CN107188533A - A kind of method of geopolymer ceramic solidification high activity liquid waste - Google Patents
A kind of method of geopolymer ceramic solidification high activity liquid waste Download PDFInfo
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- CN107188533A CN107188533A CN201710421381.4A CN201710421381A CN107188533A CN 107188533 A CN107188533 A CN 107188533A CN 201710421381 A CN201710421381 A CN 201710421381A CN 107188533 A CN107188533 A CN 107188533A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/1325—Hazardous waste other than combustion residues
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/131—Inorganic additives
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/16—Processing by fixation in stable solid media
- G21F9/162—Processing by fixation in stable solid media in an inorganic matrix, e.g. clays, zeolites
- G21F9/165—Cement or cement-like matrix
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
- C04B2235/3481—Alkaline earth metal alumino-silicates other than clay, e.g. cordierite, beryl, micas such as margarite, plagioclase feldspars such as anorthite, zeolites such as chabazite
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention discloses a kind of method of geopolymer ceramic solidification high activity liquid waste, its essence is a kind of method of aluminosilicate polymer ceramic solidification nuclear waste.It is main to include following several steps:(1)Inorganic adsorbing material carries out adsorption and enrichment to the nucleic in high activity liquid waste;(2)Sorbing material containing nucleic and inorganic solidification agent, alkali-activator are mixed with geopolymer base nuclear waste intermediate solidification body;(3)Geopolymer nucleic firming body generates the geopolymer ceramic solidification body of densification under hot pressing condition.Geopolymer intermediate solidification body performance prepared by this method is stable, is easy to temporary or transports.This method nuclear waste volume reduction amount is big, and final ceramic solidification body stability is good, and preparation technology is simple, and energy consumption is low, non-secondary pollution, it is easy to engineering application, can be widely used for the curing process of high-level waste.
Description
Technical field
The present invention relates to a kind of method of disposal of high activity liquid waste, belong to a kind of high activity liquid waste ceramic solidification treatment technology and material
Material field.
Background technology
With the increase of energy-output ratio, fossil energy deposit is drastically reduced, and nuclear energy is used as a kind of new clean energy resource
It is widely used.The treatment technology comparative maturity of low radioactive waste liquid at present, and it is used successfully to production practices, but the place of high activity liquid waste
Reason technology is also to be developed.Post processing high activity liquid waste has converged 99% or so radioactivity, with time of launch length, nucleic toxicity
The features such as big and heat generation, cause the extensive concern of domestic and foreign scholars.
The mainly pretreatment including waste liquid, waste liquid solidification, the final disposal of firming body of the processing links of high activity liquid waste.Gao Fang
Waste liquid roast treatment temperature is high, and energy consumption is big, produces a large amount of radgas, and processing cost is high.HLW-solidification is most normal
Treatment technology mainly has:Glass solidification, ceramic solidification and cement solidification etc..
Glass solidification technology is that waste is admixed to the process that glass solidified body is formed in glass base-material.At present, glass
Glass solidifying much waster liquid technology realizes extensive use in engineering.Chinese patent CN103265169A and Chinese patent
Solidification raw material are disclosed in CN101826376A respectively after high-temperature fusion, shaping annealing, the side of glass solidified body is prepared
Method, the shortcomings of still there is poor radiation resistance, poor mechanical stability and poor heat endurance in firming body obtained by this method, and
In high temperatures and humid conditions, glass is met corrosion, crystallization, and leaching rate is high, and inclusion quantity is low, is unfavorable for carrying out at long-term geology
Put.
Ceramic solidification technology is through pressurization heating preparation ceramic solidification after radionuclide is mixed with curing substrate
The process of body.Cerium monazite is utilized respectively in Chinese patent CN103408304B, CN101624267A and CN104844190A, is visitd
Ear method red mud, fluor-apatite prepare ceramic solidification body, and gained firming body stable chemical performance, safety coefficient is high, with reality
Engineer applied potentiality.Glass ceramics solidifies the one kind for belonging to ceramic solidification, Chinese patent CN104810072A and Chinese patent
The glass ceramics firming body prepared in CN102568636A using different raw material is respectively provided with preferable geological stability, chemistry
Stability, heat endurance and radiation resistance, can make up the defect of glass solidification.
