CN113979642A

CN113979642A - Glass solidified body of non-flammable radioactive waste and cooperative glass solidification method

Info

Publication number: CN113979642A
Application number: CN202111369480.5A
Authority: CN
Inventors: 李丽丽; 林鹏; 李坤锋; 文炎立; 刘春雨; 杜颖哲; 刘晓伟; 周江; 刘夏杰; 李利
Original assignee: China General Nuclear Power Corp; China Nuclear Power Technology Research Institute Co Ltd; CGN Power Co Ltd
Current assignee: China General Nuclear Power Corp; China Nuclear Power Technology Research Institute Co Ltd; CGN Power Co Ltd
Priority date: 2021-11-15
Filing date: 2021-11-15
Publication date: 2022-01-28

Abstract

The invention relates to a glass solidified body of non-flammable radioactive waste and a cooperative glass solidification method. The raw materials of the glass solidified body are derived from incombustible wastes such as radioactive glass fiber, soil, concrete and the like, and the glass fiber, the soil and the concrete can be combined in any binary or ternary manner according to actual conditions. The glass matrix has simple composition and small dosage. The glass solidified body obtained by synergistic glass solidification has good chemical stability, the leaching resistance, the compressive strength, the shock resistance and other properties meet the geological disposal requirements, the waste content is high, the volume reduction effect is obvious, and the subsequent landfill cost can be reduced.

Description

Glass solidified body of non-flammable radioactive waste and cooperative glass solidification method

Technical Field

The invention belongs to the technical field of radioactive waste treatment, and particularly relates to a glass solidified body of non-flammable radioactive solid waste and a synergistic glass solidification method.

Background

With the development of nuclear energy technology and the problem of nuclear pollution, the treatment of radioactive waste is receiving more and more attention from people. At present, a cement solidification method is mainly adopted in a nuclear power plant to treat solid waste, and a solidified body prepared by the method has high leaching rate, high capacity-increasing ratio and high subsequent treatment cost. Compared with the prior art, the glass solidified body has better chemical stability, small volume-increasing ratio and high waste containment rate, and is an effective alternative way for treating radioactive solid waste.

CN112382429A discloses a method for curing medium and low-level glass fiber and combustible solid nuclear waste incineration ash through cooperating glass, and concretely provides a method for curing glass by using medium and low-level glassThe glass fiber, cotton cloth, plastic, rubber, absorbent paper and other inflammable solid waste incineration ash slag are cooperated with glass curing treatment, and the glass additive includes: CaO, Li₂O、Na₂O、B₂O₃Is applicable only to combustible waste incineration ash. CN104318971A discloses a glass matrix composition for medium and low level radioactive glass fiber, which is melted with radioactive glass fiber waste to form a solidified body, and the glass additives used in the composition include: SiO 2₂、B₂O₃、Na₂O、CaO、Li₂O、Al₂O₃、Ti₂O, this method is also applicable to radioactive glass fiber waste, but the inventors believe that this combination is a waste of resources, not considering that glass fibers have a self-glass forming property, and are only disposed of as waste.

In view of this, there is a need for further development of a glass-solidified body of non-combustible radioactive waste and a synergistic glass-solidifying method.

Disclosure of Invention

The object of the present invention consists in providing a glass-solidified body of non-combustible radioactive waste and a corresponding synergic glass-solidification process.

The invention provides a glass solidified body of non-flammable radioactive waste, which comprises 5-35 wt% of component A and 65-95 wt% of component B:

and (2) component A: a glass matrix composition comprising B₂O₃、Na₂O, CaO;

and (B) component: simulating non-combustible radioactive waste or non-combustible radioactive waste; wherein the simulated non-combustible radioactive waste contains simulated radionuclides and non-combustible waste; the non-combustible radioactive waste contains radionuclides and non-combustible waste;

wherein the mimic radionuclide, the radionuclide each independently selected from Co₂O₃、SrO、Cs₂At least one of O(ii) a The non-combustible waste is selected from at least two of glass fiber, soil and concrete.

In some embodiments of the invention, the glass-cured body comprises: the total mass percentage of the component A and the component B in the glass solidified body is 100 wt%.

In some embodiments of the invention, the glass-cured body comprises: the glass matrix composition consists of a material selected from B₂O₃、Na₂O, CaO, any two or three glass additives; and/or the presence of a catalyst in the reaction mixture,

in the glass-cured body, B₂O₃0 to 15 wt% of Na₂The mass percentage of O is 0-15 wt%, and the mass percentage of CaO is 0-20 wt%.

In some embodiments of the invention, the glass-cured body comprises: the glass matrix composition is free of Li; and/or, the glass matrix composition is SiO-free₂。

In some embodiments of the invention, the glass-cured body comprises: co₂O₃0 to 1 wt% of SrO, and 0 to 1 wt% of Cs₂The mass ratio of O is 0-1 wt%.

In some embodiments of the present invention, the glass-solidified body is a glass-solidified body in which the non-combustible radioactive waste is selected from any one of the following cases:

the first situation is as follows: the non-combustible waste is a binary combination of soil and concrete, and the content of a glass additive contained in the glass matrix composition in the glass solidified body is 0-5 wt% of Na₂O、5wt％～15wt％B₂O₃And 0-5 wt% CaO;

case two: the non-combustible waste is a binary combination of glass fiber and concrete, and the glass matrix composition comprises a glass additive with the content of 5-15 wt% of Na in the glass solidified body₂O、0～5wt％B₂O₃And 0-5 wt% CaO;

case three: the incombustible waste is glass fiber and soil IIA glass additive contained in the glass matrix composition and having a Na content of 5 to 15 wt% in the glass-solidified body₂O、5wt％～15wt％B₂O₃And 5 to 20 weight percent CaO;

case four: the non-combustible waste is a ternary combination of glass fiber, soil and concrete, and the glass matrix composition comprises a glass additive with the content of 5-15 wt% of Na in the glass solidified body₂O、0～5wt％B₂O₃And 0-5 wt% CaO.

the first situation is as follows: the non-combustible waste is a binary combination of soil and concrete, wherein the soil: the mass ratio of the concrete is (1:4) - (4:1), and the content of the glass additive contained in the glass matrix composition in the glass solidified body is 0-5 wt% of Na₂O、5wt％～15wt％B₂O₃And 0-5 wt% CaO;

case two: the non-combustible waste is a binary combination of glass fiber and concrete, wherein the glass fiber: the mass ratio of the concrete is (1:4) - (4:1), and the content of the glass additive contained in the glass matrix composition in the glass solidified body is 5 wt% -15 wt% of Na₂O、0～5wt％B₂O₃And 0-5 wt% CaO;

case three: the non-combustible waste is a binary combination of glass fiber and soil, wherein the glass fiber: the mass ratio of the soil is (1:4) - (4:1), and the content of the glass additive contained in the glass matrix composition in the glass solidified body is 5 wt% -15 wt% of Na₂O、5wt％～15wt％B₂O₃And 5 to 20 weight percent CaO;

case four: the non-combustible waste is the ternary combination of glass fiber, soil and concrete, and the glass fiber: soil: the mass ratio of the concrete is (1-4): (1-4): (1-4), and the glass additive contained in the glass base composition is 5-15 wt% Na in the glass cured body₂O、0～5wt％B₂O₃And 0-5 wt% CaO.

A second aspect of the invention provides a method for the synergistic vitrification of non-combustible radioactive waste, comprising the steps of:

mixing the glass matrix composition with the simulated non-combustible radioactive waste or mixing the glass matrix composition with the non-combustible radioactive waste to prepare a mixture to be melted;

wherein the mass percentage of the glass matrix composition in the mixture to be melted is 5 wt% -35 wt%, and the glass matrix composition comprises B₂O₃、Na₂O, CaO; the mass percentage of the simulated non-combustible radioactive waste or the non-combustible radioactive waste in the mixture to be melted is 65 wt% -95 wt% respectively and independently;

melting the mixture to be melted, and preserving heat for the first time to prepare a glass melt;

and casting and molding the glass melt, preserving heat for the second time, and annealing to prepare a glass solidified body.

