CN112466503A - Preparation method of glass ceramic body for solidifying Cs-containing soil - Google Patents
Preparation method of glass ceramic body for solidifying Cs-containing soil Download PDFInfo
- Publication number
- CN112466503A CN112466503A CN202011586208.8A CN202011586208A CN112466503A CN 112466503 A CN112466503 A CN 112466503A CN 202011586208 A CN202011586208 A CN 202011586208A CN 112466503 A CN112466503 A CN 112466503A
- Authority
- CN
- China
- Prior art keywords
- soil
- glass ceramic
- ceramic body
- sio
- containing soil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/28—Treating solids
- G21F9/30—Processing
- G21F9/301—Processing by fixation in stable solid media
- G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
- G21F9/305—Glass or glass like matrix
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0063—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing waste materials, e.g. slags
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Soil Conditioners And Soil-Stabilizing Materials (AREA)
Abstract
The invention discloses a preparation method of a glass ceramic body for solidifying Cs-containing soil, which is characterized by comprising the following steps: taking raw material CsOH.H2O、Sol‑SiO2Metakaolin and water; the raw material CsOH.H2Adding O into a container, adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing, finally adding metakaolin, stirring, pouring the slurry into a mould, drying and demoulding to obtain the soil containing Cs; taking the soil containing the Cs and the glass powder according to the mass percentage of 50-90% of the soil containing the Cs and 10-50% of the glass powder; mixing, grinding and pressing into sheets; and heating the flaky mixture at the temperature of 700-1000 ℃ for 2-8 hours, and cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body. The glass ceramic body of the solidified Cs-containing soil prepared by the invention has good chemical stability and thermal stability, and is suitable for solidification treatment of radioactive waste cesium discharged in the fields of nuclear industry and the like.
Description
Technical Field
The invention belongs to the treatment and disposal of radioactive waste, and relates to a preparation method of a glass ceramic body for solidifying Cs-containing soil, which is suitable for solidification treatment of radioactive waste cesium (Cs) discharged in the fields of nuclear industry and the like.
Background
In the process of nuclear energy utilization, a large amount of radioactive waste is generated, and the radioactive waste contains a large amount of radioactive waste with long half-life period, high toxicity and radiationHigh actinium and fission elements. The radioactive waste is mainly from the treatment process of the retired spent fuel and nuclear tests. In the process of after-treatment of the retired spent fuel, uranium and plutonium are separated and purified to be made into mixed oxide fuel (MOX fuel for short) for reuse, and the rest fission products need to be further treated and disposed. Among the important fission products are137Cs、90Sr、144Ce、129I, and the like. The decay cycle of the cesium (Cs) radionuclide is long and over time, the proportion of cesium in the fission products in the radioactive waste increases.
The Fudao nuclear power station accident occurred in 3 and 11 months in 2011 causes the soil in the Fudao area to be subjected to radioactive elements137Serious contamination with Cs. 137Cs belongs to water-soluble long-life metal nuclides, usually exists in an ion form, has strong migration capacity in water, and can cause serious environmental pollution, particularly to soil. And is137Cs can be accumulated in organisms and is extremely harmful to human bodies. Therefore, the treatment and disposal of radioactive waste containing cesium are of great importance.
In the prior art, the curing treatment of the soil containing radioactive Cs mainly comprises glass curing, ceramic curing and cement curing. Among these, for the more cured ceramics of Cs, a variety of materials have been explored, including pollucite (CsAlSi)2O6) Analcime (BaAl)2Ti6O16) And geopolymers, and the like. Wherein pollucite compounds can be synthesized from Cs contaminated soil and can contain more than 40% Cs by mass, can form a compact waste-solidified substrate, and are considered to be a promising type of fixable and long-term storage of strongly-radioactive waste water137Research on the substance of Cs (see Wanglan, Houxi, dragon, etc. mineral solidification of Sr-containing and Cs-containing radioactive wastes [ J]Material guide, 2017(3). However, CsAlSi2O6The synthesis of (A) generally requires relatively high temperatures (> 1000 ℃), which may lead to volatilization of Cs. Therefore, there is an urgent need to develop a curing system that can be formed at a lower temperature.
At present, researches at home and abroad on the preparation of a solidified body containing Cs soil generally mainly comprise preparing a ceramic body by a hydrothermal method or a sol-gel method; the hydrothermal method is generally characterized in that water is used as a solvent in a sealed pressure container, soil is used for synthesizing polluted soil immobilized Cs, and a sol-gel method is used for dissolving all raw materials and a proper amount of acid in deionized water, stirring and heating the mixture to form gel, drying the gel and sintering the gel to obtain ceramic powder solidified Cs; although the two methods can effectively reduce the synthesis temperature and avoid volatilization of Cs, the process is complex and is not suitable for engineering.
No literature report on the preparation method of the Cs-containing soil glass ceramic solidified body is found in the prior art.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a glass ceramic body for solidifying Cs-containing soil. The invention adopts the glass binder which is sodium borosilicate or borosilicate glass powder, and the glass binder is directly mixed with soil polluted by Cs to be fired to prepare the pollucite glass ceramic body, thereby providing a new preparation method of the glass ceramic cured body with good performance for the curing treatment of the soil containing Cs.
