CN104310781B - A kind of glass basis composition and glass solidified body prepared therefrom for middle low-level radioactivity combustible waste burning ash - Google Patents
A kind of glass basis composition and glass solidified body prepared therefrom for middle low-level radioactivity combustible waste burning ash Download PDFInfo
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- CN104310781B CN104310781B CN201410534421.2A CN201410534421A CN104310781B CN 104310781 B CN104310781 B CN 104310781B CN 201410534421 A CN201410534421 A CN 201410534421A CN 104310781 B CN104310781 B CN 104310781B
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- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
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Abstract
The invention discloses a kind of glass basis composition and glass solidified body prepared therefrom for middle low-level radioactivity combustible waste burning ash.The special physico-chemical property of the middle low-level radioactivity combustible wastes such as blotting paper, cotton products, plastic cloth, the rubber produced for nuclear facilities, the present invention each provides the glass basis composition suitable for combustible wastes such as blotting paper, cotton products, plastic cloth, rubber.Glass solidified body of the present invention can meet density, compression strength, impact strength and radiation-resistant property requirement after the weight-loss ratio of solidification of radwaste body, immersion.
Description
Technical field
The invention belongs to Radwastes treatment solidification field, in particular it relates to a kind of can for middle low-level radioactivity
The glass basis composition and glass solidified body prepared therefrom of combustion incineration of waste ash.
Background technology
The middle cool waste that nuclear facilities runs and retired period produces includes process waste and technology waste, and species is multiple
It is miscellaneous, enormous amount.By taking Daya Bay nuclear power plant as an example, the accounting such as blotting paper, cotton products, plastics and rubber in its common technique waste
More than 80%.How these flammable radwastes to be processed, is disposed, be a challenging technical barrier, at present
Each advanced country is all carrying out relation technological researching.
For the treatment of middle low-level radioactivity combustible waste, mainly there is the cement of compacting solidification method and burning ash at present
Solidification method, bitumen solidification method, plastics solidification method etc..Compacting solidification method be the waste after burning is added after certain chemical substance
Confined space carries out hot pressing, and its anti-leaching and volume reduction ratio are preferable compared with cement solidification method, but still undesirable；Cement solidification method
Shortcoming be waste increase-volume substantially, flatulence can occur after being immersed in water it is swelling so as to cause the cracking of firming body and destruction, and
Anti-leaching is poor；The shortcoming of bitumen solidification method is poor heat endurance, and vented exhaust requirement is high, and danger coefficient is big, rotten to equipment
Erosion is big；The shortcoming of plastics solidification method is complicated process route, and additive types are various, explosive and relatively costly.
The glass solidification of radwaste is by the generally accepted form for meeting safe disposal of present people.Being of glass
The inactive material of property is learned, has liquid property in the condition of high temperature, many oxides can be dissolved so that the element in waste contains
It is fixed in glass network structure, radwaste is burned, radionuclide is embedded in hyaloid host material,
The migration of radionuclide so can will be effectively controlled, the leaching rate of vitreum is very low and is suitable to final disposal, and its performance is far excellent
In solidified cement body.In the past, glass solidification technology was the technology of a complexity and costliness, is generally used only for high activity liquid waste and uses it
The reluctant special waste of its technology.At present, the maturation with technology and development, its excellent firming body performance and corrosion are anti-
The improvement of nurse's skill promotes glass solidification technology to process Directional Extension to middle low-level waste（Low medium level waste, high radioactivity
The classification of waste is with reference to GB 9133-1995《The classification of radwaste》）.
China introduces glass solidification technical finesse high activity liquid waste by 821 factories earliest, but using plasma is burned and combines glass
Low-level waste research aspect is just at the early-stage in the treatment of glass curing technology.Therefore, find a kind of suitable for middle low-level radioactivity
Glass basis composition, glass solidified body of combustible waste and preparation method thereof are very urgent for nuclear industry field
's.
The content of the invention
The technical problems to be solved by the invention are to provide one kind and can be used in middle low-level radioactivity combustible waste burning
The glass basis composition of ash.
Further, the present invention also provides a kind of glass solidified body and preparation method thereof.