In some embodiments of the invention, the method for the synergistic vitrification of non-combustible radioactive waste comprises: further comprising the step of preparing said simulated non-combustible radioactive waste by:

providing non-combustible waste and a simulated radionuclide, wherein the non-combustible waste is selected from at least two of glass fiber, soil and concrete, and mixing the non-combustible waste with the simulated radionuclide to prepare the simulated non-combustible radioactive waste.

In some embodiments of the invention, the method for the synergistic vitrification of non-combustible radioactive waste comprises: further comprising preparing the glass matrix composition and/or preparing the non-combustible radioactive waste;

in the glass matrix composition, B₂O₃With B₂O₃Or H₃BO₃Form introduction, and/or, Na₂O is Na₂CO₃The method is introduced in a form of,and/or, CaO as CaCO₃Introducing the form;

introducing Co into the mixture to be melted by simulating non-combustible radioactive waste or non-combustible radioactive waste₂O₃、SrO、Cs₂At least one of O; wherein, Co₂O₃With Co₂O₃In the form of SrO and/or SrCl₂Or SrCO₃Is added in the form of, and/or, Cs₂O as Cs₂CO₃Or CsCl.

In some embodiments of the invention, the method for the synergistic vitrification of non-combustible radioactive waste comprises: the simulated non-combustible radioactive waste contains simulated radionuclides; the non-combustible radioactive waste contains radionuclides.

In some embodiments of the invention, the method for the synergistic vitrification of non-combustible radioactive waste comprises: the non-combustible waste comprises the concrete and the average particle size of the concrete does not exceed 2mm and/or the maximum dimension of the concrete does not exceed 2 mm.

In some embodiments of the invention, the method for the synergistic vitrification of non-combustible radioactive waste comprises:

the temperature T1 for the melting is 850-1300 ℃; and/or the presence of a catalyst in the reaction mixture,

the temperature T2 for the first heat preservation is 850-1300 ℃; and/or the presence of a catalyst in the reaction mixture,

the temperature T3 for casting molding is 300-1000 ℃; and/or the presence of a catalyst in the reaction mixture,

the temperature T4 for the second heat preservation is 300-1000 ℃; and/or the presence of a catalyst in the reaction mixture,

the heat preservation time of the first heat preservation is 0.5 h-5 h; and/or the presence of a catalyst in the reaction mixture,

the heat preservation time of the second heat preservation is 0.5 h-3 h; and/or the presence of a catalyst in the reaction mixture,

the annealing is in the form of furnace cooling to room temperature.

The invention provides a method for treating non-flammable radioactive waste by synergistic glass solidification and a glass solidified body for the first time. The method can avoid the pretreatment steps such as chemical decontamination and the like required by the conventional treatment method and the secondary pollution possibly caused by the pretreatment steps.

The domestic glass curing technology can be practically applied only in the field of high-level waste treatment, and has no case of engineering application in the field of medium-low level waste treatment. In particular, the incombustible radioactive wastes such as soil and concrete are mainly generated in the process of decommissioning of nuclear facilities, and because the construction of the nuclear facilities is relatively late, no published article for curing concrete glass exists, and no published article for co-processing soil and other wastes exists. The invention fully considers that the glass fiber, the soil and the concrete contain a large amount of SiO₂、K₂O、Al₂O₃And the glass matrix composition components and proportion of the BaO and other common glass matrix composition components are close to those of a common base glass system under the condition of mixing a plurality of wastes, only a small amount of glass additive is needed to be added to improve the performance of a glass solidified body, and the addition amount of the glass matrix composition is reduced to the maximum extent, so that the waste containment rate is obviously improved. Through the glass fiber, soil, concrete and other non-combustible waste cooperative glass curing treatment, different waste combination cooperative glass curing treatment can be realized according to the actual types and the number of different non-combustible waste, the radioactive glass fiber, the soil and the concrete to be treated are combined randomly and dually to prepare a cured body, the treatment is not limited to the treatment of one waste in the glass fiber, the soil and the concrete, the waste treatment cost is reduced to the maximum degree, and the concepts of treating waste with waste and minimizing waste are realized.

The glass matrix composition of the glass solidified body of the non-flammable radioactive waste provided by the invention has the advantages that the glass additive is few in types, simple in components, easy to obtain raw materials, low in price and small in addition amount, and the treatment cost can be greatly reduced; preferably, expensive Li may not be required, such as may only contain B₂O₃、Na₂O, CaO in any combination.

The solidified body of the non-flammable radioactive waste provided by the invention has the advantages that the chemical stability, the compressive strength, the impact resistance and other properties meet the geological disposal requirements, the waste content is high (up to 95 wt%), the volume reduction effect is obvious, and the waste disposal site requirement and the disposal cost can be greatly reduced.

Compared with a cement solidified body, the glass solidified body has more excellent chemical stability, can reduce or block the outflow of radioactive substances to the maximum extent, and has higher disposal safety.

The method for treating the non-flammable radioactive waste by cooperating with the glass solidification can utilize B₂O₃、Na₂O, CaO (may not contain Li with high price), realizes the solidification treatment of random binary incombustible wastes such as glass fiber, soil, concrete and the like and glass, and furthest practices the environmental protection idea of 'treating waste with waste'; the glass solidified body provided by the method has the advantages of good chemical stability, low leaching rate, high volume reduction ratio and low treatment cost.

Drawings

FIG. 1 is a real comparison of glass-cured bodies of different compositions, wherein A is a glass-cured body prepared in comparative example 1 and containing no glass additive and waste source of glass fiber and concrete (mass ratio of glass fiber to concrete 1:1), B is a glass-cured body prepared in comparative example 2 and containing no glass additive and waste source of glass fiber and concrete (mass ratio of glass fiber to concrete 75:25), and C is a glass-cured body prepared in example 2 and containing glass additive and waste source of glass fiber and concrete (mass ratio of glass fiber to concrete: glass additive 70:25: 5);

FIG. 2 is an XRD diffraction pattern of a glass-cured body prepared in example 2;

FIG. 3 is a real comparison of glass-cured bodies of different compositions, wherein A is a glass-cured body prepared in comparative example 3, which does not contain a glass additive and has a waste source of concrete and soil (mass ratio of concrete to soil 1:1), B is a glass-cured body prepared in comparative example 4, which does not contain a glass additive and has a waste source of concrete and soil (mass ratio of concrete to soil 50:40), and C is a glass-cured body prepared in example 3, which contains a glass additive and has a waste source of concrete and soil (mass ratio of concrete to soil to glass additive 50:40: 10);

FIG. 4 is an XRD diffraction pattern of a glass-cured body prepared in example 3;

FIG. 5 is a real comparison of glass-set bodies of different compositions, wherein A is a glass-set body prepared in comparative example 5, which does not contain glass additives and has glass fibers, concrete and soil as waste sources (mass ratio of glass fibers: concrete: soil 1:1:1), B is a glass-set body prepared in example 4, which contains glass additives and has glass fibers, concrete and soil as waste sources (mass ratio of glass fibers: concrete: soil: glass additives 30:30: 10);

FIG. 6 is an XRD diffraction pattern of the cured glass prepared in example 4.

Detailed Description

The invention is further illustrated below with reference to the figures, embodiments and examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the teachings of the present invention, and such equivalents also fall within the scope of the invention as defined by the appended claims.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments and examples only and is not intended to be limiting of the invention.

Term(s) for

Unless otherwise stated or contradicted, terms or phrases used herein have the following meanings:

the term "and/or", "and/or" as used herein is intended to be inclusive of any one of the two or more items listed in association, and also to include any and all combinations of the items listed in association, including any two or more of the items listed in association, any more of the items listed in association, or all combinations of the items listed in association. It should be noted that when at least three items are connected by at least two conjunctive combinations selected from "and/or", "or/and", "and/or", it should be understood that, in the present application, the technical solutions definitely include the technical solutions all connected by "logic and" and also the technical solutions all connected by "logic or". For example, "A and/or B" includes A, B and A + B. For example, the embodiments of "a, and/or, B, and/or, C, and/or, D" include any of A, B, C, D (i.e., all embodiments using "logical or" connection "), any and all combinations of A, B, C, D (i.e., any two or any three of A, B, C, D), and four combinations of A, B, C, D (i.e., all embodiments using" logical and "connection).

