, phosphates and sulphide compounds. Blast furnace slag is generally granulated and ground to a fineness of about 100-800 S m '/ kg to give a binder capable of N eo in the presence of an alkali activator. . . .
    e to act as a hydraulic binder.
    © - “Alkali activator” means an alkaline substance such as alkali or earth a = 30 - alkali metal hydroxide, carbonate, bicarbonate or a mixture thereof or other O o. . . . . .
    S an inorganic or organic alkaline substance.
    co N In the first application, the radioactive waste is a mixture of cement and blast furnace slag and a blast furnace slag activator, wherein at least part of the water used for solidification consists of a boron-containing evaporative waste solution.
    Most preferably, the amount of boron-containing evaporative waste solution in the curable composition is at least 10% by weight, especially about 15-50% by weight, of the ion exchange resin waste. In one application, the radioactive waste comprises more than 50% by volume, especially at least 55% by volume, and at least 10% by weight. radioactive waste is waste that does not bind to the ion exchange resin. In one preferred embodiment, the compressed strength of the cured solidification product is - greater than 5 MPa, especially greater than about 10 MPa, preferably about 12-18 MPa. In one application, in the casting of a solidification product, an evaporative waste solution, which is a basic solution containing boron compounds and salts of alkali and alkaline earth metals, is added to the cement and blast furnace slag and any alkali.
    It has a pH of at least 10, in particular at least 11 and preferably at least 11.5. In one application, the cement and blast furnace slag are mixed dry, e.g. with a level mixer, and their mixture is metered as a single unit. Other wastes, - alkali activator and water / evaporation wastes, are dispensed in separate units along a separate line directly into the waste bin where they are mixed. In one application, the substances of the solidifying body are added, i.e. dosed, in stages, e.g. in stages 2-10. This helps to accommodate a large amount of waste - in a disposal container. In addition, phasing ensures the homogeneity of the waste matrix 5 inside the container and avoids the formation of deposits. Homogeneity is quite advantageous in terms of the surface dose rate of the AN waste package and its handling. If the waste matrix A is inhomogeneous, there may be more waste at some point than elsewhere, = which may lead to the surface dose rate of the predetermined container being exceeded. > 30
    O 3 Typically, evaporation waste is the evaporation residue obtained when N radioactivity-free liquid has been removed from the mother liquor = sewage sludge and sludge mother liquor by evaporation.
    The pH of the evaporative waste solution used in one application is about 10-14, especially about 11-13.5. It has a boron content (as H3BO3) of about 1 to 15% by weight of the solution, in particular about 2.5 to 7.5% by weight. In one application, the waste content of the evaporative waste solution is 5-40%, in particular 10-30%, preferably 15-25% by weight of the solution. In one preferred embodiment, the evaporation waste solution used is free of Ni-63 nuclide. - As an example of the composition of a typical evaporative waste solution, the following is given: Table 1. Composition of evaporative waste solution Analysis | | 10-14 | | Concentration Boron (as H3BO3) 50-60 g / kg NPOC 0.1 - 1 vol% 1-2-2 g / l 5-15 g / kg 50-90 g / l 1-2.5 g / l 1 -2.5 g / l 10-100 g / l 0.1-1 g / l <1.5 g / l 5-50 me 50-250 g / kg In one application the evaporation waste acts as an activator for blast furnace slag.
    = Optionally, the blast furnace slag activator further comprises a basic substance, N such as alkali or alkaline earth metal carbonate. Especially at least part of the blast furnace slag
    N a of the alkali or alkaline earth metal carbonate used as activator is added as a separate T chemical, i.e. as a solid powder.
    I E 20 8 In one application, a solidification product is provided comprising radioactive waste, ce solidified in a concrete mass, the binder of which comprises cement, blast furnace slag and | an alkali metal carbonate mixture, wherein the waste comprises more than 50% by weight of the solidification product and wherein at least 10% by weight of the waste is unbound to the ion exchange resin.
    In one application, 100 parts by weight of waste per 100 parts by weight of waste, 10 to 200 parts by weight of cement, 50 to 300 parts by weight of blast furnace slag and 10 to 100 parts by weight of water and 0.1 to 10 parts by weight of alkali activator per blast furnace slag are used for the solidification mixture. .
    As an example of the composition of a typical solidification mixture, the following is given (Table 2): Table 2. Composition of the solidification mixture Ion exchange resin 25-75 100-200 Soda (sodium carbonate) Additional water (tank evaporation solution) Typically, the solidification product is wherein the open end is closed with a concrete lid to form a waste package.