The middle low-level radioactivity such as blotting paper, cotton products, plastic cloth, the rubber that the present inventor produces for nuclear facilities are flammable
The special physico-chemical property of waste, mainly considers the oxidation that ash content is stayed after various middle low-level radioactivity combustible wastes are burned
Thing（Weight portion sum is 100wt%）With Co, Sr, Cs oxide added as tracer（Weight portion sum is 0.6wt%, should
Part it is that the oxide of ash content is stayed with after burning is 100wt% calculating）, study and obtain its respective glass basis optimum formula, obtain
To the glass basis composition that can be applied to the radioactive blotting paper of middle low-level, cotton products, plastic cloth, rubber, and by it
The chemical stability of obtained glass solidified body, mechanical stability and radiation-resistant property are good.
A kind of glass basis composition for middle low-level radioactivity cotton products burning ash, including following weight portion group
Point：
SiO2：45-70 weight portions, B2O3：9-15 weight portions, Na2O：10-18 weight portions, CaO：3-10 weight portions, Al2O3：
3-6 weight portions, Li2O：0-3 weight portions, TiO2：0-3 weight portions.
Wherein, in the glass basis composition of the cotton products burning ash, the SiO2Content can be 50-65 weight
Part, further preferred 55-65 weight portions.The B2O3Content can be 9-13 weight portions, further preferred 11-13 weight
Part.The Na2The content of O can be 10-15 weight portions, further preferred 12-15 weight portions.The content of the CaO can be
3-8 weight portions, further preferred 3-6 weight portions.The Al2O3Content can preferred 4-6 weight portions.The Li2The content of O
Can preferred 0-2 weight portions.The TiO2Content can preferred 1-3 weight portions.
A kind of glass basis composition for middle low-level radioactivity blotting paper burning ash, including following weight portion group
Point：
SiO2：45-70 weight portions, B2O3：9-18 weight portions, Na2O：6-14 weight portions, CaO：6-12 weight portions, Al2O3：
3-6 weight portions, Li2O：0-3 weight portions, TiO2：0-3 weight portions.
Wherein, in the glass basis composition of the blotting paper burning ash, the SiO2Content can be 50-70 weight
Amount part, still more preferably further preferred 50-65 weight portions, 50-60 weight portions.The B2O3Content can be 9-15 weight
Amount part, further preferred 12-15 weight portions.The Na2The content of O can be 9-14 weight portions, further preferred 9-11 weight
Part.The content of the CaO can be 8-12 weight portions, further preferred 10-12 weight portions.The Al2O3Content can be with excellent
Select 4-6 weight portions.The Li2The content of O can preferred 0-2 weight portions.The TiO2Content can preferred 1-3 weight portions
。
A kind of glass basis composition for middle low-level radioactivity rubber burning ash, including following weight portion group
Point：
SiO2：45-70 weight portions, B2O3：9-18 weight portions, Na2O：8-16 weight portions, CaO：0-3 weight portions, Al2O3：3-
6 weight portions, Li2O：0-3 weight portions, TiO2：0-3 weight portions.
Wherein, in the glass basis composition of the rubber burning ash, the SiO2Content can be 50-65 weight
Part, further preferred 55-65 weight portions.The B2O3Content can be 9-15 weight portions, further preferred 10-13 weight
Part.The Na2The content of O can be 8-14 weight portions, further preferred 8-11 weight portions.The content of the CaO can be
1-3 weight portions, further preferred 2-3 weight portions.The Al2O3Content can preferred 4-6 weight portions.The Li2O's contains
Amount can preferred 0-2 weight portions.The TiO2Content can preferred 1-3 weight portions.
A kind of glass basis composition for middle low-level radioactivity plastic cloth burning ash, including following weight portion group
Point：
SiO2：45-70 weight portions, B2O3：9-15 weight portions, Na2O：10-18 weight portions, CaO：1-4 weight portions, Al2O3：
3-6 weight portions, Li2O：0-3 weight portions, TiO2：0-3 weight portions.
Wherein, in the glass basis composition of the plastic cloth burning ash, the SiO2Content can be 50-65 weight
Amount part, further preferred 55-65 weight portions.The B2O3Content can be 9-14 weight portions, further preferred 10-12 weight
Part.The Na2The content of O can be 10-15 weight portions, further preferred 10-13 weight portions.The content of the CaO can be with
It is 1-3 weight portions, further preferred 2-3 weight portions.The Al2O3Content can preferred 4-6 weight portions.The Li2O's
Content can preferred 0-2 weight portions.The TiO2Content can preferred 1-3 weight portions.