Herein, "preferred" merely describes a more effective embodiment or example, and it should be understood that the scope of the present invention is not limited thereto.

In the present invention, the terms "first", "second", etc. in the terms "first", "second", "first incubation", "second incubation", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor is it to be construed as implicitly indicating the importance or quantity of the technical feature indicated. Also, "first," "second," etc. are used for non-exhaustive enumeration of description purposes only and should not be construed as constituting a closed limitation to the number.

In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.

The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a variation within a certain temperature range. It will be appreciated that the described thermostatic process allows the temperature to fluctuate within the accuracy of the instrument control. For example, fluctuations in the range of, for example,. + -. 5 ℃,. + -. 10 ℃,. + -. 15 ℃,. + -. 20 ℃,. + -. 25 ℃ are allowed.

The percentage contents referred to in the present invention refer to volume% for a gas-gas mixture, weight% for a solid-solid phase mixture, volume% (v/v) for a liquid-liquid phase mixture, and weight% or solid-liquid% (w/v) for a solid-liquid mixture, unless otherwise specified.

In the present invention,% (w/w) and wt% each represent a weight percentage.

In the present invention, where a range of values (i.e., a numerical range) is recited, unless otherwise specified, alternative distributions of values within the range are considered to be continuous, and include both the numerical endpoints of the range (i.e., the minimum and maximum values), and each numerical value between the numerical endpoints. Unless otherwise specified, when a numerical range refers to integers only within the numerical range, both endpoints of the numerical range are inclusive of the integers and each integer between the endpoints is inclusive of the integer. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.

In the present invention, the numerical ranges of the mass ratio, for example, "(1: 4) - (4: 1)" and (0.25-4): 1, have the same meaning. For example, the mass ratio of the glass fiber to the concrete is (1:4) to (4:1), and the numerical value indicates that the mass of the glass fiber is 0.25 to 4 times that of the concrete.

In the present invention, the size, particle diameter and diameter are not particularly limited, but generally mean values.

The first aspect of the present invention provides a glass-solidified body of non-combustible radioactive waste, which comprises 5 to 35% by mass of component a and 65 to 95% by mass of component B:

wherein the mimic radionuclide, the radionuclide each independently selected from Co₂O₃、SrO、Cs₂At least one of O; the non-combustible waste is selected from at least two of glass fiber, soil and concrete.

The glass solidified body of the non-flammable radioactive waste provided by the first aspect of the invention has the advantages of high waste containing rate, small consumption of the required glass matrix, simple composition of the glass matrix and low price; according to the actual situation, the incombustible radioactive glass fiber, the concrete and the soil can be combined in any binary or ternary way; the glass forming property of the glass fiber waste can be fully utilized, and the component characteristics of concrete or/and soil can be utilized, so that the using amount of the glass matrix composition is greatly reduced, and the waste containing rate is remarkably improved; the glass solidified body has strong chemical stability, meets the treatment standard of the radioactive waste solidified body, has obvious volume reduction effect and low subsequent treatment cost.

In some embodiments, the total mass percentage of component a and component B in the glass-solidified body is 100%.

In some embodiments, the component B comprises the following components: component B1: the mimic radionuclide or the radionuclide; and component B2: the non-combustible waste.

In some embodiments, the mass percentage of component a is 5 wt% to 35 wt%, and the mass percentage of component B is 65 wt% to 95 wt%.

In some embodiments, the mass percentage of component a is 5 wt% to 35 wt%, the mass percentage of component B is 65 wt% to 95 wt%, and the total content is 100%.

In some specific embodiments, the mass percentage of component a to component B is 5 wt% and 95 wt%, 10 wt% and 90 wt%, 15 wt% and 85 wt%, 20 wt% and 80 wt%, 25 wt% and 75 wt%, 30 wt% and 70 wt%, 35 wt% and 65 wt%.

In some embodiments, the glass matrix composition comprises B₂O₃、Na₂O, CaO toAnd at least one glass additive which is an auxiliary agent required for glass solidification of the non-flammable radioactive waste so as to form a glass solidified body meeting the disposal requirements from the solid waste.

Conventional glass matrix compositions for glass curing treatments generally require Al in addition to₂O₃、Ti₂O、Li₂O、K₂O、B₂O₃、Na₂O, CaO, etc., not only are the components complex, but also the increase of the waste containment rate is limited. According to the invention, the characteristics of incombustible radioactive glass fiber, concrete and soil can be fully utilized, and the reduction of the dosage of the glass matrix composition and the reduction of the types of glass additives can be realized by using waste to treat waste.

The reduction in the amount of glass additive may result in a significant increase in the waste holding rate, which may be up to 95% in some embodiments. In some embodiments, the glass matrix composition comprises a glass additive in an amount of 5 wt% to 35 wt% by weight of the glass-solidified body (waste containment rate may be 65 wt% to 95 wt%, respectively). Preferred examples include, but are not limited to, 5 wt% to 10 wt%, 5 wt% to 20 wt%, 10 wt% to 20 wt%, 15 wt% to 35 wt%, 15 wt% to 25 wt%. Specific examples include, but are not limited to: 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%.

The reduction of the types of the glass additives can reduce the types of raw materials, simplify the operation and reduce the cost. B preferably used in the present invention₂O₃、Na₂O, CaO the raw material is easy to obtain and cheap, the addition amount is small, and the treatment cost can be greatly reduced. In some embodiments, expensive Li may not be required, thereby further reducing costs. In some embodiments, the glass matrix composition is free of SiO₂. In some preferred embodiments, the glass matrix composition consists of a material selected from B₂O₃、Na₂O, CaO or any two or three of the above glass additives.

When the kind of the additive is more than one, the content ratio of the different kinds of additives is not particularly limited.

In some embodiments, the glass-solidified body is a glass-solidified body in which B is a glass-solidified body₂O₃0 to 15 wt% of Na₂The mass percentage of O is 0-15 wt%, and the mass percentage of CaO is 0-20 wt%; further preferably, the total content is 5 wt% to 35 wt%.

In a specific embodiment of the present invention, in the glass-solidified body, B₂O₃Is 0 wt% of Na₂The mass percentage of O is 5 wt%, the mass percentage of CaO is 0 wt%, and the total content is 5 wt%.

In one embodiment of the present invention, in the glass-solidified body, B₂O₃Is 10 wt% of Na₂The mass percentage of O is 0 wt%, the mass percentage of CaO is 0 wt%, and the total content is 10 wt%.

In one embodiment of the present invention, in the glass-solidified body, B₂O₃Is 0 wt% of Na₂The mass percentage of O is 10 wt%, the mass percentage of CaO is 0 wt%, and the total content is 10 wt%.

The simulated non-combustible radioactive waste consists of non-combustible radioactive waste containing simulated radionuclides.

In some embodiments, the mimic radionuclide may be selected from, including but not limited to, Co, Sr, Cs.

In some embodiments, the mimic radionuclide may be selected from, including but not limited to, Co₂O₃、SrO、Cs₂O。

In some embodiments, the simulated non-combustible radioactive waste is Co₂O₃0 to 1 wt% of SrO, and 0 to 1 wt% of Cs₂The mass ratio of O is 0-1 wt%.

In some embodiments of the invention, Co₂O₃Is 0.2 wt%, SrO is 0.2 wt%, and Cs is₂The mass ratio of O is 0.2 wt%.

The non-combustible waste is the matrix of nuclear waste to be treated, preferablyAt least two of glass fiber, soil and concrete. The invention carries out synergistic glass curing treatment on soil and concrete for the first time, is not limited to the treatment of glass fiber, and can also treat wastes with wastes and provide SiO instead₂And the like, thereby reducing the types and the use amount of the glass additives in the glass matrix composition and reducing the waste treatment cost to the maximum extent.