    One application does not use a container that is completely open at its end, but an end with a plate provided with holes for all products to be dispensed into the waste container. Such a perforated plate can prevent, or at least significantly reduce, the splashing of the wet solidification product during mixing.
    Most preferably, the surface dose rate of the waste package formed from the solidification product is - at most 5 mSv / h, typically about 0.05 mSv / h. co a In one application, the present technology is used to bind the radioactive components of an aqueous evaporation waste S, whereby the aqueous evaporation waste is fed to a hardenable E 25 mixture containing radioactive ion exchange waste and a hydraulic binder. The volume of the evaporation waste is about 10-50% of the total liquid volume of the mixture to be cured. >
    O co> The following diagram illustrates the solidification process according to one application.
    The purpose of the solidification process in the solidification plant is to convert radioactive liquid waste, ie evaporation waste, spent ion exchange resins and sludges and sludges, into a final form by solidifying them in a batch process into a concrete matrix.
    Evaporation waste is generated from the sewage treatment system when the solution deposited on the fines and sludges is run to evaporate. With the evaporator, the activity-free condensate is evaporated from the solution, which is discharged into the sea after filtration and check measurements. The remaining concentrated evaporative waste is an alkaline solution containing - boron compounds, salts and very small amounts of solids. Concentrated evaporation waste is temporarily stored in liquid waste storage 1. When one tank is filled, small amounts of solids have precipitated at the bottom of the tank and the solution formed on top is recovered. For example, cesium can be separated from the solution by a selective ion exchange mass. The solution is pumped to the liquid waste storage tank 1. After any separation or purification, the radioactivity of the solution is so low that it can be pumped from the power plant into the sea in a controlled manner in accordance with approved procedures. The column containing the ion exchange mass used for the separation of cesium is disposed of in a concrete disposal vessel.
    In addition to evaporation waste, the power plant generates ion exchange resin waste. Ion exchange resins are used e.g. for the maintenance of primary circuit water chemistry and, for example, in filters for borate water and decontamination solution treatment plants. When the ion exchange resins are saturated, they are not revitalized but are pumped into a liquid waste storage tank and solidified directly into the concrete. g AN The solidification process before the ion exchange resin or evaporative waste is transferred from the liquid A waste storage tank 1 to the solidification plant in mixing tank 2. i - The mixing tanks for tonic exchange resins and evaporative waste are separate tanks into which 3 batches of waste to be solidified are initially transferred. A waste batch means an amount of about 4 m, which = is transferred from a liquid waste storage facility to a solidification plant.
    N The waste is mixed as homogeneously as possible by circulating it in a circuit between the mixing and dosing tanks. Each batch of waste to be solidified is sampled through a sampling cycle for radiochemical analyzes and quality control of the concrete matrix, i.e. the so-called for the preliminary test. Solidification cannot be started from a new batch of waste until the power plant laboratory has determined the nuclide-specific activity of the sample, ie the "waste fingerprint", and calculated the theoretical waste batch rate, which assesses whether the transferred waste meets the waste bin design criteria, including surface batch rate. may not exceed 5 mSv / h.
    The purpose of the preliminary test is to ensure that the selected solidification recipe is functional and that - the concrete chemical properties set for the solidification product are met, ie to ensure that the waste to be treated works as desired in the solidification process and meets the specified requirements.
    Once the batch of waste has been analyzed by the radiochemistry laboratory and the preliminary tests have been carried out, solidification can be started. If a gamma analysis or preliminary test has shown that the dose rate limit for the waste package is exceeded or the waste is not bound, the waste can also be returned to the liquid waste storage facility and a new waste batch taken to the solidification plant.
    - The solidification process begins by moving the waste bin with 12 cranes to the beginning of the line. The waste container is then moved by rails along the rails to the solidification point. The required amount of waste is transferred from the mixing tank 2 to the dosing tank, from where the waste is dispensed into the waste container 12. At the solidification point, the waste is dispensed with soda ash (sodium carbonate or a mixture of sodium carbonate and sodium bicarbonate 4 The metered substances are mixed with the waste container mixer A to form a homogeneous solidification product.
    © I In one application, the ion exchange resin waste is first mixed as a powdered chemical * 30 - to be added with an alkali activator, after which a hydraulic binder and an evaporating waste solution are added in 3 portions to the mixture thus formed.