A kind of glass solidified body of middle low-level radioactivity cotton products burning ash, including glass basis composition and described
Cotton products burning ash simulation substance,
The glass basis composition, including following weight portion component：
SiO2：45-70 weight portions, B2O3：9-15 weight portions, Na2O：10-18 weight portions, CaO：3-10 weight portions, Al2O3：
3-6 weight portions, Li2O：0-3 weight portions, TiO2：0-3 weight portions；
The cotton products burning ash simulation substance, is counted with the cotton products burning ash simulation substance as 100 weight portions, bag
Include the component of following weight portion：
SiO2：14.6 weight portions, B2O3：4.00 weight portions, Na2O：1.00%、CaO：73.3 weight portions, Al2O3：：2.34 weights
Amount part, Fe2O3：2.96 weight portions, SO3：1.80 weight portions, CoO：0.2 weight portion, Cs2O：0.2 weight portion, SrO：0.2 weight
Part.
A kind of glass solidified body of middle low-level radioactivity blotting paper burning ash, including glass basis composition and described
Blotting paper burning ash simulation substance,
The glass basis composition, including following weight portion component：
SiO2：45-70 weight portions, B2O3：9-18 weight portions, Na2O：6-14 weight portions, CaO：6-12 weight portions, Al2O3：
3-6 weight portions, Li2O：0-3 weight portions, TiO2：0-3 weight portions；
The blotting paper burning ash simulation substance, is counted with the blotting paper burning ash simulation substance as 100 weight portions, bag
Include the component of following weight portion：
SiO2：24.7 weight portions, B2O3：1.74 weight portions, Na2O：17.8 weight portions, CaO：49.1 weight portions, Al2O3：
2.67 weight portions, Fe2O3：1.65 weight portions, SO3：2.34 weight portions, CoO：0.2 weight portion, Cs2O：0.2 weight portion, SrO：
0.2 weight portion.
A kind of glass solidified body of middle low-level radioactivity rubber burning ash, including glass basis composition and the rubber
Glue burning ash simulation substance,
The glass basis composition, including following weight portion component：
SiO2：45-70 weight portions, B2O3：9-18 weight portions, Na2O：8-16 weight portions, CaO：0-3 weight portions, Al2O3：3-
6 weight portions, Li2O：0-3 weight portions, TiO2：0-3 weight portions；
The rubber burning ash simulation substance, is counted with the rubber burning ash simulation substance as 100 weight portions, including with
The component of lower weight portion：
SiO2：0.867 weight portion, Na2O：0.054 weight portion, CaO：94.3 weight portions, Al2O3：0.489 weight portion, SO3：
4.29 weight portions, CoO：0.2 weight portion, Cs2O：0.2 weight portion, SrO：0.2 weight portion.
A kind of glass solidified body of middle low-level radioactivity plastic cloth burning ash, including glass basis composition and described
Plastic cloth burning ash simulation substance,
The glass basis composition, including following weight portion component：
SiO2：45-70 weight portions, B2O3：9-15 weight portions, Na2O：10-18 weight portions, CaO：1-4 weight portions, Al2O3：
3-6 weight portions, Li2O：0-3 weight portions, TiO2：0-3 weight portions；
The plastic cloth burning ash simulation substance, is counted with the plastic cloth burning ash simulation substance as 100 weight portions, bag
Include the component of following weight portion：
SiO2：2.24 weight portions, B2O3：0.750 weight portion, Na2O：0.080 weight portion, CaO：85.6 weight portions, Al2O3：
1.50 weight portions, Fe2O3：1.58 weight portions, SO3：8.25 weight portions, CoO：0.2 weight portion, Cs2O：0.2 weight portion, SrO：
0.2 weight portion.
Wherein, the middle low-level radioactivity cotton products be primarily referred to as nuclear industry with the article being made up of cotton material, such as
Cotton, cotton yarn, cotton earplug, work clothes, mitten etc..
Wherein, the middle low-level radioactivity plastic cloth is mainly including nuclear industry by polyvinyl chloride（PVC）, polyurethane
（TPU), polypropylene（PP), high density polyethylene (HDPE)（) or the cloth that is made of the various materials such as low density polyethylene (LDPE) (LDPE) HDPE.
Wherein, the middle low-level radioactivity rubber generally refers to the rubbers such as the Labor protection shoes sole of nuclear industry.