The non-flammable radioactive waste can be any binary combination or ternary combination among non-flammable radioactive glass fiber, concrete and soil. That is, the non-combustible waste may be any binary combination or ternary combination between glass fiber, concrete, and soil. When the composition is a binary composition or a ternary composition, the content ratio of the components to each other is not particularly limited.

Examples of the aforementioned binary combination or ternary combination include, but are not limited to, the following schemes.

In some embodiments, the glass-solidified body of non-combustible radioactive waste is a binary combination of soil and concrete. Preferably, the ratio of soil: the mass ratio of the concrete is (1:4) - (4: 1).

In some embodiments, the glass-solidified body of non-combustible radioactive waste is a binary combination of glass fiber and concrete. Preferably, the glass fiber: the mass ratio of the concrete is (1:4) - (4: 1).

In some embodiments, the glass-solidified body of non-combustible radioactive waste is a binary combination of glass fiber and soil. Preferably, the glass fiber: the mass ratio of the soil is (1:4) - (4: 1).

In some embodiments, the glass-solidified body of non-combustible radioactive waste is a ternary combination of glass fiber, soil, and concrete. Preferably, the glass fiber: soil: the mass ratio of the concrete is (1-4) to (1-4).

In some embodiments, the glass solidification body of the non-flammable radioactive waste is a binary combination of soil and concrete, and the glass matrix composition contains 0-5 wt% of Na₂O、5wt％～15wt％B₂O₃And 0-5 wt% CaO. Preferably, the ratio of soil: the mass ratio of the concrete is (1:4) - (4: 1).

In some embodiments, the glass-solidified body of non-combustible radioactive waste is a binary combination of glass fiber and concrete, and the glass matrix composition contains 5 wt% to 15 wt% of Na₂O、0～5wt％B₂O₃And 0-5 wt% CaO. Preferably, the glass fiber: the mass ratio of the concrete is (1:4) - (4: 1).

In some embodiments, the glass solidification body of non-combustible radioactive waste is a binary combination of glass fiber and soil, and the glass matrix composition contains 5 wt% to 15 wt% of Na₂O、5wt％～15wt％B₂O₃And 5 to 20 weight percent CaO. Preferably, the glass fiber: the mass ratio of the soil is (1:4) - (4: 1).

In the glass-solidified body of non-combustible radioactive waste of some embodiments, the non-combustible waste is a ternary combination of glass fiber, soil, concrete, and the glass matrix composition contains 5 wt% to 15 wt% of Na₂O、0～5wt％B₂O₃And 0-5 wt% CaO. Preferably, the glass fiber: soil: the mass ratio of the concrete is (1-4) to (1-4).

In a particular embodiment, in the vitreous solidification of non-combustible radioactive waste, the non-combustible waste is a binary combination of soil, concrete, soil: the mass ratio of the concrete is 50:40, and the component of the glass matrix composition is Na₂O, the mass percentage is 10 wt%. The waste containment rate was 90%.

In a particular embodiment, in the glass solidified body of non-combustible radioactive waste, the non-combustible waste is a binary combination of glass fiber, concrete, glass fiber: the mass ratio of the concrete is 70:25, and the glass matrix composition component is B₂O₃The mass ratio is 5 wt%. The waste containment rate was 95%.

In a specific embodiment, in the glass solidified body of the non-combustible radioactive waste, the non-combustible waste is glass fiberThe ternary combination of soil and concrete, glass fiber: soil: the mass ratio of the concrete is 30:30:30, and the glass matrix composition component is B₂O₃The mass ratio is 10 wt%. The waste containment rate was 90%.

s200 (ingredients): mixing the glass matrix composition with simulated non-combustible radioactive waste, or mixing the glass matrix composition with non-combustible radioactive waste to prepare a mixture to be melted;

s400 (glass melting): melting the mixture to be melted (at the temperature of T1), and carrying out primary heat preservation (at the temperature of T2) to prepare a glass melt;

s500 (glass forming and glass annealing): and (3) carrying out casting molding (at the temperature of T3) on the glass melt, carrying out secondary heat preservation (at the temperature of T4), and annealing to prepare the glass solidified body of the first aspect.

The cooperative glass curing method can realize high volume reduction ratio (for example, the volume reduction ratio can be up to 10), can remarkably reduce the volume of incombustible wastes such as glass fiber, soil, concrete and the like, and can greatly reduce the demand of waste disposal sites and the disposal cost; compared with the traditional curing treatment means such as cement curing and the like, the obtained glass cured product has more excellent chemical stability, can reduce or block the outflow of radioactive substances to the maximum extent, and has higher disposal safety. The cooperative glass curing method can also realize the cooperative glass curing treatment of different waste combinations according to the actual types and the number of different incombustible wastes, fully benefit the characteristics of the wastes, change wastes into valuables, realize the minimization of glass additives (namely the glass additives), and realize the environment-friendly concept of 'treating wastes with processes of wastes against one another'. The method fully utilizes the glass forming property of the glass fiber wastes and also utilizes the component characteristics of concrete or/and soil to reduce the using amount of the glass additive, thereby obviously improving the waste containing rate which can reach 95 percent or more.

The definitions, contents, preferred modes and specific examples of the glass matrix composition, the non-combustible radioactive waste, the radionuclide, the simulated non-combustible radioactive waste, the simulated radionuclide, and the non-combustible waste include, but are not limited to, those described in the first section. In addition, the following detailed explanation is also made.

In some embodiments, before the step S200, the method further comprises a step S100 of preparing the simulated non-combustible radioactive waste,

s100: providing non-combustible waste and a simulated radionuclide, wherein the non-combustible waste is selected from at least two of glass fiber, soil and concrete, and mixing the non-combustible waste with the simulated radionuclide to prepare the simulated non-combustible radioactive waste.

In some embodiments, the average particle size of the concrete is no more than 2mm, preferably no more than 2mm in the largest dimension. The control of the particle size may be achieved by crushing or shearing.

S200: preparing a mixture to be melted.

S200 (ingredients): the glass matrix composition is mixed with simulated non-combustible radioactive waste or the glass matrix composition is mixed with non-combustible radioactive waste to prepare a mixture to be melted.

The simulated non-combustible radioactive waste is used for simulating the cooperative glass solidification of the non-combustible radioactive waste, and the non-combustible radioactive waste can be used for the actual cooperative glass solidification engineering of the non-combustible radioactive waste.

The glass matrix composition mainly includes glass additive components, which are additives required for cooperative glass curing. As long as synergistic glass curing can be realized, the fewer the types, the more beneficial the simplification of the operation and the reduction of the glass forming cost, and the less the amount, the more beneficial the improvement of the waste containment rate. Reference is made to the first aspect of the invention.

In some embodiments, the glass additive in the glass matrix composition is selected from B₂O₃、Na₂O, CaO.

In some embodiments, the glass matrix composition comprises B₂O₃、Na₂O, CaO, preferably B₂O₃、Na₂O, CaO the total content of the mixture to be melted is 5 wt% -35 wt%.

In some embodiments, B₂O₃With B₂O₃Or H₃BO₃Form introduction, and/or, Na₂O is Na₂CO₃Introducing CaO in the form of CaCO, and/or₃And introducing the mixture in a form.

In some embodiments, B₂O₃With B₂O₃Or H₃BO₃Form introduction of Na₂O is Na₂CO₃Introduced in the form of CaCO₃And introducing the mixture in a form.

In some embodiments, the glass matrix composition is free of Li. In some embodiments, the glass matrix composition is SiO-free₂. In some preferred embodiments, the glass matrix composition consists of a material selected from B₂O₃、Na₂O, CaO or any two or three of the above glass additives.

In some embodiments, the component B comprises the following components: component B1: a mimic radionuclide or radionuclide; and component B2: non-combustible waste.

The non-combustible waste can be any binary combination or ternary combination among glass fiber, concrete and soil. When the composition is a binary composition or a ternary composition, the content ratio of the components to each other is not particularly limited. The waste combination condition and proportion can be adjusted according to the actual waste type and quantity, the waste combination form is flexible and variable, and finally the waste treatment by waste is realized.