The content of the invention is as follows: a preparation method of a glass ceramic body for solidifying Cs-containing soil is characterized by comprising the following steps:
a. preparing Cs-containing soil: taking raw material CsOH.H2O、Sol-SiO2(i.e., silica sol), metakaolin and water (preferably deionized water); the raw material CsOH.H2Adding O into a container (such as beaker), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (namely silica sol) and dissolving in an alkali activator, finally adding metakaolin, stirring for 5-30 min to obtain slurry, pouring the slurry (stirred) into a mould, drying in a (constant temperature blast) drying oven at the temperature of 60-80 ℃ for 24-48 h, taking out, cooling to room temperature, and demoulding to obtain the soil containing Cs;
b. preparing materials: taking the soil containing the Cs and the glass powder according to the mass percentage of 50-90% of the soil containing the Cs and 10-50% of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture;
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and (3) heating and preserving the temperature of the flaky mixture at 700-1000 ℃ (preferably 700-900 ℃) for 2-8 hours, and then cooling along with a furnace to obtain the cured glass ceramic body containing the Cs soil.
The invention comprises the following steps: taking the raw material CsOH & H in the step a2O、Sol-SiO2(i.e., silica sol), metakaolin and water in a CsOH. H ratio2O3.016 weight portions and Sol-SiO22.8504 parts of (namely silica sol), 2 parts of metakaolin and 0.649 part of water (preferably deionized water) by mass, and the raw material CsOH & H is taken2O、Sol-SiO2(i.e., silica sol), metakaolin, and water.
The invention comprises the following steps: the Cs-containing soil prepared in the step a mainly comprises the following chemical components in percentage by mass: Si/Al is fixed to be 2, Cs/Al is fixed to be 1, and the water-gel ratio is fixed to be 0.3, wherein Si and Al are composed of metakaolin and Sol-SiO2Introducing Cs from CsOH. H2And introducing O.
The invention comprises the following steps: in the ingredient of the step b, the main chemical compositions and mass percentages of the glass powder are as follows: SiO 22 41%～59%、B2O3 8%～25%、Na2O 20%～33%、A12O3 0%～7%、CaO 0%～5%、ZrO20 to 3 percent, and the sum of all the components is 100 percent.
The invention comprises the following steps: the glass powder in the ingredients in the step b can be prepared from the following main chemical components in percentage by mass: SiO 22 58.87%、B2O3 8.98%、Na2O 20.17%、A12O3 5.99%、CaO 3.99%、ZrO2 2.00%。
The invention comprises the following steps: the glass powder in the ingredients in the step b can be prepared from the following main chemical components in percentage by mass: SiO 22 42.50%、B2O3 24.60%、Na2O 32.88%。
The invention comprises the following steps: and c, grinding in the mixing step is carried out by adopting a ball mill, and the particle size of the mixed material after grinding is less than 200 meshes.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) by adopting the method, the process of polluting soil by Cs is simulated, and the pollucite glass ceramic body is prepared in the process of firing the glass ceramic. Moreover, because the high-melting-point glass is applied, the required temperature in the preparation process of the glass ceramic is lower than the volatilization temperature of Cs, and the Cs is not easy to volatilize;
(2) by adopting the method, in the process of preparing the pollucite glass ceramic body, Cs does not need to be independently processed and prepared into pollucite ceramic powder for solidification, but Cs-containing soil and glass powder can be directly mixed and then sintered to directly form the pollucite glass ceramic solidified body;
(3) the method is used for the solidification treatment of the glass ceramic of the soil containing Cs to prepare the glass ceramic solidified body of the soil containing Cs, and the chemical stability and the thermal stability of the solidified body of the soil containing Cs are good (the weight loss rate of the Cs element is less than 1 multiplied by 10 after 28 days of leaching)-2 g·m-2·d-1) Good mechanical stability and radioactive waste containing capacity (forming stable pollucite crystal structure), and small weight loss rate (the weight loss rate of Cs element is less than 1 × 10 after 28 days of leaching)-2 g·m-2·d-1) (ii) a Excellent physical properties and high hardness (hardness of over 600 Hv);
(4) the invention uses glass to bind soil polluted by Cs, and then burns the soil into pollucite-containing glass ceramic, which is a preparation method of glass ceramic, wherein Cs is fixed in pollucite phase contained in sintered glass matrix; these types of glass-ceramics are sometimes also referred to as glass composites; the preparation of these glass ceramics only needs lower sintering temperature to avoid Cs volatilization; the glass binder helps to reduce porosity, induce crystallization of the target phase encapsulating the target radionuclide, and immobilize radionuclides that are not incorporated into the crystalline phase in the glass phase;
(5) in the preparation process, the firing temperature is lower than the volatilization temperature of Cs, and Cs is not easy to volatilize; compared with a hydrothermal method and a sol-gel method, the method has the advantages of cheap and easily-obtained raw materials, simple preparation process, easy operation, easy control of production process, easy engineering and strong practicability.