Wherein, in above-mentioned middle low-level radioactivity cotton products, blotting paper, rubber, the glass solidified body of plastic cloth burning ash,
The burning ash simulation substance（Calculated by oxide）With the glass basis composition（Calculated by oxide）Mass ratio be
2:10-7:10。
The present invention also provides a kind of preparation method of the glass solidified body of middle low-level radioactivity combustible waste burning ash, wraps
Include following steps：
A. dispensing：The component in the glass basis composition, and corresponding burning ash simulation substance are weighed in proportion
In component, ground and mixed；
B high-temperature calcinations：Founded at a temperature of more than 300 DEG C, in 1100-1300 DEG C of constant temperature 2-5h；
C is molded：Glass melts are cast in 400-600 DEG C of die for molding, glass solidified body is obtained；
D anneals：0.8-1.2 hours is incubated under conditions of 400-600 DEG C, room temperature is cooled to the furnace.
Wherein, the glass solidified body of the middle low-level radioactivity combustible waste burning ash includes middle low-level radioactivity rubber
The glass solidified body of glue burning ash, the glass solidified body of middle low-level radioactivity plastic cloth burning ash, middle low-level radioactivity cotton
The glass solidified body of the glass solidified body of product burning ash, middle low-level radioactivity blotting paper burning ash.
Wherein, in step a, the component in the burning ash simulation substance and glass basis composition is right with addition raw material
Should be related to for：1 part of quality Fe2O31 part of quality Fe of correspondence2O3Or 3.475 parts of quality FeSO4·7H2O；1 part of quality SO3Correspondence
3.475 parts of quality FeSO4·7H2O or 2.77 part of quality Al2(SO4)3·18H2O；1 part of quality CoO correspondence, 1 part of quality CoO；1 part
Quality Cs21.195 parts of quality CsCl of O correspondences；1 part of quality SrO correspondence, 1.425 parts of quality SrCO3；1 part of quality SiO21 part of correspondence
Quality SiO2；1 part of quality B2O31.8 parts of quality H of correspondence3BO3；1 part of quality Na21.71 parts of quality Na of O correspondences2CO3；1 part of quality
1 part of quality CaO of CaO correspondences；1 part of quality Li21 part of quality Li of O correspondences2O；1 part of quality Al2O31 part of quality Al of correspondence2O3；1 part of matter
Amount TiO21 part of quality TiO of correspondence2。
Wherein, in step a, the burning ash simulation substance（Calculated by oxide）With the glass basis composition（Press
Oxide is calculated）Mass ratio be 2:10-7:10.
The present inventor improves final firming body properties to improve combustible waste containing rate, analyzes nuclear facilities use
The chemical composition of middle low-level radioactivity combustible waste burning ash, employs Orthogonal Method and preferably goes out optimal glass solidified body and match somebody with somebody
Side, and firming body has been carried out weight-loss ratio, immersion after density, compression strength, impact strength, radiation-resistant property detection checking this
The properties of the described glass solidified body of invention are good：
1st, combustible waste volume reduction ratio is improved
Glass basis composition of the present invention only needs the component of certain content, you can make blotting paper, cotton products, plastics
The combustible wastes such as cloth, rubber turn into the glass solidified body that volume significantly reduces under high-temperature calcination, and comprehensive volume reduction ratio is significantly carried
It is high.
2nd, firming body mechanical strength is improved
The compression strength of traditional cement solidification method gained firming body need to only meet ＞ 7MPa, generally 10-20MPa, and
The present invention develop obtained by glass solidified body compression strength be all higher than 80MPa, impact strength≤3cm2/ J, meets to solidification
Impact strength≤the 12cm of body2The requirement of/J, the raising of mechanical strength is conducive to the transhipment and disposal of solidification of waste body.
3rd, anti-leaching sexual satisfaction firming body performance requirement
The weight-loss ratio of glass solidified body of the present invention is below 15g/m2, low-level radioactive waste solidification in satisfaction
The related request of body（With reference to GB 14569.1-2011）.
4th, firming body radiation-resistant property is improved
Glass solidified body of the present invention increases less than 20% by its weight-loss ratio after irradiation.
In glass solidification technology, for waste different characteristics, the type selecting to matrix material is key link.Borosilicate
Glass is considered as the optimal material for solidifying activation products, fission product and actinides, is once commented in 20 kinds of solidified materials
Excellent middle score value highest, this research is using glass based on the type glass.