In component B2 of some embodiments, the non-combustible waste is a binary combination of soil, concrete. Preferably, the ratio of soil: the mass ratio of the concrete is (1:4) - (4: 1).

In component B2 of some embodiments, the non-combustible waste is a binary combination of fiberglass, concrete. Preferably, the glass fiber: the mass ratio of the concrete is (1:4) - (4: 1).

In component B2 of some embodiments, the non-combustible waste is a binary combination of fiberglass, soil. Preferably, the glass fiber: the mass ratio of the soil is (1:4) - (4: 1).

In component B2 of some embodiments, the non-combustible waste is a ternary combination of glass fiber, soil, concrete. Preferably, the glass fiber: soil: the mass ratio of the concrete is (1-4) to (1-4).

In one particular embodiment, in component B2, the non-combustible waste is a binary combination of soil, concrete, soil: the mass ratio of the concrete is 50:40, and the component of the glass matrix composition is Na₂And O, the mass percentage is 5 wt% (taking the total mass of the mixture to be melted as a base number).

In one particular embodiment, in component B2, the non-combustible waste is a binary combination of glass fiber, concrete, glass fiber: the mass ratio of the concrete is 70:25, and the glass matrix composition component is B₂O₃The mass ratio is 10 wt% (taking the total mass of the mixture to be melted as a base number).

In one particular embodiment, in component B2, the non-combustible waste is a ternary combination of glass fiber, soil, concrete, glass fiber: soil: the mass ratio of the concrete is 30:30:30, and the glass matrix composition component is B₂O₃The mass ratio is 10 wt% (taking the total mass of the mixture to be melted as a base number).

In some implementations, component B1 (a mimic radionuclide or radionuclide) is included in the mix to be melted. The species of component B1 reflects the radionuclide species that can be cured. The level of component B1 reflects the level of radioactivity in the waste that can be treated by setting.

In some embodiments, Co₂O₃With Co₂O₃In the form of SrO and/or SrCl₂Or SrCO₃Is added in the form of, and/or, Cs₂O as Cs₂CO₃Or CsCl.

In some embodiments, Co₂O₃With Co₂O₃In the form of SrO, SrCl₂Or SrCO₃Is added in the form of Cs₂O as Cs₂CO₃Or CsCl.

In some embodiments, B₂O₃With B₂O₃Or H₃BO₃Form introduction of Na₂O is Na₂CO₃Introduced in the form of CaCO₃Introducing the form; co₂O₃With Co₂O₃In the form of SrO, SrCl₂Or SrCO₃Is added in the form of Cs₂O as Cs₂CO₃Or CsCl.

S400: a glass melt is prepared.

The temperature T1 at which melting is carried out is preferably not lower than 850 ℃ taking into consideration the melting points of the components of the mixture to be melted. The temperature T1 may be a constant temperature condition or a variable temperature condition.

In some embodiments, the temperature T1 is 850 ℃ to 1300 ℃, examples of preferred modes include, but are not limited to 850 ℃ to 950 ℃, 850 ℃ to 1050 ℃, 850 ℃ to 1150 ℃, 850 ℃ to 1250 ℃, 1000 ℃ to 1300 ℃, 1150 ℃ to 1300 ℃, 1200 ℃ to 1300 ℃, 900 ℃ to 1200 ℃, 950 ℃ to 1050 ℃.

In some specific embodiments, the temperature T1 is selected from any one of the temperature conditions of 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃. Allowing fluctuations in a range such as + -5 deg.C, + -10 deg.C, + -15 deg.C, + -20 deg.C, 25 deg.C.

The temperature T2 at which the first heat-retaining is carried out is preferably not lower than the melting temperature T1.

In some embodiments, the temperature T2 is 850 ℃ to 1300 ℃, examples of preferred modes include, but are not limited to 850 ℃ to 950 ℃, 850 ℃ to 1050 ℃, 850 ℃ to 1150 ℃, 850 ℃ to 1250 ℃, 1000 ℃ to 1300 ℃, 1150 ℃ to 1300 ℃, 1200 ℃ to 1300 ℃, 900 ℃ to 1200 ℃, 950 ℃ to 1050 ℃.

In some specific embodiments, the temperature T2 is selected from any one of the temperature conditions of 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃. Allowing fluctuations in a range such as + -5 deg.C, + -10 deg.C, + -15 deg.C, + -20 deg.C, 25 deg.C.

The heat preservation time of the first heat preservation is required to be enough to complete melting, and is preferably not less than 0.5 h.

In some embodiments, the first incubation time is 0.5h to 5h, and examples of preferred modes include, but are not limited to, 0.5h to 4h, 0.5h to 3h, 0.5h to 2h, 0.5h to 1h, 2h to 5h, 3h to 5h, 4h to 5h, 2h to 4h, and 2.5h to 3.5 h.

In some specific embodiments, the first incubation time is selected from 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5 h.

In the step S400, the temperature T2 is preferably higher than or equal to the temperature T1 so that the mixture to be melted is sufficiently melted.

In some embodiments, S400 (glass fusion): and melting the mixture to be melted at the temperature of 850-1300 ℃ and T1, and carrying out primary heat preservation at the temperature of 850-1300 ℃ and T2 to prepare a glass melt.

In some embodiments, the temperature T1 ranges from 850 ℃ to 1300 ℃, and the temperature T2 ranges from 850 ℃ to 1300 ℃ (preferably T2 ≧ T1).

In some embodiments, the temperature T1 ranges from 850 ℃ to 1100 ℃ and the temperature T2 ranges from 850 ℃ to 1100 ℃ (preferably T2 ≧ T1).

In some embodiments, the temperature T1 ranges from 1000 ℃ to 1300 ℃ and the temperature T2 ranges from 1000 ℃ to 1300 ℃ (preferably T2 ≧ T1).

In some embodiments, the temperature T1 is 850 ℃ and the temperature T2 is 1000 ℃ to 1300 ℃ (preferably T2 ≧ T1).

In the step S400, preferably, the holding time is not less than 1h when the temperature T2 is not more than 1000 ℃, so that the mixture to be melted is fully dissolved.

In some embodiments, the temperature T2 is 850 ℃ to 1300 ℃ and the first incubation time is 0.5h to 5 h.

In some preferred embodiments, the temperature T2 is 1000 ℃ to 1300 ℃ and the first holding time is 0.5h to 1 h.

In some preferred embodiments, the temperature T2 is 850 ℃ to 1000 ℃ and the first holding time is 1h to 5 h.

In some embodiments, the temperature T2 is 850 ℃ and the first incubation time is 1.5h, 2h, 3h, 4h, or 5 h.

S500: a glass-solidified body of non-combustible radioactive waste is prepared.

The temperature T3 of the container when casting and forming is carried out is preferably not higher than the first heat preservation temperature T2, and T3 is required to ensure that the glass melt is in a heat preservation homogenization state, and the phenomena of crystallization and the like are avoided.

In some embodiments, the temperature T3 is 300 ℃ to 1000 ℃, and examples of preferred modes include, but are not limited to, 300 ℃ to 900 ℃, 300 ℃ to 800 ℃, 300 ℃ to 700 ℃, 300 ℃ to 600 ℃, 500 ℃ to 1000 ℃, 600 ℃ to 1000 ℃, 700 ℃ to 1000 ℃, 800 ℃ to 1000 ℃, 400 ℃ to 900 ℃, 500 ℃ to 800 ℃.

In some embodiments, the temperature T3 is selected from any one of 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃.

The temperature T4 for the second heat preservation is 300-1000 ℃, the heat preservation is carried out at the temperature T4, the glass melt can be clarified, and the temperature range of T4 can be 300-900 ℃, 300-800 ℃, 300-700 ℃, 300-600 ℃, 500-1000 ℃, 600-1000 ℃, 700-1000 ℃, 800-1000 ℃, 400-900 ℃ and 500-800 ℃.

The heat preservation time of the second heat preservation is preferably not less than 0.5 h.

In some embodiments, the second incubation time is 0.5h to 3h, and examples of preferred modes include, but are not limited to, 0.5h to 2.5h, 0.5h to 1.5h, 1.5h to 3h, 2.5h to 3h, 0.5h to 2h, and 1.5h to 2 h.