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
Example 1:
a preparation method of a glass ceramic body for solidifying Cs-containing soil comprises the following steps:
a. preparing Cs-containing soil: taking raw material CsOH.H2O 3.016 g、Sol-SiO22.8504 g (namely silica sol), 2 g of metakaolin and 0.649 g of water; the raw material CsOH.H2Adding O into a container (such as beaker), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (i.e. silica sol) and dissolving in an alkali activator, finally adding metakaolin, stirring for 20min to obtain slurry, pouring the slurry (stirred) into a mould, drying in a (constant temperature blast) drying oven at the temperature of 70 ℃ for 36h, taking out, cooling to room temperature, and demoulding to obtain the soil containing Cs;
b. preparing materials: taking the Cs-containing soil and the glass powder according to the mass percentage of 90% of the Cs-containing soil and 10% of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture (the particle size of the mixed material is less than 200 meshes);
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 700 ℃ for 2 hours, and then cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body.
Through detection: the prepared glass ceramic body of the solidified Cs-containing soil is soaked in deionized water at the temperature of 90 ℃ for 28 days, and the weight loss rate of the Cs element is less than 1 multiplied by 10-2 g·m-2·d-1The microhardness of the glass ceramic solidified body is more than 500 MPa.
Example 2:
a preparation method of a glass ceramic body for solidifying Cs-containing soil comprises the following steps:
a. preparing Cs-containing soil: taking raw material CsOH.H2O 3.016 g、Sol-SiO22.8504 g (namely silica sol), 2 g of metakaolin and 0.649 g of water; the raw material CsOH.H2Adding O into a container (such as beaker), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (i.e. silica sol) and dissolving in an alkali activator, finally adding metakaolin, stirring for 5min to obtain slurry, pouring the slurry (stirred) into a mould, drying in a drying oven (constant temperature blast) at the temperature of 60 ℃ for 48h, taking out, cooling to room temperature, and demoulding to obtain the soil containing Cs;
b. preparing materials: taking the Cs-containing soil and the glass powder according to the mass percentage of 90% of the Cs-containing soil and 10% of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture (the particle size of the mixed material is less than 200 meshes);
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 700 ℃ for 8 hours, and then cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body.
Through detection: the prepared glass ceramic body of the solidified Cs-containing soil is soaked in deionized water at the temperature of 90 ℃ for 28 days, and the weight loss rate of the Cs element is less than 1 multiplied by 10-2 g·m-2·d-1The microhardness of the glass ceramic solidified body is more than 550 MPa.
Example 3:
a preparation method of a glass ceramic body for solidifying Cs-containing soil comprises the following steps:
a. preparing Cs-containing soil: taking raw material CsOH.H2O 3.016 g、Sol-SiO22.8504 g (namely silica sol), 2 g of metakaolin and 0.649 g of water; the raw material CsOH.H2O in a container(such as beaker, etc.), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (i.e. silica sol) and dissolving in an alkali activator, finally adding metakaolin, stirring for 30min to obtain slurry, pouring the slurry (stirred) into a mould, drying in a drying oven (constant temperature blast) at the temperature of 80 ℃ for 24h, taking out, cooling to room temperature, and demoulding to obtain the soil containing Cs;
b. preparing materials: taking the Cs-containing soil and the glass powder according to the mass percentage of 90% of the Cs-containing soil and 10% of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture (the particle size of the mixed material is less than 200 meshes);
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 800 ℃ for 8 hours, and then cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body.
Through detection: the prepared glass ceramic body of the solidified Cs-containing soil is soaked in deionized water at the temperature of 90 ℃ for 28 days, and the weight loss rate of the Cs element is less than 1 multiplied by 10-2 g·m-2·d-1The microhardness of the glass ceramic solidified body is more than 650 MPa.
Example 4:
a preparation method of a glass ceramic body for solidifying Cs-containing soil comprises the following steps:
a. preparing Cs-containing soil: taking raw material CsOH.H2O 3.016 g、Sol-SiO22.8504 g (namely silica sol), 2 g of metakaolin and 0.649 g of water; the raw material CsOH.H2Adding O into a container (such as beaker), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (i.e. silica sol) and dissolving in an alkali activator, finally adding metakaolin, stirring for 15min to obtain slurry, pouring the slurry (stirred) into a mould, drying in a drying oven (constant temperature blast) at the temperature of 68 ℃ for 35h, taking out, cooling to room temperature, and demoulding to obtain the soil containing Cs;
b. preparing materials: taking the Cs-containing soil and the glass powder according to the mass percentage of 80% of the Cs-containing soil and 20% of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture (the particle size of the mixed material is less than 200 meshes);
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 800 ℃ for 8 hours, and then cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body.
Through detection: the prepared glass ceramic body of the solidified Cs-containing soil is soaked in deionized water at the temperature of 90 ℃ for 28 days, and the weight loss rate of the Cs element is less than 1 multiplied by 10-2 g·m-2·d-1And the microhardness of the glass ceramic solidified body is more than 800 MPa.