Alkali-excited cement novel gelled material can also realize the solidification to high activity liquid waste.Chinese patent CN101261887A is public
A kind of method of solidifying much waster liquid based on alkali slag cement of cloth, high activity liquid waste is pre-processed through ferrocyanide nickel potassium, alkalize and with
Zeolite, alkali-activated slag, exciting agent mixing, firming body is prepared under certain water-cement ratio.The technology is then right by the use of zeolite as adsorbent
High activity liquid waste is solidified, with good curing performance, stronger impermeability and preferably shock resistance, but should
Still there is the shortcomings of long-term thermal stability is poor in technology.In order to overcome the defect that alkali-excited cement solidifies, the present invention utilizes nothing
Machine aluminosilicate adsorbent adsorbs high activity liquid waste, then will contain core sorbing material, inorganic solidification agent and alkali-activator and be mixed with
Geopolymer firming body, and be further densified geopolymer firming body and refractory ceramics under hot pressing condition.The present invention
Middle geopolymer solidification process need not add any organic additive, with absorption-curing integrated characteristic, further plus
Press after ceramic, gained ceramic solidification body consistency is high, can be more with preferable high temperature resistance, resistance to irradiation and anti-leaching performance
The deficiency of cement solidification is mended, and the technical matters is simple, energy consumption is small, non-secondary pollution, it is easy to engineering application.
The content of the invention
The invention provides a kind of method of geopolymer ceramic solidification high activity liquid waste, the specific content of the invention is as follows:
(1)The present invention using inorganic adsorbing material be enriched with high activity liquid waste in nucleic, while will contain core sorbing material, curing agent and
Alkali-activator is mixed with geopolymer intermediate solidification body.Inorganic adsorbing material polymerize anti-with participating under alkali-activator effect
Should, the effect of adsorbent had both been served, the effect of curing agent is served again;
(2)The present invention is further densified and refractory ceramics to geopolymer intermediate solidification body, improves final nucleic solidification
The high temperature resistance of body, resistance to irradiation and anti-leaching performance.
Beneficial effects of the present invention:
(1)Abundant raw materials of the present invention, energy consumption is low, and technique is simple, it is easy to engineer applied;
(2)The present invention is not required to add any organic additive, and intermediate solidification body need not be press-formed, and can voluntarily pour hardening;
(3)Intermediate solidification body can direct hot pressed ceramics, be not required to any other additive, ceramic solidification body function admirable;
(4)Whole preparation process involved in the present invention and use process are produced without any toxic organic pollutant, safety and environmental protection.
Embodiment
Case study on implementation 1:
A kind of method of geopolymer ceramic solidification high activity liquid waste, with containing brewsterite and metakaolin mass ratio 1:1 mixing, water glass
Glass modulus 1.5, sode ash compares 2:3, the ratio of mud 0.35 prepares geopolymer intermediate solidification body, conserves 20d, and compression strength reaches 48MPa.
Geopolymer firming body is 1200 °C in vacuum sintering funace, under 20MPa pressure, and sintering 6h obtains geopolymer ceramic solidification
Body.Firming body is analyzed according to PCT methods confrontation leaching performance in ASTM standards, the standardization leaching of the 28d strontium elements measured
Extracting rate is 10-5Below.
Case study on implementation 2:
A kind of method of geopolymer ceramic solidification high activity liquid waste, with containing brewsterite and metakaolin mass ratio 1:1 mixing, water glass
Glass modulus 1.2, sode ash compares 3:5, the ratio of mud 0.35 prepares geopolymer intermediate solidification body, conserves 20d, and compression strength reaches 45MPa.
Geopolymer firming body is 1400 DEG C in vacuum sintering funace, under 20MPa pressure, and sintering 6h obtains geopolymer ceramic solidification
Body.Firming body is analyzed according to PCT methods confrontation leaching performance in ASTM standards, the standardization leaching of the 28d strontium elements measured
Extracting rate is 10-5Below.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be
Various change is made to it in form and in details, without departing from claims of the present invention limited range.
Claims (6)
1. the invention discloses a kind of method of geopolymer ceramic solidification high activity liquid waste, its essence is a kind of polymerization of aluminosilicate
The method of thing ceramic solidification nuclear waste, it is main to include following several steps:
(1)The enrichment of nucleic:Inorganic adsorbing material is enriched with to the nucleic in high activity liquid waste;
(2)The preparation of geopolymer nuclear waste intermediate solidification body:Step(1)In be enriched the inorganic adsorbing material of nucleic with it is inorganic
Curing agent, alkali-activator mixing, adds water and stirs, pour maintenance and produce geopolymer base intermediate solidification body;
(3)Geopolymer firming body refractory ceramics:Gather on the ground that geopolymer nucleic firming body generates densification under hot pressing condition
Compound ceramic solidification body.
2. the inorganic adsorbing material according to claim 1, its principal character is as follows:Inorganic adsorbing material is inorganic silicon
Aluminate adsorbent, it is main to include one kind in titanium sodium metasilicate, zeolite, bentonite, clay, montmorillonite, sepiolite and galapectite
Or it is several.
3. the inorganic solidification agent according to claim 1, its principal character is as follows:Inorganic solidification agent is to have volcanic ash
The mineral or industrial residue of characteristic, mainly including one kind in metakaolin, flyash, solid sulfur ash, slag, blast furnace slag or several
Kind.