The performance indications that glass solidified body must reach are taken into full account, influence to personnel health and environment and to technique
Control the need for performance and to cost, the parent glass of this work is made up of 7 kinds of components：SiO2、B2O3、Na2O、CaO、
Li2O、Al2O3And TiO2.Wherein SiO2And B2O3It is glass network formers, is the element of borosilicate glass；
Na2O is glass network modifier oxides, is the good cosolvent of glass；CaO is also glass network modifier oxides, can be appropriate
The chemical stability and mechanical strength of glass are improved, the containing ability to sulfate is improved；Li2O fluxing actions are strong, are to help by force
Solvent, it is possible to decrease the glass melting temperature of firming body；Al2O3Belong to glass intermediate oxide, the crystallization tendency of glass can be reduced, carry
The chemical stability of glass high, heat endurance and mechanical strength；TiO2Thermal coefficient of expansion can be reduced, the acid resistance of glass is improved,
The stronger compound of stability can be formed with the element such as Cs, Si.
To sum up, glass basis composition of the present invention, can be suitably used for middle low-level radioactivity combustible waste burning ash,
And density, compression strength, impact strength, radiation-resistant property can meet the requirements after its weight-loss ratio, immersion.
Specific embodiment
With reference to embodiment, detailed description further is made to the present invention, but embodiments of the present invention are not limited to
This.
Firming body described in following examples carries out performance test according to following standard：
Static leaching is tested：
Static leaching experiment is carried out with reference to the Static leaching test method MCC-1 that test center of the U.S. formulates.After annealing
Simulated waste glass solidified body for regular shape cylinder, accurately measure its radius and length, calculate its surface area, spend from
Sub- water by surface clean it is clean after, dried at 105 DEG C and weighed, be designated as W0。
In experimentation, sample is placed in vinyon bottle, is soaked at 90 DEG C with deionized water, control sample table
Area（SA）With the volume of leachate（V）Compare SA/V=0.1cm-1, soak time is 28d.After the completion of leaching test, solidification is taken out
Body carries out drying and weighs, and is designated as W1, calculate its weight-loss ratio, weight-loss ratio=（W0- W1）/ W0。
Density after immersion：Firming body to soaking 28 days by deionized water at 90 DEG C, according to buoyancy method（GB/T 5432-
2008）Carry out glass solidified body density measurement.
Compression strength：The compression strength of glass solidified body is tested using NYL-30 types pressure testing machine.
Impact strength：Using weight freely falling body impact test apparatus, examination is impacted according to related weight freely falling body
Proved recipe method（EJ 1186-2005）Impact strength to glass solidified body is measured, non-notch.
Resistance to irradiation test：
Incineration of waste gray glass firming body sample is fitted into small measuring cup, is neatly placed in rustless steel container, placed
Irradiated in γ irradiation fields, γ irradiation intergal doses are 106Gy, takes out after expected irradiation dose value to be achieved.To non-spoke
Static immersing experiment is carried out according to the glass solidified body sample after irradiation, comparative test result further investigates γ irradiation to glass
The influence of firming body performance.
Embodiment 1
The determination of middle low-level radioactivity combustible waste burning ash main analog composition
Overall consideration is carried out to the oxide composition in radwaste.Main analog nuclear power plant blotting paper, cotton products
Labour protection, plastic cloth, rubber gloves burned after institute's ash point oxide and nucleic composition.Main oxides content is by chemistry
Analysis is obtained, and radionuclide mainly considers fission product137Cs、90Sr and activation products60Co.Simulated waste is constituted and content
See the table below 1.
Wherein, the data in upper table 1 draw on the basis of being 100 weight portions in each combustible waste burning ash, and on
CoO, Cs in table 1 in unlisted various simulated waste burning ashs2O, SrO, its content are respectively burning ash oxide aggregate
0.2wt%。
The selection of glass basis composition
In order to study influence of the change of each component to glass basis composition properties, while improving test efficiency again, use
Less experiment obtains preferable result, the dispensing that this work is formulated using orthogonal experiment design method design basis glass test
Composition.With SiO2/B2O3、Na2O/CaO、Li2O、Al2O3、TiO2As 5 factors, and fixed w（Na2O+CaO）It is 20 weight
Part come the Orthogonal Experiment and Design that is formulated, each factor takes 4 levels, as follows respectively：
（1）Factor A（SiO2/B2O3）：2.0,3.5,5.0,6.5；
（2）Factor B（Na2O/CaO）：0.2,0.8,1.4,2.0；
（3）Factor C（Li2O）：2 weight portions, 3 weight portions, 4 weight portions, 5 weight portions；
（4）Factor D（Al2O3）：2 weight portions, 3 weight portions, 4 weight portions, 5 weight portions；
（5）Factor E（TiO2）：1 weight portion, 1.5 weight portions, 2.0 weight portions, 2.5 weight portions.