    ©
    O N In one application, the hydraulic binder is added in 1 to 20 doses, especially 2 to 10 doses. In one application, the evaporation waste solution is added in 1-20 doses, especially in 2-10 doses.
    In one application, the evaporation waste is dispensed at half the volume of the waste container. This can be done, for example, if no other waste is solidified in the waste container. In another application, about 1/10 to 1/5 of the volume of the waste container is dispensed into the vessel. This application is suitable for a situation where other waste is also mixed into the pulp. When dosing and mixing are complete, the waste container is transferred to the transfer trolley for binding. The binding reaction of the solidification product, i.e. the hydration reaction, releases heat. Therefore, the binding is monitored by means of temperature measurements installed on the solidification line. If the temperature on the surface of the waste container does not rise at all or the temperature rises too high, the binding has not taken place as desired. In addition, during mixing and binding, the waste container can be monitored with two cameras. After the waste has set for at least 24 hours, the hardened and cooled waste container is transferred to the deck pouring point 13 by means of a transfer trolley.
    The lid can be cast when no separated water is visible on the surface of the solidification product. The operator prepares the correct amount of lid concrete in the deck level mixer. After the operator has given permission to lower, the cover concrete 7, 8 flows by gravity through the dosing tank 10 onto the waste container and spreads as a lid. The operation and deck casting of the deck concrete mixer can be monitored with a camera. After the lid casting, the finished waste batch is called waste pack 13. The waste pack is transferred to the end of the track and the cover casting is allowed to dry. At the earliest on the day following the deck casting, the waste package is transferred to the monthly warehouse 14. Waste packages are handled by means of a remote-controlled bridge crane from outside the monthly warehouse. In a monthly warehouse, the waste package is at least 28 days, after which it can be transferred to the unloading space on a transport platform and 5 is finally transported to the power plant waste cave 15.
    N © All devices for storing, dosing and feeding powdered substances 2-11 are placed = on the solidification line. The chemical storage, blast furnace slag and cement silo 4-8 * 30 - with auxiliary systems are in normal process space and located outside the controlled area 3 in their own silo space. ©
    O N Powdered substances are transferred with compressed air. The control room of the solidification plant is located in a radiation-free area so that the control room window can be seen in the control area.
    The solidification process is operated from the solidification plant's control room, which minimizes the radiation dose received by the personnel. As stated above, the present method significantly reduces - the storage requirement due to the storage of evaporative waste. This is illustrated by the following example: The maximum target for solidification of a power plant solidification plant is, for example, 200-250 solidifications per year. A medium-sized power plant produces about 40-50 - m per year evaporation waste. The use of evaporation waste as additional water for ion exchange resin solidification as described above, for example in at least 200 solidifications, reduces the amount of evaporation waste stored by -20-25 m ”, which in practice halves the amount of evaporation waste generated annually. - Example On a laboratory scale, a pulp suitable for the production of solidification bodies was prepared. The experiments followed the conditions and proportions shown in Table 3. 00 O OF
    N ©
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    Table 3. Solidification test results Recipe data Alkali activator weight fraction Additional water (evaporation waste) weight fraction 0.35 Pulp input data 0 | Resin temperature [° C] HartsinpH | 006 | Auxiliary water temperature [° C] Auxiliary water pH Laboratory temperature [° C] - Fresh pulp characteristics | Temperature [° C] Density [kg / m] 1733 Properties of hardened concrete Density 1 d [kg / m3] 1710 Compressive strength N / mm] | | 12.92 As can be seen from the table, the use of resin or evaporative waste in the pulp did not substantially - change the pH of the fresh concrete in the undesired, i.e. acidic, direction, but the pulp remained basic. 00> At the end of the mixing, the mass of the experiment was supple and malleable. No water separated on the pulp and the resin granules were evenly distributed in the pulp. Small pieces came off the daily © 10 piece when the mold was removed, so the dry density value z cannot be considered completely reliable. a
    B 2 The temperature of the fresh mass in the experiment was only slightly higher than that of the raw materials = temperature, which predicts a favorable setting time. N 15 The properties of fresh and hardened mass were determined according to the following standards: e SFS-EN 12350-5 Testing of fresh concrete. Part 5: Leviämäe SFS EN 12350-6 Testing of fresh concrete.
    Part 6: Density e SFS-EN 12390-3 Testing hardened concrete.
    Part 3: Compressive strength of test pieces The solidification product must be shaped and mixed after completion.