Example 5:
a preparation method of a glass ceramic body for solidifying Cs-containing soil comprises the following steps:
a. preparing Cs-containing soil: taking raw material CsOH.H2O 3.016 g、Sol-SiO22.8504 g (namely silica sol), 2 g of metakaolin and 0.649 g of water; the raw material CsOH.H2Adding O into a container (such as beaker), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (i.e. silica sol) and dissolving in an alkali activator, finally adding metakaolin, stirring for 25min to obtain slurry, pouring the slurry (stirred) into a mould, drying in a drying oven (constant temperature blast) at the temperature of 75 ℃ for 40h, taking out, cooling to room temperature, and demoulding to obtain the soil containing Cs;
b. preparing materials: taking the Cs-containing soil and the glass powder according to the mass percentage of 80% of the Cs-containing soil and 20% of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture (the particle size of the mixed material is less than 200 meshes);
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 900 ℃ for 8 hours, and then cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body.
Through detection: the prepared glass ceramic body of the solidified Cs-containing soil is soaked in deionized water at the temperature of 90 ℃ for 28 days, and the weight loss rate of the Cs element is less than 1 multiplied by 10-2 g·m-2·d-1The microhardness of the glass ceramic solidified body is more than 900 MPa.
Example 6:
a preparation method of a glass ceramic body for solidifying Cs-containing soil comprises the following steps:
a. preparing Cs-containing soil: taking raw material CsOH.H2O 3.016 g、Sol-SiO22.8504 g (namely silica sol), 2 g of metakaolin and 0.649 g of water; the raw material CsOH.H2Adding O into a container (such as beaker), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (i.e. silica sol) and dissolving in an alkali activator, finally adding metakaolin, stirring for 30min to obtain slurry, pouring the slurry (stirred) into a mould, drying in a drying oven (constant temperature blast) at the temperature of 80 ℃ for 24h, taking out, cooling to room temperature, and demoulding to obtain the soil containing Cs;
b. preparing materials: taking the Cs-containing soil and the glass powder according to the mass percentage of 70% of the Cs-containing soil and 30% of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture (the particle size of the mixed material is less than 200 meshes);
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 900 ℃ for 8 hours, and then cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body.
Through detection: the prepared glass ceramic body of the solidified Cs-containing soil is soaked in deionized water at the temperature of 90 ℃ for 28 days, and the weight loss rate of the Cs element is less than 1 multiplied by 10-2 g·m-2·d-1The microhardness of the glass ceramic solidified body is more than 1000 MPa.
Example 7:
a preparation method of a glass ceramic body for solidifying Cs-containing soil comprises the following steps:
a. preparing Cs-containing soil: taking raw material CsOH.H2O 3.016 g、Sol-SiO22.8504 g (namely silica sol), 2 g of metakaolin and 0.649 g of water; the raw material CsOH.H2Adding O into a container (such as beaker), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (i.e. silica sol) and dissolving in an alkali activator, finally adding metakaolin, stirring for 28min to obtain slurry, pouring the slurry (stirred) into a mould, drying for 43h in a (constant temperature blast) drying oven at the temperature of 73 ℃, taking out, cooling to room temperature, and demoulding to obtain the soil containing Cs;
b. preparing materials: taking the Cs-containing soil and the glass powder according to the mass percentage of 70% of the Cs-containing soil and 30% of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture (the particle size of the mixed material is less than 200 meshes);
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 900 ℃ for 2 hours, and then cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body.
Through detection: the prepared glass ceramic body of the solidified Cs-containing soil is soaked in deionized water at the temperature of 90 ℃ for 28 days, and the weight loss rate of the Cs element is less than 1 multiplied by 10-2 g·m-2·d-1And the microhardness of the glass ceramic solidified body is more than 800 MPa.
Example 8:
a preparation method of a glass ceramic body for solidifying Cs-containing soil comprises the following steps:
a. preparing Cs-containing soil: according to CsOH.H2O3.016 weight portions and Sol-SiO22.8504 parts of (namely silica sol), 2 parts of metakaolin and 0.649 part of water (preferably deionized water) by mass, and the raw material CsOH & H is taken2O、Sol-SiO2(i.e., silica sol), metakaolin, and water; the raw material CsOH.H2Adding O into a container (such as beaker), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (namely silica sol) and dissolving in an alkali activator, finally adding metakaolin, stirring for 5-30 min to obtain slurry, pouring the slurry (stirred) into a mould, drying in a (constant temperature blast) drying oven at the temperature of 60-80 ℃ for 24-48 h, taking out, cooling to room temperature, and demoulding to obtain the soil containing Cs;
b. preparing materials: taking the Cs-containing soil and the glass powder according to the mass percentage of 40% of the Cs-containing soil and 60% of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture;
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 700 ℃ for 2 hours, and then cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body.
Through detection: the prepared glass ceramic body of the solidified Cs-containing soil is soaked in deionized water at the temperature of 90 ℃ for 28 days, and the weight loss rate of the Cs element is less than 1 multiplied by 10-2 g·m-2·d-1The microhardness of the glass ceramic solidified body is more than 600 MPa.