By orthogonal experiment design, L is selected16（45）Orthogonal arrage arrangement is tested, and correlated performance test is carried out, according to result
Quadrature analysis are carried out, middle low-level radioactivity blotting paper, cotton products, plastic cloth, the parent glass of rubber is respectively obtained and is most preferably matched somebody with somebody
Side, refers to table 2 below.
In example 2 below -8, CoO, 0.2 weight portion of 0.2 weight portion are added in the simulated waste of 100 weight portions
Cs2The SrO of O, 0.2 weight portion, corresponding addition raw material is 0.2 part of quality CoO, 0.24 part of quality CsCl and 0.28 respectively
Part quality SrCO3。
Embodiment 2-4
The processing method of middle low-level radioactivity cotton products：Proportionally by the group of listed weight portion in upper table 1 and table 3 below
Divide and weigh corresponding raw material, often weigh 100 parts of glass basis compositions of quality（Calculated by oxide）, while weighing 60 parts
The simulated waste of quality（Calculated by oxide）.Dispensing ground and mixed is uniformly fitted into corundum crucible afterwards, and feeding is preheated to 300 DEG C
Founded in chamber type electric resistance furnace above.Poured into after constant temperature 2-5h at 1100-1300 DEG C in the 400-600 DEG C of graphite-pipe of preheating
In, room temperature is then naturally cooled in stove in annealing furnace annealing at such a temperature.
Embodiment 5-6
The processing method of middle low-level radioactivity blotting paper：
The component of listed weight portion in upper table 1 and table 4 below is proportionally weighed into corresponding raw material.Often weigh 100 parts
The glass basis composition of quality（Calculated by oxide）, while weighing 50 parts of simulated wastes of quality（Calculated by oxide）.
During raw material is fitted into corundum crucible after finely ground, careful mixing in mortar, feeding is preheated in more than 300 DEG C of chamber type electric resistance furnace and melts
System.Poured into after constant temperature 2-5h at 1100-1300 DEG C 400-600 DEG C preheating graphite-pipe in, then at such a temperature in
Annealing furnace annealing, naturally cools to room temperature in stove.
Embodiment 7
The processing method of middle low-level radioactivity rubber：
Corresponding chemical reagent needed for proportionally the component of listed weight portion in upper table 1 and table 5 below is weighed.Often weigh
100 parts of glass basis compositions of quality（Calculated by oxide）, while weighing 40 parts of simulated wastes of quality（Based on oxide
Calculate）.During raw material is fitted into corundum crucible after finely ground, careful mixing in mortar, feeding is preheated to more than 300 DEG C of chamber type electric resistance furnace
Inside found.Poured into after constant temperature 2-5h at 1100-1300 DEG C in the 400-600 DEG C of graphite-pipe of preheating, then in the temperature
Under in annealing furnace annealing, room temperature is naturally cooled in stove.
Embodiment 8
The processing method of middle low-level radioactivity plastic cloth：
Corresponding chemical reagent needed for proportionally the component of listed weight portion in upper table 1 and table 6 below is weighed.Often weigh
100 parts of glass basis compositions of quality（Calculated by oxide）, while weighing 30 parts of simulated wastes of quality（Based on oxide
Calculate）.During raw material is fitted into corundum crucible after finely ground, careful mixing in mortar, feeding is preheated to more than 300 DEG C of chamber type electric resistance furnace
Inside found.Poured into after constant temperature 2-5h at 1100-1300 DEG C in the 400-600 DEG C of graphite-pipe of preheating, then in the temperature
Under in annealing furnace annealing, room temperature is naturally cooled in stove.