    The good miscibility of the pulp also ensures the homogeneity of the solidification product in the waste container.
    The spread test determines the flexibility of the solidification product.
    The test mass spread result was quite favorable (185 mm); such a mass is not too flexible, so that part of the active solidification product could spill out of the waste container during mixing, and not too rigid, but very workable.
    With pulp, the difference between wet and dry densities is about 20 kg / m3. This is a fairly good value - it can be concluded that the evaporation of moisture from the concrete is suitably fast.
    The compressive strength is also suitable to meet the compressive strength requirement set by the authority for a 28-day-old solidification product.
    Figure 3 and the associated Table 4 show the criteria for assessing water retention resistance: - Table 4. Criteria for assessing water retention resistance | Small surface cracking B | | Crumbling and small splitting D | The water storage bodies made from the above mass were kept in the groundwater of the power plant waste cave N for nine days.
    Thereafter, their condition was O “A” according to Table 4, i.e. the body was intact (see Figure 3). After the water storage bodies had been kept in water for 35 E 25 days, their condition was “B”, ie there was a slight surface cracking, but this was irrelevant to the functionality of the bodies. 3 = The part must be able to withstand water storage and must not crack, crumble or crack.
    N The solidification product is monitored in water storage for at least 14 days.
    When - the power plant waste cave is closed in due course, it will be filled with groundwater.
    It can be assumed that when the technical barriers to progress break down, at the earliest after 500 years, the groundwater of the cave will come into contact with the solidification product itself. Elution specimens were prepared and sampling intervals were selected according to both ANSI / ANS
    16.1-2003 standard and general concrete standards. Sampling of the elution experiments itself was performed according to the above standard. Three nuclides were considered, from which the total activity of the resin waste mainly consists of Co-60, Cs-134 and Cs-137. The activity from the evaporation waste has also been taken into account in the elution test results. The results are shown in Figure 4.
    As can be seen from the figure, the elution test results have been made up to a piece of 365 days old and the results clearly show a slowing down of the elution rate. The test gives a good estimate of the water resistance of the part. After one year of water storage, no cracks or crumbs were visible in the elution specimen by visual inspection, and it is assumed that no cracks had formed at least significantly, because if cracks had appeared in the body, the elution area would have increased and so did the elution rate. - List of reference numbers
    1. Liquid waste storage tank 2 Mixing tank 3, 9, 10 Dosing tank 00 25 4 Cement storage silo N 5 Blast furnace slag storage silo = 6 Additive tank = 7 Cement storage silo z 8 Water tank 8 30 11 Scale 3 12 Waste tank 2 13 Waste packaging 14 Storage 15 Storage
    权利要求:
    Claims (1)
    [1]
    Claims:
    A method for solidifying radioactive waste, the method comprising: - the radioactive waste comprises a spent intermediate ion exchange resin mixed with a mixture of a hydraulic binder and water, followed by - curing the resulting mixture to a solidifying product containing the waste, characterized in that - the hydraulic binder comprises cement and blast furnace and a mixture of blast furnace slag activator and - at least a portion of the water used for solidification consists of a boron-containing evaporative waste solution.
    Process according to Claim 1, characterized in that the amount of boron-containing evaporative waste solution in the curable mixture is at least 10% by weight, in particular about 15 to 50% by weight, of the amount of ion exchange resin waste.
    Process according to Claim 1 or 2, characterized in that the proportion of radioactive waste in the solidification product is more than 50% by volume, in particular at least 55% by volume, and at least 10% by weight of the radioactive waste is non-ion exchange resin-bound waste.
    Method according to one of the preceding claims, characterized in that the compressed strength of the cured solidification product is greater than 5 MPa, in particular greater than about 10 MPa, preferably about 12 to 18 MPa. Process according to one of the preceding claims, characterized in that the O evaporation waste solution is a basic solution containing boron compounds and salts of alkali and alkaline earth metals. a 2 30 3 6. A method according to any one of the preceding claims, characterized in that = the pH of the evaporative waste solution is at least 11, in particular at least 12.5 and preferably at least
    OF
    13.
    Method according to one of the preceding claims, characterized in that the evaporation residue is an evaporation residue obtained after the removal of radioactivity-free liquid from the mother liquor sludge solution and sludge solution by evaporation.
    Method according to one of the preceding claims, characterized in that the evaporation waste acts as an activator for the blast furnace slag.
    Process according to one of the preceding claims, characterized in that the blast furnace slag activator comprises an alkali or alkaline earth metal carbonate.