Example 9:
a preparation method of a glass ceramic body for solidifying Cs-containing soil comprises the following steps:
a. preparing Cs-containing soil: according to CsOH.H2O3.016 weight portions and Sol-SiO22.8504 parts of (namely silica sol), 2 parts of metakaolin and 0.649 part of water (preferably deionized water) by mass, and the raw material CsOH & H is taken2O、Sol-SiO2(i.e., silica sol), metakaolin, and water; the raw material CsOH.H2Adding O into a container (such as beaker), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (i.e. silica sol) with alkali activator, adding metakaolin, stirring for 5min to obtain slurry, and mixingPouring the good) slurry into a mold, drying in a (constant temperature blast) drying oven at the temperature of 60 ℃ for 48h, taking out, cooling to room temperature, and demolding to obtain the soil containing Cs;
b. preparing materials: taking the soil containing the Cs and the glass powder according to the mass percentage of 50 percent of the soil containing the Cs and 50 percent of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture;
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 700 ℃ for 8 hours, and then cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body.
Through detection: the prepared glass ceramic body of the solidified Cs-containing soil is soaked in deionized water at the temperature of 90 ℃ for 28 days, and the weight loss rate of the Cs element is less than 1 multiplied by 10-2 g·m-2·d-1The microhardness of the glass ceramic solidified body is more than 600 MPa.
Example 10:
a preparation method of a glass ceramic body for solidifying Cs-containing soil comprises the following steps:
a. preparing Cs-containing soil: according to CsOH.H2O3.016 weight portions and Sol-SiO22.8504 parts of (namely silica sol), 2 parts of metakaolin and 0.649 part of water (preferably deionized water) by mass, and the raw material CsOH & H is taken2O、Sol-SiO2(i.e., silica sol), metakaolin, and water; the raw material CsOH.H2Adding O into a container (such as beaker), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (i.e. silica sol) and dissolving in an alkali activator, finally adding metakaolin, stirring for 30min to obtain slurry, pouring the slurry (stirred) into a mould, drying in a drying oven (constant temperature blast) at the temperature of 80 ℃ for 24h, taking out, cooling to room temperature, and demoulding to obtain the soil containing Cs;
b. preparing materials: taking the Cs-containing soil and the glass powder according to the mass percentage of 60 percent of the Cs-containing soil and 40 percent of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture;
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 1000 ℃ for 2 hours, and then cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body.
Through detection: the prepared glass ceramic body of the solidified Cs-containing soil is soaked in deionized water at the temperature of 90 ℃ for 28 days, and the weight loss rate of the Cs element is less than 1 multiplied by 10-2 g·m-2·d-1And the microhardness of the glass ceramic solidified body is more than 800 MPa.
Example 11:
a preparation method of a glass ceramic body for solidifying Cs-containing soil comprises the following steps:
a. preparing Cs-containing soil: according to CsOH.H2O3.016 weight portions and Sol-SiO22.8504 parts of (namely silica sol), 2 parts of metakaolin and 0.649 part of water (preferably deionized water) by mass, and the raw material CsOH & H is taken2O、Sol-SiO2(i.e., silica sol), metakaolin, and water; the raw material CsOH.H2Adding O into a container (such as beaker), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (i.e. silica sol) and dissolving in an alkali activator, finally adding metakaolin, stirring for 17min to obtain slurry, pouring the slurry (stirred) into a mould, drying in a drying oven (constant temperature blast) at the temperature of 72 ℃ for 38h, taking out, cooling to room temperature, and demoulding to obtain the soil containing Cs;
b. preparing materials: taking the Cs-containing soil and the glass powder according to the mass percentage of 70% of the Cs-containing soil and 30% of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture;
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 850 ℃ for 5 hours, and then cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body.
Through detection: the prepared glass ceramic body of the solidified Cs-containing soil is soaked in deionized water at the temperature of 90 ℃ for 28 days, and the weight loss rate of the Cs element is less than 1 multiplied by 10-2 g·m-2·d-1And the microhardness of the glass ceramic solidified body is more than 700 MPa.
Example 12:
a preparation method of a glass ceramic body for solidifying Cs-containing soil comprises the following steps:
a. preparing Cs-containing soil: according to CsOH.H2O3.016 weight portions and Sol-SiO22.8504 parts of (namely silica sol), 2 parts of metakaolin and 0.649 part of water (preferably deionized water) by mass, and the raw material CsOH & H is taken2O、Sol-SiO2(i.e., silica sol), metakaolin, and water; the raw material CsOH.H2Adding O into a container (such as beaker), adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing (i.e. silica sol) and dissolving in an alkali activator, finally adding metakaolin, stirring for 22min to obtain slurry, pouring the slurry (stirred) into a mould, drying in a drying oven (constant temperature blast) at the temperature of 78 ℃ for 45h, taking out, cooling to room temperature, and demoulding to obtain the soil containing Cs;
b. preparing materials: taking the Cs-containing soil and the glass powder according to the mass percentage of 80% of the Cs-containing soil and 20% of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding (or called grinding, or grinding by using a ball mill) to obtain a mixture;
d. tabletting: pressing the mixture (by a hydraulic press) into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 900 ℃ for 6 hours, and then cooling along with the furnace to obtain the cured Cs-containing soil glass ceramic body.