In some specific embodiments, the second incubation time is selected from 0.5h, 1h, 1.5h, 2h, 2.5h, 3 h.

In step S500, it is preferable that the second holding time is not less than 1 hour when the temperature T4 does not exceed 500 ℃ so that the glass melt has a sufficient fining time.

In some embodiments, the temperature T4 is 300 ℃ to 1300 ℃ and the first incubation time is 0.5h to 3 h.

In some preferred embodiments, the temperature T4 is 300 ℃ to 500 ℃ and the first incubation time is 0.5h to 3 h.

In some preferred embodiments, the temperature T4 is 500 ℃ to 1300 ℃ and the first holding time is 1h to 3 h.

In some embodiments, the temperature T2 is 500 ℃ and the first incubation time is 1h, 1.5h, 2h, 2.5h, or 3 h.

In one embodiment of the invention, the temperature T1 at which melting is carried out is 1200 ℃; the temperature T2 for carrying out the first heat preservation is 1200 ℃, and the heat preservation time for the first heat preservation is 1 h; the temperature T3 during casting molding is 850 ℃; the temperature T4 of the second heat preservation is 850 ℃, and the heat preservation time of the second heat preservation is 2 h.

In one embodiment of the invention, the temperature T1 at which melting is performed is 1150 ℃; the temperature T2 for carrying out the first heat preservation is 1150 ℃, and the heat preservation time for the first heat preservation is 2 h; the temperature T3 during casting molding is 600 ℃; the temperature T4 of the second heat preservation is 600 ℃, and the heat preservation time of the second heat preservation is 2 h.

In one embodiment of the invention, the temperature T1 at which melting is carried out is 1250 ℃; the temperature T2 for carrying out the first heat preservation is 1250 ℃, and the heat preservation time for the first heat preservation is 2 h; the temperature T3 during casting molding is 500 ℃; the temperature T4 of the second heat preservation is 500 ℃, and the heat preservation time of the second heat preservation is 2 h.

The synergistic glass curing method provided by the second aspect of the invention can reduce the use amount of additives, improve the waste containment rate, treat wastes with processes of wastes against one another and has flexible waste combination forms. Any single waste in radioactive and incombustible wastes (such as glass fiber, soil, concrete and the like) needs to be added with a certain glass additive to form a glass solidified body with the performance meeting the disposal requirement, and in the field of synergistic glass solidification, the usage amount of the glass additive is not more than 50 wt%. According to the invention, different non-combustible wastes are combined and cooperatively treated according to the glass forming characteristics of the non-combustible wastes, so that a glass solidified body with the performance meeting the requirement can be formed under the condition of adding a small amount of glass additive. In the case of the multi-waste co-processing of the present invention, the waste packing capacity is higher than that of the single waste (i.e., the glass additive to be added in the case of the multi-waste co-processing is much smaller than that in the case of the single waste). Under the condition of the combined synergistic treatment of the non-combustible waste, the usage amount of the glass additive can be reduced to 5 wt%, and the comprehensive containing rate of the waste can be as high as 95 wt%; the treatment and disposal costs can be further reduced by reducing the use amount of the additive and improving the waste containment rate.

The synergistic glass-setting process provided in the second aspect of the invention also allows for an increase in the volume-reduction ratio of non-combustible waste. The glass matrix composition of the invention only needs less components, and can melt the incombustible waste into the glass solidified body with greatly reduced volume at high temperature, and the comprehensive volume reduction ratio is obviously improved. In particular, the volume reduction ratios in the case of the different wastes in conjunction with the vitrification treatment are higher, on average, by up to 10, than in the case of the vitrification treatment of the single wastes separately.

The synergistic glass-setting method provided in the second aspect of the present invention can also improve the mechanical strength of the set body. The compressive strength of the cured body obtained by the traditional cement curing method only needs to meet the requirement>7MPa, generally 10-20 MPa, and the compressive strength and impact strength of the glass solidified body developed by the invention are both more than 30MPa and all<4cm²a/J, the impact strength of the glass solidified body to the solidified body is less than or equal to 12cm²Requirement of/J, increase of mechanical strength is advantageous for waste solidsTransport and disposal of the chemosomes.

The synergistic glass curing method provided by the second aspect of the invention also has good leaching resistance and meets the performance requirements of a cured body. The total weight loss of the glass solidified body per unit surface area of the glass solidified body after static soaking for 28 days is lower than 15g/m²Meets the relevant requirements of radioactive waste glass solidification body (refer to GB 14569.1-2011 and EJ 1186-.

The cooperative glass curing method provided by the second aspect of the invention has the advantages of simple process and wide prospect. The method for preparing the glass solidified body has simple process, can be implemented on glass melting equipment such as a ceramic electric melting furnace, a cold crucible melting furnace and the like, is suitable for treating various radioactive incombustible wastes (glass fiber, soil and concrete) in the field of nuclear industry, and has good application prospect.

Some specific examples are as follows.

Experimental parameters not described in the following specific examples are preferably referred to the guidelines given in the present application, and may be referred to experimental manuals in the art or other experimental methods known in the art, or to experimental conditions recommended by the manufacturer.

The starting materials and reagents mentioned in the following specific examples can be commercially available or can be prepared by a person skilled in the art according to known means. In the following examples, in order to improve the holding rate of the incombustible waste and improve various properties of the final solidified body, the chemical components of the radioactive incombustible waste (glass fiber, soil, concrete and the like) for nuclear facilities are analyzed, the glass matrix composition and the generated solidified body under the conditions of different waste combinations (including binary combination and ternary combination of glass fiber, soil and concrete) and different waste proportions under the same waste combination are researched by an orthogonal method, the respective optimal glass solidified body formula under the different waste combinations is preferably selected, the solidified body is tested for weight loss rate, density after soaking, compressive strength, impact strength and irradiation resistance, and the obtained glass solidified body is good in various properties according to the test results.

The following examples employ simulated radionuclides for simulating actual radionuclides and simulated non-combustible radioactive waste (containing simulated radionuclides and non-combustible waste) for simulating actual non-combustible radioactive waste. The processing method for cooperative glass curing provided by the invention is not only used for research of a simulation scene, but also used for actual engineering processing.

Example 1 waste Source item composition testing

The oxide components of the waste source items play a crucial role in the design of the glass formula, directly influence the applicability and the performance of a solidified body of the formula and integrally consider the oxide composition in the radioactive waste. The method comprises performing component test on non-combustible waste (glass fiber, soil, and concrete) by X-ray fluorescence spectrometer (XRF, PANALYTICAL. B.V. and Zetium) and full spectrum direct reading plasma emission spectrometer (ICP-OES, LEEMAN LABS, Prodigy), wherein the radionuclide mainly considers fission product¹³⁷Cs、⁹⁰Sr and activation product⁶⁰Co。

The waste sources used in the examples section include glass fiber, soil, concrete, and the results are shown in table 1.

TABLE 1 main oxide component of non-radioactive combustible waste (glass fibre, soil, concrete)

Composition (I)	Glass fiber	Soil(s)	Concrete and its production method
				SiO₂	56.83	65.17	17.18
CaO	10.57	3.44	69.60
				K₂O	7.60	2.99	0.25
Na₂O	7.13	1.70	0.17
				Al₂O₃	6.11	17.29	5.22
B₂O₃	4.94	/	/
				BaO	3.27	/	/
Others	3.55	9.41	7.04
				Total up to	100	100	100

Other: comprising MgO, SO₃，TiO₂，Fe₂O₃，SrO，P₂O₅Etc. of

The radioactive components and contents not listed in table 1: CoO 0.2 wt%, Cs₂O 0.2wt％、SrO 0.2wt％。

Example 2 preparation of glass fiber + concrete non-combustible waste (binary combination) hybrid glass cured body

2.1 preparation of glass-cured body

(1) Pretreatment: the large-volume glass fiber in the non-flammable radioactive waste is crushed or sheared, and soil is dried to facilitate the accuracy of the measuring result.