Weight-loss ratio, density, compression strength, impact strength is carried out to above-described embodiment 2-8 to be tested and remember result
Record in table 7 below：
Note：Index request to glass solidified body is：After being soaked 28 days in 90 DEG C of deionized waters, firming body weight-loss ratio≤
15 g·m-2, density >=2.5 gcm after firming body immersion-3；Compression strength >=7Mpa, impact strength≤12 m2·J-1。
The glass that can be seen that middle low-level radioactivity rubber of the present invention from above-described embodiment and performance test is consolidated
Change body, the glass solidified body of middle low-level radioactivity plastic cloth, the glass solidified body of middle low-level radioactivity cotton products, in low water
The glass solidified body of flat radioactivity blotting paper has density, compression strength, impact strength after preferable weight-loss ratio, immersion, especially
It is that compression strength and impact strength are substantially more excellent.The compression strength of the firming body obtained by the present invention can reach 80 MPa
More than, even 100 more than MPa, and the compression strength of generally existing firming body formula is only 10-20 MPa or so, because
This, the glass basis composition of formula of the present invention and substantially preferable by the performance of its obtained firming body.
In addition, each glass solidified body tests weight-loss ratio after carrying out resistance to irradiation test in above-described embodiment 2-8, its weight-loss ratio phase
Weight-loss ratio to non-irradiated glass solidified body increases respectively less than 20%, and radiation-resistant property is good.
As described above, the present invention can be realized preferably.
The above, is only presently preferred embodiments of the present invention, and any formal limitation is not made to the present invention, according to
According to technical spirit of the invention, within the spirit and principles in the present invention, any simple modification made to above example,
Equivalent and improvement etc., still fall within the protection domain of technical solution of the present invention.
Claims (5)
1. a kind of glass solidified body of middle low-level radioactivity cotton products burning ash, including glass basis composition and the cotton
Product burning ash simulation substance,
The glass basis composition, including following weight portion component：
SiO2：45-70 weight portions, B2O3：9-15 weight portions, Na2O：10-18 weight portions, CaO：3-10 weight portions, Al2O3：3-6
Weight portion, Li2O：2-3 weight portions, TiO2：1-3 weight portions；
The cotton products burning ash simulation substance, including following weight portion component：
SiO2：14.6 weight portions, B2O3：4.00 weight portions, Na2O：1.00 weight portions, CaO：73.3 weight portions, Al2O3：2.34 weights
Amount part, Fe2O3：2.96 weight portions, SO3：1.80 weight portions, CoO：0.2 weight portion, Cs2O：0.2 weight portion, SrO：0.2 weight
Part；
Wherein, according to the Mass Calculation of oxide, glass basis composition and corresponding combustible waste burning ash simulation substance
Mass ratio is 10:2-10:7.
2. a kind of glass solidified body of middle low-level radioactivity blotting paper burning ash, including glass basis composition and the suction
Water paper burning ash simulation substance,
The glass basis composition, including following weight portion component：
SiO2：45-70 weight portions, B2O3：9-18 weight portions, Na2O：6-14 weight portions, CaO：6-12 weight portions, Al2O3：3-6 weights
Amount part, Li2O：1-3 weight portions, TiO2：2-3 weight portions；
The blotting paper burning ash simulation substance, including following weight portion component：
SiO2：24.7 weight portions, B2O3：1.74 weight portions, Na2O：17.8 weight portions, CaO：49.1 weight portions, Al2O3：2.67 weights
Amount part, Fe2O3：1.65 weight portions, SO3：2.34 weight portions, CoO：0.2 weight portion, Cs2O：0.2 weight portion, SrO：0.2 weight
Part；
Wherein, according to the Mass Calculation of oxide, glass basis composition and corresponding combustible waste burning ash simulation substance
Mass ratio is 10:2-10:7.
3. a kind of glass solidified body of middle low-level radioactivity rubber burning ash, including glass basis composition and the rubber
Burning ash simulation substance,
The glass basis composition, including following weight portion component：
SiO2：45-70 weight portions, B2O3：9-18 weight portions, Na2O：8-16 weight portions, CaO：0-3 weight portions, Al2O3：3-6 weights
Amount part, Li2O：1-3 weight portions, TiO2：3 weight portions；
The rubber burning ash simulation substance, including following weight portion component：
SiO2：0.867 weight portion, Na2O：0.054 weight portion, CaO：94.3 weight portions, Al2O3：0.489 weight portion, SO3：4.29
Weight portion, CoO：0.2 weight portion, Cs2O：0.2 weight portion, SrO：0.2 weight portion；
Wherein, according to the Mass Calculation of oxide, glass basis composition and corresponding combustible waste burning ash simulation substance
Mass ratio is 10:2-10:7.