Through detection: the prepared glass ceramic body of the solidified Cs-containing soil is soaked in deionized water at the temperature of 90 ℃ for 28 days, and the weight loss rate of the Cs element is less than 1 multiplied by 10-2 g·m-2·d-1And the microhardness of the glass ceramic solidified body is more than 800 MPa.
In the above embodiment: the Cs-containing soil prepared in the step a mainly comprises the following chemical components in percentage by mass: Si/Al is fixed to be 2, Cs/Al is fixed to be 1, and the water-gel ratio is fixed to be 0.3, wherein Si and Al are composed of metakaolin and Sol-SiO2Introducing Cs from CsOH. H2And introducing O.
In the above embodiment: the glass powder in the ingredients in the step b can be prepared from the following main chemical components in percentage by mass: SiO 22 41%～59%、B2O3 8%～25%、Na2O 20%～33%、A12O3 0%～7%、CaO 0%～5%、ZrO20 to 3 percent, and the sum of all the components is 100 percent.
In examples 1-6 above: the glass powder in the ingredients in the step b comprises the following main chemical components in percentage by mass: SiO 22 58.87%、B2O3 8.98%、Na2O 20.17%、A12O3 5.99%、CaO 3.99%、ZrO2 2.00%。
In examples 7 to 12 above: the glass powder in the ingredients in the step b comprises the following main chemical components in percentage by mass: SiO 22 42.50%、B2O3 24.60%、Na2O 32.88%。
In the above embodiment: all the raw materials are commercially available products.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the parts by mass (by weight) may all be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, etc.) and the numerical values of the components in each step are in the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above embodiments are the same as the prior art.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (8)
1. A preparation method of a glass ceramic body for solidifying Cs-containing soil is characterized by comprising the following steps:
a. preparing Cs-containing soil: taking raw material CsOH.H2O、Sol-SiO2Metakaolin and water; the raw material CsOH.H2Adding O into a container, adding water, mixing to obtain alkali activator, adding Sol-SiO2Mixing, finally adding metakaolin, stirring for 5-30 min to obtain slurry, pouring the slurry into a mold, drying in a drying oven at the temperature of 60-80 ℃ for 24-48 h, taking out, cooling to room temperature, and demolding to obtain the soil containing Cs;
b. preparing materials: taking the soil containing the Cs and the glass powder according to the mass percentage of 50-90% of the soil containing the Cs and 10-50% of the glass powder;
c. mixing: mixing the Cs-containing soil and the glass powder, and grinding to obtain a mixture;
d. tabletting: pressing the mixture into a sheet shape to obtain a sheet-shaped mixture;
e. firing: and heating and preserving the temperature of the flaky mixture at 700-1000 ℃ for 2-8 hours, and then cooling along with a furnace to obtain the cured Cs-soil-containing glass ceramic body.
2. The process for producing a glass ceramic body of solidified Cs-containing soil as set forth in claim 1 or 2, wherein: taking the raw material CsOH & H in the step a2O、Sol-SiO2Metakaolin and water in a ratio CsOH. H2O3.016 weight portions and Sol-SiO22.8504 parts by mass, 2 parts by mass of metakaolin and 0.649 part by mass of water, and taking the raw material CsOH & H2O、Sol-SiO2Metakaolin and water.
3. The process for producing a glass ceramic body of solidified Cs-containing soil as set forth in claim 1 or 2, wherein: the Cs-containing soil prepared in the step a mainly comprises the following chemical components in percentage by mass: Si/Al is fixed to be 2, Cs/Al is fixed to be 1, and the water-gel ratio is fixed to be 0.3, wherein Si and Al are composed of metakaolin and Sol-SiO2Introducing Cs from CsOH. H2And introducing O.
4. The process for producing a glass ceramic body of solidified Cs-containing soil as set forth in claim 1 or 2, wherein: in the ingredient of the step b, the main chemical compositions and mass percentages of the glass powder are as follows: SiO 22 41%～59%、B2O3 8%～25%、Na2O 20%～33%、A12O3 0%～7%、CaO 0%～5%、ZrO20 to 3 percent, and the sum of all the components is 100 percent.
5. The process for producing a glass ceramic body of solidified Cs-containing soil as set forth in claim 1 or 2, wherein: the glass powder in the ingredients in the step b comprises the following main chemical components in percentage by mass: SiO 22 58.87%、B2O3 8.98%、Na2O 20.17%、A12O3 5.99%、CaO 3.99%、ZrO2 2.00%。
6. The process for producing a glass ceramic body of solidified Cs-containing soil as set forth in claim 1 or 2, wherein: the glass powder in the ingredients in the step b comprises the following main chemical components in percentage by mass: SiO 22 42.50%、B2O3 24.60%、Na2O 32.88%。
7. The process for producing a glass ceramic body of solidified Cs-containing soil as set forth in claim 1 or 2, wherein: and c, grinding in the mixing step is carried out by adopting a ball mill, and the particle size of the mixed material after grinding is less than 200 meshes.