(2) Burdening (preparing a mixture to be melted): weighing 70 wt% of glass fiber and 25 wt% of concrete, wherein the weight of the non-combustible waste accounts for 95 wt% of the mixture to be melted. Weighing glass additive Na₂O is used as a glass matrix composition, and accounts for 5 wt% of the weight of the mixture to be melted, and Na₂O is Na₂CO₃And introducing the mixture in a form. Weighing 0.2 wt% of CoO and 0.2 wt% of Cs in the glass solidified body₂O, 0.2 wt% SrO. And uniformly mixing the glass fiber, the concrete, the glass matrix composition and the simulated radionuclide to obtain a mixture to be melted. And weighing 20g of mixture to be melted for glass melting.

(3) Melting glass: and adding the mixture to be melted into a 100mL corundum crucible, melting in a muffle furnace at 1200 ℃, and preserving heat at 1200 ℃ for 1h to prepare a glass melt.

(4) Glass forming: the glass melt was cast on a preheated copper plate at a preheating temperature of 850 ℃ to obtain a cast body.

(5) Glass annealing: and (3) preserving the heat of the cast body at 850 ℃ for 2h, and cooling the cast body to room temperature along with the furnace to obtain the glass solidified body.

2.2 Performance testing

2.2.1 Density test

Respectively carrying out density tests on the glass solidified body for 5 times at room temperature by adopting an Archimedes drainage method, and averaging to obtain the density of the glass solidified body of 2.70g/cm³。

2.2.2 XRD testing

The phase analysis of the glass-cured body was carried out by means of an X-ray diffractometer (XRD, Bruker, D8 Discovery), and the results of the measurement are shown in FIG. 2. In fig. 2, the horizontal axis represents the diffraction angle and the vertical axis represents the diffraction intensity. According to fig. 2, the typical amorphous steamed bun peaks are present overall, reflecting that the prepared glass-solidified body is in a glassy state.

2.2.3 uniformity test

The glass solidified body was observed by an optical microscope, and was uniform as a whole, and no other inclusions were found.

2.2.4 testing of leach resistance

The anti-leaching performance test was performed using the method described in characterisation of radioactive waste and waste bags (EJ1186- & 2005) 4.1.5.1.2 anti-leaching. The 28-day total leaching value of the element of the glass solidified body was measured to be 6.99g/m²The leaching rate of the normalized elements of Si, B, Na, Cs and U is less than 1 g/(m)²·d)。

2.2.5 compression resistance test

With reference to GB/T8489-. The compressive strength of the glass-solidified body was found to be 55.62 MPa.

2.2.6 impact resistance test

The impact resistance test was carried out by the hammer free fall impact method in appendix D of characterisation of radioactive waste and waste bags (EJ1186-2005), and the impact resistance was characterized by an SA/E value. Wherein the SA/E value is the ratio of the increase in surface area of the sample after disruption to the energy used. The SA/E value of the glass-cured product was found to be 1.27cm²/J。

2.2.7 volume reduction ratio test

The calculation method of the volume reduction ratio comprises the following steps: the volume ratio of the volume of the mixture to be melted to the volume of the glass solidified body is measured by a drainage method. The volume reduction ratio of the glass-solidified body was found to be 10 from the test results.

2.2.8 waste Containment Rate

The method for calculating the waste containment rate comprises the following steps:

waste containment ratio-quality of non-combustible radioactive waste/quality of mixture to be melted

The containment rate was calculated to be 95%.

According to the comparison table of the multi-waste mixed glass solidified body, the single waste and the standard indexes in the table 2, the prepared glass solidified body has good performances and meets the related requirements of the radioactive waste glass solidified body in the character identification of radioactive waste and waste bags (EJ 1186-2005).

Table 2 example 2 comparative table of multi-waste hybrid glass solidified body and single waste, standard index

Example 3 preparation of a glass-set body with soil + concrete as a binary Combined waste Source

3.1. Preparation of glass-cured body

(1) Pretreatment: the method comprises the following steps of crushing or shearing mass concrete in the non-flammable radioactive wastes to enable the maximum size of a concrete raw material to be not more than 2mm, and drying the soil to facilitate the accuracy of a measuring result.

(2) Burdening (preparing a mixture to be melted): weighing 50 wt% of concrete and 40 wt% of soil, wherein the weight of the non-combustible waste accounts for 90 wt% of the mixture to be melted. Weighing glass additive B₂O₃As glass matrix composition, the weight proportion in the mixture to be melted is 10 wt%, B₂O₃With H₃BO₃And introducing the mixture in a form. Weighing 0.2 wt% of CoO and 0.2 wt% of Cs in the glass solidified body₂O, 0.2 wt% SrO. Mixing concrete, soil and glass matrixAnd uniformly mixing the simulated radionuclides to obtain a mixture to be melted. And weighing 10kg of mixture to be melted for glass melting.

(3) Melting glass: adding 10kg of mixture to be melted into a melting furnace system in batches, melting at 1150 ℃, and then preserving heat for 2h at 1150 ℃ to prepare glass melt.

(4) Glass forming: and (3) casting the glass melt in a preheated slag receiving container, wherein the preheating temperature is 600 ℃, and obtaining a casting body.

(5) Glass annealing: and (3) preserving the heat of the casting body for 2 hours at the temperature of 600 ℃, and cooling the casting body to room temperature along with the furnace to obtain the glass solidified body.

3.2 Performance testing

3.2.1 Density test

The density of the glass solidified body was measured to be 2.80g/cm by Archimedes drainage method³。

3.2.2 XRD testing

The glass-cured body was subjected to XRD test by the method of 2.2.2 in example 2. The test results are shown in fig. 4. In fig. 4, the horizontal axis represents the diffraction angle and the vertical axis represents the diffraction intensity. As can be seen from fig. 4, the typical amorphous steamed bun peaks are present overall, reflecting that the prepared glass-solidified body is in a glassy state.

3.2.3 uniformity test

3.2.4 Leaching resistance test

The test was carried out using the method of 2.2.4 in example 2.

The 28-day total leaching value of the element of the glass solidified body was measured to be 3.84g/m²The leaching rate of the normalized elements of Si, B, Na, Cs and U is less than 1 g/(m)²·d)。

3.2.5 crush resistance test

The test was carried out using the method of 2.2.5 in example 2. The compressive strength of the glass-solidified body was measured to be 32.51 MPa.

3.2.6 impact resistance test

The test was carried out using the method of 2.2.6 in example 2. Measuring the glass-solidified bodySA/E value of 3.93cm²/J。

3.2.7 volume reduction ratio test

The method 2.2.7 in example 2 was used for testing and calculation. The volume reduction ratio of the glass-solidified body was calculated to be 2 from the test results.

3.2.8 waste containment rate

The calculation was carried out using the method of 2.2.8 in example 2. The containment rate was calculated to be 90%.

According to the comparison table of the multi-waste mixed glass solidified body, the single waste and the standard indexes in the table 3, the prepared glass solidified body has good performances and meets the related requirements of the radioactive waste glass solidified body in the character identification of radioactive waste and waste bags (EJ 1186-2005).

Table 3 example 3 comparative table of multi-waste hybrid glass solidified body with single waste and standard index

Example 4 preparation of a glass-set body of concrete + glass fiber + soil as a ternary combination waste Source

4.1 preparation of glass-cured body

(1) Pretreatment: the method comprises the following steps of crushing or shearing mass concrete and glass fibers in the non-combustible radioactive wastes, wherein the maximum size of the concrete is not more than 2mm, and soil drying treatment is convenient for measuring result accuracy.

(2) Burdening (preparing a mixture to be melted): weighing 30 wt% of glass fiber, 30 wt% of concrete and 30 wt% of soil, wherein the weight of the non-combustible waste accounts for 90 wt% of the mixture to be melted. Weighing glass additive Na₂O as a glass base composition in a glass-to-be-melted mixture in an amount of 10 wt%, Na₂O is Na₂CO₃And introducing the mixture in a form. Weighing 0.2 wt% of CoO and 0.2 wt% of Cs in the glass solidified body₂O, 0.2 wt% SrO. And uniformly mixing the glass fiber, the concrete, the soil, the glass matrix composition and the simulated radionuclide to obtain a mixture to be melted.And weighing 10kg of mixture to be melted for glass melting.