4. a kind of glass solidified body of middle low-level radioactivity plastic cloth burning ash, including glass basis composition and the modeling
Material cloth burning ash simulation substance,
The glass basis composition, including following weight portion component：
SiO2：45-70 weight portions, B2O3：9-15 weight portions, Na2O：10-18 weight portions, CaO：1-4 weight portions, Al2O3：3-6 weights
Amount part, Li2O：2-3 weight portions, TiO2：3 weight portions；
The plastic cloth burning ash simulation substance, including following weight portion component：
SiO2：2.24 weight portions, B2O3：0.750 weight portion, Na2O：0.080 weight portion, CaO：85.6 weight portions, Al2O3：1.50
Weight portion, Fe2O3：1.58 weight portions, SO3：8.25 weight portions, CoO：0.2 weight portion, Cs2O：0.2 weight portion, SrO：0.2 weight
Amount part；
Wherein, according to the Mass Calculation of oxide, glass basis composition and corresponding combustible waste burning ash simulation substance
Mass ratio is 10:2-10:7.
5. it is a kind of to prepare such as the glass solidified body of low-level radioactivity combustible waste burning ash in any one of Claims 1-4
Method, it is characterised in that comprise the following steps：
A. dispensing：The component in the glass basis composition any one of Claims 1-4 is weighed in proportion, and it is right
Component in the burning ash simulation substance answered, ground and mixed, the burning ash simulation substance is accordingly selected from following material
One kind：The blotting paper burning ash analogies described in cotton products burning ash simulation substance, claim 2 described in claim 1
The plastic cloth burning ash simulation substance described in rubber burning ash simulation substance or claim 4 described in matter, claim 3,；
B high-temperature calcinations：Founded at a temperature of more than 300 DEG C, in 1100-1300 DEG C of constant temperature 2-5h；
C is molded：Glass melts are cast in 400-600 DEG C of die for molding, glass solidified body is obtained；
D anneals：0.8-1.2 hours is incubated under conditions of 400-600 DEG C, room temperature is cooled to the furnace；
Wherein, in step a, according to the Mass Calculation of oxide, the burning ash simulation substance and the glass basis composition
Mass ratio be 2:10-7:10.
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| CN106935305A (en) * | 2017-01-19 | 2017-07-07 | 杨红波 | The low technique for putting degradable waste in a kind of gasification process |
| CN106875997A (en) * | 2017-01-19 | 2017-06-20 | 杨红波 | The low technique for putting degradable waste in a kind for the treatment of |
| CN112382429B (en) * | 2020-11-16 | 2022-12-23 | 武汉理工大学 | Method for curing medium-low level glass fiber and combustible solid nuclear waste incineration ash through cooperating with glass |
| CN112551889A (en) * | 2020-12-02 | 2021-03-26 | 中广核研究院有限公司 | Glass matrix composition of lead-boron-polyethylene, glass solidified body and preparation method thereof |
| CN115677214B (en) * | 2022-11-10 | 2024-03-15 | 中国建筑材料科学研究总院有限公司 | Glass solidified body for improving precious metal deposition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10167754A (en) * | 1996-12-06 | 1998-06-23 | Toshiba Glass Co Ltd | Vitrifying material for solidifying waste and waste-solidified glass |
| CN102543237A (en) * | 2012-02-21 | 2012-07-04 | 浙江大学 | Glass solidified body and preparation method thereof |
| CN103265169A (en) * | 2013-05-24 | 2013-08-28 | 杭州电子科技大学 | Method for preparing high-radioactivity nuclear waste glass solidified base material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03235098A (en) * | 1990-02-10 | 1991-10-21 | Nippon Electric Glass Co Ltd | Vitrification material for vitrification treatment of low level radioactive waste |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10167754A (en) * | 1996-12-06 | 1998-06-23 | Toshiba Glass Co Ltd | Vitrifying material for solidifying waste and waste-solidified glass |
| CN102543237A (en) * | 2012-02-21 | 2012-07-04 | 浙江大学 | Glass solidified body and preparation method thereof |
| CN103265169A (en) * | 2013-05-24 | 2013-08-28 | 杭州电子科技大学 | Method for preparing high-radioactivity nuclear waste glass solidified base material |
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