8. The process for producing a glass ceramic body of solidified Cs-containing soil as set forth in claim 1 or 2, wherein: and e, firing, namely heating and insulating the flaky mixture at the temperature of 700-900 ℃ for 2-8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011586208.8A CN112466503A (en) | 2020-12-29 | 2020-12-29 | Preparation method of glass ceramic body for solidifying Cs-containing soil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011586208.8A CN112466503A (en) | 2020-12-29 | 2020-12-29 | Preparation method of glass ceramic body for solidifying Cs-containing soil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112466503A true CN112466503A (en) | 2021-03-09 |
Family
ID=74804586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011586208.8A Pending CN112466503A (en) | 2020-12-29 | 2020-12-29 | Preparation method of glass ceramic body for solidifying Cs-containing soil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112466503A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113979642A (en) * | 2021-11-15 | 2022-01-28 | 中广核研究院有限公司 | Glass solidified body of non-flammable radioactive waste and cooperative glass solidification method |
| CN114213019A (en) * | 2021-12-31 | 2022-03-22 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of sodium-calcium geopolymer glass ceramic filled with phosphate glass |
| CN114276060A (en) * | 2021-12-31 | 2022-04-05 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of glass-doped radioactive nuclear waste geopolymer solidified body applicable to microwave method |
| CN114550964A (en) * | 2021-12-27 | 2022-05-27 | 中国原子能科学研究院 | Method for the ceramic curing of radioactive cesium waste in a zeolite-silica gel system |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2497188A1 (en) * | 1980-12-27 | 1982-07-02 | Central Glass Co Ltd | ENAMELLED CERAMIC SUBSTRATE |
| CN103680660A (en) * | 2013-12-03 | 2014-03-26 | 南京大学 | Application of cullet in solidifying radionuclide and normal temperature solidifying method for waste comprising radioactive Cs+ |
| CN104528746A (en) * | 2014-12-04 | 2015-04-22 | 西南科技大学 | Preparation method of microcrystalline pollucite |
| US20150299036A1 (en) * | 2012-11-20 | 2015-10-22 | Ljerka Ukrainczyk | Method of making three dimensional glass ceramic article |
| CN105731899A (en) * | 2016-02-04 | 2016-07-06 | 哈尔滨工业大学 | Method for synthesizing pollucite by means of aluminosilicate polymer |
| CN105810279A (en) * | 2016-03-30 | 2016-07-27 | 中国科学院上海应用物理研究所 | Fluorine-containing and/or fluorine radioactive waste glass ceramic solidified body and preparation method thereof |
| CN107352550A (en) * | 2017-08-16 | 2017-11-17 | 西南科技大学 | A kind of preparation method of kilogram of yield level pollucite sub-micron ball |
| WO2018143205A1 (en) * | 2017-02-03 | 2018-08-09 | 株式会社東芝 | Geopolymer molding production method and geopolymer molding production system |
| JP2019045453A (en) * | 2017-09-07 | 2019-03-22 | 太平洋セメント株式会社 | Method of immobilizing cesium of cesium-containing waste |
| CN109704351A (en) * | 2019-03-05 | 2019-05-03 | 西南科技大学 | A kind of low temperature of pollucite exempts to calcine preparation method |
| WO2020055337A1 (en) * | 2018-09-14 | 2020-03-19 | Vuje, A.S. | Additives for vitrification of liquid radioactive cesium radionuclides-containing wastes having high retention efficiency of said radionuclides over the entire range of vitrification temperature, method of their preparation and their use |
| CN110970146A (en) * | 2019-11-27 | 2020-04-07 | 中国建筑材料科学研究总院有限公司 | Borosilicate glass ceramic curing substrate and preparation method and application thereof |
| CN110981205A (en) * | 2019-12-25 | 2020-04-10 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of microcrystalline glass for treating radioactive cesium polluted soil |
| CN111233336A (en) * | 2020-02-26 | 2020-06-05 | 西南科技大学 | Low-temperature preparation method of strontium and cesium glass ceramic co-cured body |
-
2020
- 2020-12-29 CN CN202011586208.8A patent/CN112466503A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2497188A1 (en) * | 1980-12-27 | 1982-07-02 | Central Glass Co Ltd | ENAMELLED CERAMIC SUBSTRATE |
| US20150299036A1 (en) * | 2012-11-20 | 2015-10-22 | Ljerka Ukrainczyk | Method of making three dimensional glass ceramic article |
| CN103680660A (en) * | 2013-12-03 | 2014-03-26 | 南京大学 | Application of cullet in solidifying radionuclide and normal temperature solidifying method for waste comprising radioactive Cs+ |
| CN104528746A (en) * | 2014-12-04 | 2015-04-22 | 西南科技大学 | Preparation method of microcrystalline pollucite |
| CN105731899A (en) * | 2016-02-04 | 2016-07-06 | 哈尔滨工业大学 | Method for synthesizing pollucite by means of aluminosilicate polymer |
| CN105810279A (en) * | 2016-03-30 | 2016-07-27 | 中国科学院上海应用物理研究所 | Fluorine-containing and/or fluorine radioactive waste glass ceramic solidified body and preparation method thereof |
| WO2018143205A1 (en) * | 2017-02-03 | 2018-08-09 | 株式会社東芝 | Geopolymer molding production method and geopolymer molding production system |