(3) Melting glass: adding the mixture to be melted into a melting furnace system in batches, melting at 1250 ℃, and preserving heat for 2 hours at 1250 ℃ to prepare the glass melt.

(4) Glass forming: and (3) casting the glass melt in a preheated slag receiving container, wherein the preheating temperature is 500 ℃, and thus a casting body is prepared.

(5) Glass annealing: and (3) preserving the heat of the cast body at 500 ℃ for 2h, and cooling the cast body to room temperature along with the furnace to obtain the glass solidified body.

4.2 Performance testing

4.2.1 Density test

The density of the glass solidified body was measured to be 2.63g/cm by Archimedes drainage method³。

4.2.2 XRD testing

The glass-cured body was subjected to XRD test by the method of 2.2.2 in example 2. The test results are shown in fig. 6. In fig. 6, the horizontal axis represents the diffraction angle and the vertical axis represents the diffraction intensity. As can be seen from fig. 6, the typical amorphous steamed bun peaks are present overall, reflecting that the prepared solidified body is in a glassy state.

4.2.3 uniformity test

4.2.4 Leaching resistance test

The test was carried out using the method of 2.2.4 in example 2. The 28-day total leaching value of the element of the glass solidified body was measured to be 6.32g/m²The leaching rate of the normalized elements of Si, B, Na, Cs and U is less than 1 g/(m)²·d)。

4.2.5 compression resistance test

The compressive strength of the glass-set product was measured to be 35.45MPa by the method of 2.2.5 in example 2.

4.2.6 impact resistance test

The test was carried out using the method of 2.2.6 in example 2. The SA/E value of the glass-cured body was found to be 4.43cm²/J。

4.2.7 volume reduction ratio test

The method 2.2.7 in example 2 was used for testing and calculation. The volume reduction ratio of the glass-solidified body was calculated to be 7 from the test results.

4.2.8 waste holding ratio

According to the comparison table of the multi-waste mixed glass solidified body, the single waste and the standard indexes in the table 4, the prepared glass solidified body has good performances and meets the related requirements of the radioactive waste glass solidified body in the character identification of radioactive waste and waste bags (EJ 1186-2005).

Table 4 example 4 comparative table of multi-waste hybrid glass solidified body with single waste and standard index

COMPARATIVE EXAMPLE 1 (corresponding to A in FIG. 1)

The waste source adopts a binary combination of glass fiber and concrete in a mass ratio of 1:1, and no glass additive (namely no glass matrix composition) is added. The rest corresponds to example 2.

COMPARATIVE EXAMPLE 2 (corresponding to B in FIG. 1)

The waste source was a binary combination of glass fiber and concrete in a mass ratio of 75:25 with no glass additive added (i.e., no glass matrix composition added). The rest corresponds to example 2.

COMPARATIVE EXAMPLE 3 (corresponding to A in FIG. 3)

The waste source adopts a binary combination of concrete and soil in a mass ratio of 1:1, and no glass additive (namely no glass matrix composition) is added. The rest corresponds to example 3.

COMPARATIVE EXAMPLE 4 (corresponding to B in FIG. 3)

The waste source adopts a binary combination of concrete and soil with a mass ratio of 50:40, and no glass additive (namely no glass matrix composition) is added. The rest corresponds to example 3.

COMPARATIVE EXAMPLE 5 (corresponding to A in FIG. 5)

The waste source adopts glass fiber with the mass ratio of 1:1: 1: concrete: the soil was ternary combined and no glass additive was added (i.e., no glass matrix composition was added). The rest corresponds to example 4.

Comparison results

FIG. 1 is a physical comparison of the glass-shaped articles prepared in example 3 and comparative examples 1 and 2, and it can be seen that the articles were glassy and homogeneous when the glass matrix composition (i.e., glass additive) was added, and the articles were not glassy when the glass matrix composition was not present.

FIG. 3 is a physical comparison of the glass-cured products prepared in example 3 and comparative examples 3 and 4, and it can be seen that the cured product was glassy and homogeneous in the presence of the additive, and was not glassy in the absence of the glass additive.

FIG. 5 is a comparison of the glass-cured products of example 4 and comparative example 5, and it can be seen that the cured product was glassy and homogeneous in the presence of the additive, and that the cured product was glassy but too viscous to be practically used in the absence of the glass additive.

The technical features of the embodiments and examples described above can be combined in any suitable manner, and for the sake of brevity, all possible combinations of the technical features of the embodiments and examples described above are not described, but should be considered within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.

Claims

1. The glass solidified body of the non-flammable radioactive waste is characterized by comprising 5-35 wt% of a component A and 65-95 wt% of a component B:

2. The glass-solidified body of claim 1, wherein: the total mass percentage of the component A and the component B in the glass solidified body is 100 wt%.

3. The glass-solidified body of claim 1, wherein: the glass matrix composition consists of a material selected from B₂O₃、Na₂O, CaO, any two or three glass additives; and/or the presence of a catalyst in the reaction mixture,

4. The glass-solidified body of claim 1, wherein: the glass matrix composition is free of Li; and/or, the saidGlass matrix composition free of SiO₂。

5. The glass-cured body according to any one of claims 1 to 4, wherein: in the glass solidified body, Co₂O₃0 to 1 wt% of SrO, and 0 to 1 wt% of Cs₂The mass ratio of O is 0-1 wt%.

6. The glass-solidified body of claim 1, wherein: the non-combustible radioactive waste is selected from any one of the following situations:

case three: the non-combustible waste is a binary combination of glass fiber and soil, and the glass matrix composition comprises a glass additive with the content of 5-15 wt% of Na in the glass solidified body₂O、5wt％～15wt％B₂O₃And 5 to 20 weight percent CaO;

7. The glass-solidified body of claim 6, wherein: the non-combustible radioactive waste is selected from any one of the following situations:

the first situation is as follows: the non-combustible wasteThe soil is a binary combination of soil and concrete, wherein the soil: the mass ratio of the concrete is (1:4) - (4:1), and the content of the glass additive contained in the glass matrix composition in the glass solidified body is 0-5 wt% of Na₂O、5wt％～15wt％B₂O₃And 0-5 wt% CaO;

8. A method for the synergistic vitrification of non-combustible radioactive wastes, characterized by comprising the following steps:

wherein the mass percentage of the glass matrix composition in the mixture to be melted is 5 wt% -35 wt%, and the glass matrix composition comprises B₂O₃、Na₂O, CaO; the simulation isThe mass percentage of combustible radioactive waste or the non-combustible radioactive waste in the mixture to be melted is respectively and independently 65-95 wt%;

9. The synergistic vitrification of non-combustible radioactive waste as set forth in claim 8, wherein: further comprising the step of preparing said simulated non-combustible radioactive waste by:

10. The synergistic vitrification of non-combustible radioactive waste as set forth in claim 8, wherein: further comprising preparing the glass matrix composition and/or preparing the non-combustible radioactive waste;

in the glass matrix composition, B₂O₃With B₂O₃Or H₃BO₃Form introduction, and/or, Na₂O is Na₂CO₃Introducing CaO in the form of CaCO, and/or₃Introducing the form;

11. The synergistic vitrification of non-combustible radioactive waste as set forth in claim 8, wherein: the simulated non-combustible radioactive waste contains simulated radionuclides; the non-combustible radioactive waste contains radionuclides.

12. The synergistic vitrification of non-combustible radioactive waste as set forth in claim 8, wherein: the non-combustible waste comprises concrete and the average particle size of the concrete does not exceed 2mm and/or the maximum dimension of the concrete does not exceed 2 mm.

13. The synergistic glassing process for non-combustible radioactive waste according to any one of claims 8 to 12, wherein: the temperature T1 for the melting is 850-1300 ℃; and/or the presence of a catalyst in the reaction mixture,

the annealing is in the form of furnace cooling to room temperature.