    Process according to Claim 9, characterized in that at least part of the alkali or alkaline earth metal carbonate used as blast furnace slag activator is added as a separate chemical to the cement and blast furnace slag.
    Method according to one of the preceding claims, characterized in that the solidification mixture contains 100 parts by weight of waste per 10 to 200 parts by weight of cement, 50 to 300 parts by weight of blast furnace slag and 10 to 100 parts by weight of water and 0.1 to 10 parts by weight. -partizes an alkali activator for blast furnace slag.
    Method according to one of the preceding claims, characterized in that the solidification mixture contains cement and blast furnace slag in a weight ratio of 1: 0.5 to 1:10, in particular 1: 1 to 1: 5, and preferably the total amount of cement and blast furnace slag is 50 to 500 parts by weight. , especially 100 to 300 parts by weight, per 100 parts by weight of ion exchange resin.
    Process according to one of the preceding claims, characterized in that the N-ion exchange resin waste is first mixed with O alkali activator to be added as a powdered chemical, after which a hydraulic binder and> 30 evaporative waste solution are added portionwise to the mixture thus formed. method according to Claim 13, characterized in that the N hydraulic binder is added in 1 to 20 portions, in particular in 2 to 10 portions, and the evaporating waste solution is added in 1 to 20 portions, in particular in 2 to 10 portions.
    Process according to one of the preceding claims, characterized in that the evaporation waste solution has a pH of about 10 to 14, in particular about 11 to 13.5, and a boron content (as H 3 BO 3) of about 1 to 15% by weight, in particular about 2.5 to 7.5% by weight.
    A solidification product comprising radioactive waste solidified in a concrete mass, the binder comprising a mixture of cement, blast furnace slag and alkali metal carbonate, wherein the waste comprises more than 50% by weight of the solidification product and at least 10% by weight of the waste is non-ion exchange resin.
    Solidification product according to Claim 16, characterized in that the proportion of waste in the solidification product is more than 55% by volume, preferably at least 58% by volume.
    A solidification product according to claim 16 or 17, characterized in that the solidification product is closed at one end inside at least a partially open shell, - wherein the open end is closed with a concrete lid to form a waste package.
    Solidification product according to one of Claims 16 to 18, characterized in that the surface dose rate of the waste package formed therefrom is at most 5 mSv / h.
    A method for binding the radioactive components of an aqueous evaporative waste, characterized in that the aqueous evaporative waste is fed to a curable mixture containing radioactive ion exchange waste and a hydraulic binder.
    A method according to claim 20, characterized in that the aqueous - evaporation waste is fed to a curable mixture containing a binder containing blast furnace slag, wherein the evaporation waste is used as an activator of the blast furnace slag.
    A method according to claim 20 or 21, characterized in that the volume of the evaporation = waste is about 10-50% of the total liquid volume of the mixture to be cured. > 30 S. oo. Process according to one of Claims 20 to 22, characterized in that = the evaporative waste is fed in the form of an evaporative waste solution having a pH of N of about 10 to 14, in particular about 11 to 13.5, and having a boron content (H3BO3: na) about 1-15% by weight of the solution, especially about 2.5-7.5% by weight.
    Process according to Claim 23, characterized in that an evaporative waste solution having a waste content of 5 to 40%, in particular 10 to 30%, preferably 15 to 25%, based on the weight of the solution, is fed.
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    同族专利:
    公开号 | 公开日
    FI129112B|2021-07-15|
    EP3895185A1|2021-10-20|
    WO2020128158A1|2020-06-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    SE412658B|1977-07-05|1980-03-10|Asea Atom Ab|SET IN CEMENT BEDDING ACID OR BORATE-RADIOACTIVE WASTE|
    FR2440778B1|1978-11-09|1987-08-21|Macedo Pedro|FIXING BY ION EXCHANGE OF TOXIC MATERIALS IN A GLASS MATRIX|
    FR2901270B1|2006-05-18|2008-08-22|Commissariat Energie Atomique|CEMENT-BASED COMPOSITION FOR COATING AQUEOUS BORON-CONTAINING SOLUTION, COATING PROCESS AND CEMENTITIOUS GROUT COMPOSITION|
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    EP19848927.0A| EP3895185A1|2018-12-16|2019-12-16|Method for treatment and solidification of liquid waste|
    PCT/FI2019/050897| WO2020128158A1|2018-12-16|2019-12-16|Method for treatment and solidification of liquid waste|
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