| CN107352550A (en) * | 2017-08-16 | 2017-11-17 | 西南科技大学 | A kind of preparation method of kilogram of yield level pollucite sub-micron ball |
| JP2019045453A (en) * | 2017-09-07 | 2019-03-22 | 太平洋セメント株式会社 | Method of immobilizing cesium of cesium-containing waste |
| WO2020055337A1 (en) * | 2018-09-14 | 2020-03-19 | Vuje, A.S. | Additives for vitrification of liquid radioactive cesium radionuclides-containing wastes having high retention efficiency of said radionuclides over the entire range of vitrification temperature, method of their preparation and their use |
| CN109704351A (en) * | 2019-03-05 | 2019-05-03 | 西南科技大学 | A kind of low temperature of pollucite exempts to calcine preparation method |
| CN110970146A (en) * | 2019-11-27 | 2020-04-07 | 中国建筑材料科学研究总院有限公司 | Borosilicate glass ceramic curing substrate and preparation method and application thereof |
| CN110981205A (en) * | 2019-12-25 | 2020-04-10 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of microcrystalline glass for treating radioactive cesium polluted soil |
| CN111233336A (en) * | 2020-02-26 | 2020-06-05 | 西南科技大学 | Low-temperature preparation method of strontium and cesium glass ceramic co-cured body |
Non-Patent Citations (1)
| Title |
|---|
| 刘东亮: "《材料科学基础》", 30 September 2016 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113979642A (en) * | 2021-11-15 | 2022-01-28 | 中广核研究院有限公司 | Glass solidified body of non-flammable radioactive waste and cooperative glass solidification method |
| CN114550964A (en) * | 2021-12-27 | 2022-05-27 | 中国原子能科学研究院 | Method for the ceramic curing of radioactive cesium waste in a zeolite-silica gel system |
| CN114550964B (en) * | 2021-12-27 | 2024-02-20 | 中国原子能科学研究院 | Method for solidifying zeolite-silica gel system ceramic of radioactive cesium waste |
| CN114213019A (en) * | 2021-12-31 | 2022-03-22 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of sodium-calcium geopolymer glass ceramic filled with phosphate glass |
| CN114276060A (en) * | 2021-12-31 | 2022-04-05 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of glass-doped radioactive nuclear waste geopolymer solidified body applicable to microwave method |
| CN114213019B (en) * | 2021-12-31 | 2023-07-21 | 中建材玻璃新材料研究院集团有限公司 | Preparation method of phosphate glass filled sodium-calcium geopolymer glass ceramic |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112466503A (en) | Preparation method of glass ceramic body for solidifying Cs-containing soil | |
| US4297304A (en) | Method for solidifying aqueous radioactive wastes for non-contaminating storage | |
| US6133498A (en) | Method for producing chemically bonded phosphate ceramics and for stabilizing contaminants encapsulated therein utilizing reducing agents | |
| US4514329A (en) | Process for vitrifying liquid radioactive waste | |
| CN110092588B (en) | Borosilicate glass ceramic curing substrate and preparation method and application thereof | |
| US4097401A (en) | Thermodynamically stable product for permanent storage and disposal of highly radioactive liquid wastes | |
| US4354954A (en) | Method for solidifying aqueous radioactive wastes for noncontaminating storage | |
| CN110970146A (en) | Borosilicate glass ceramic curing substrate and preparation method and application thereof | |
| US4661291A (en) | Method for fixation of incinerator ash or iodine sorbent | |
| CN109994240B (en) | Method for reducing solidifying and melting temperature of radionuclide-polluted sandy soil glass | |
| CN110291593B (en) | Compositions and methods for treating hazardous sludge and ion exchange media | |
| US4094809A (en) | Process for solidifying high-level nuclear waste | |
| JPS6120839B2 (en) | ||
| CN110606664B (en) | Method for preparing pyrochlore phase borosilicate glass ceramic cured substrate by one-step method | |
| Yang et al. | Effect of on the Immobilization of High-Level Waste with Magnesium Potassium Phosphate Ceramic | |
| US4482481A (en) | Method of preparing nuclear wastes for tansportation and interim storage | |
| US3993579A (en) | Method of encapsulating solid radioactive waste material for storage | |
| EP0054604B1 (en) | Process for preparing spent solid bodies for the final disposal of radioactive wastes | |
| US5875407A (en) | Method for synthesizing pollucite from chabazite and cesium chloride | |
| KR101578623B1 (en) | A method of making low-melting temperature glass to immobilize radioactive cesium spent filter | |
| RU2727711C1 (en) | Conditioning method of tritium-containing water | |
| CN110028248B (en) | Method for preparing pollucite microcrystalline glass by low-temperature liquid phase sintering | |
| CN114394784A (en) | Preparation method of glass-doped radioactive nuclear waste geopolymer-based solidified body | |
| RU2165110C2 (en) | Ceramic sponge for concentration and hardening of liquid extrahazardous waste and method for its production | |
| EP1412950B1 (en) | Encapsulation of waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210309 |
|
| RJ01 | Rejection of invention patent application after publication |