4. the preparation of the geopolymer base nuclear waste intermediate solidification body according to claim 1, its principal character is as follows:m
Curing agent:M adsorbents=0.25-4.0.
5. the refractory ceramics equipment according to claim 1, its principal character is as follows:Refractory ceramics equipment is microwave
Hot pressed sintering, vacuum sintering funace or discharge plasma sintering furnace.
6. according to the refractory ceramics process write in claim 1, its principal character is as follows:Sinter 1200 DEG C of furnace temperature with
On, pressure 20 more than MPa, more than sintering time 2h.
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CN201710421381.4A CN107188533B (en) | 2017-06-07 | 2017-06-07 | Method for solidifying high-level radioactive waste liquid by geopolymer ceramic |
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CN201710421381.4A CN107188533B (en) | 2017-06-07 | 2017-06-07 | Method for solidifying high-level radioactive waste liquid by geopolymer ceramic |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109903875A (en) * | 2019-02-28 | 2019-06-18 | 西南科技大学 | A kind of method that phosphate polymer solidifies boracic nuclear waste |
CN110028248A (en) * | 2019-06-03 | 2019-07-19 | 西南交通大学 | A kind of method that low-temp liquid-phase sintering prepares pollucite devitrified glass |
CN111250039A (en) * | 2020-03-13 | 2020-06-09 | 常熟理工学院 | Method for preparing hydroxyapatite functionalized geopolymer adsorbent by using tuff |
WO2020225483A1 (en) * | 2019-05-06 | 2020-11-12 | Teknologian Tutkimuskeskus Vtt Oy | Method for treating waste material |
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 |
CN114394784A (en) * | 2021-12-13 | 2022-04-26 | 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-based solidified body |
CN116161948A (en) * | 2023-02-25 | 2023-05-26 | 武汉理工大学 | Geopolymer-based multi-phase ceramic high-level radioactive waste liquid curing material and curing method thereof |
WO2024126963A1 (en) * | 2022-12-16 | 2024-06-20 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Continuous process for separating strontium cations from a liquid medium, with a material comprising a geopolymer and particles of an ion exchanger |
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CN104282353A (en) * | 2014-09-24 | 2015-01-14 | 深圳航天科技创新研究院 | Geological cement for radioactive steam residual liquid solidifying and solidifying method thereof |
CN104538076A (en) * | 2014-12-02 | 2015-04-22 | 西南科技大学 | Total radioactivity-mass concentration gradient combined progressive decreasing method for treating high-medium radioactivity waste liquid |
JP2015231610A (en) * | 2014-06-10 | 2015-12-24 | 国立大学法人山口大学 | Method for processing contaminated water |
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EP0180308A1 (en) * | 1984-10-25 | 1986-05-07 | Mobil Oil Corporation | Borosilicate zeolite for nuclear waste disposal |
CN101261887A (en) * | 2008-04-22 | 2008-09-10 | 南京瑞迪高新技术公司 | Method for solidifying much waster liquid based on alkali slag cement |
JP2015231610A (en) * | 2014-06-10 | 2015-12-24 | 国立大学法人山口大学 | Method for processing contaminated water |
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109903875A (en) * | 2019-02-28 | 2019-06-18 | 西南科技大学 | A kind of method that phosphate polymer solidifies boracic nuclear waste |
WO2020225483A1 (en) * | 2019-05-06 | 2020-11-12 | Teknologian Tutkimuskeskus Vtt Oy | Method for treating waste material |
CN110028248A (en) * | 2019-06-03 | 2019-07-19 | 西南交通大学 | A kind of method that low-temp liquid-phase sintering prepares pollucite devitrified glass |
CN110028248B (en) * | 2019-06-03 | 2020-03-31 | 西南交通大学 | Method for preparing pollucite microcrystalline glass by low-temperature liquid phase sintering |
CN111250039A (en) * | 2020-03-13 | 2020-06-09 | 常熟理工学院 | Method for preparing hydroxyapatite functionalized geopolymer adsorbent by using tuff |
CN111250039B (en) * | 2020-03-13 | 2021-10-19 | 常熟理工学院 | Method for preparing hydroxyapatite functionalized geopolymer adsorbent by using tuff |
CN114394784A (en) * | 2021-12-13 | 2022-04-26 | 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-based solidified body |
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 |
WO2024126963A1 (en) * | 2022-12-16 | 2024-06-20 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Continuous process for separating strontium cations from a liquid medium, with a material comprising a geopolymer and particles of an ion exchanger |
FR3143831A1 (en) * | 2022-12-16 | 2024-06-21 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | CONTINUOUS PROCESS FOR SEPARATING STRONTIUM CATIONS FROM A LIQUID MEDIUM, WITH A MATERIAL COMPRISING A GEOPOLYMER AND PARTICLES OF AN ION EXCHANGER |
CN116161948A (en) * | 2023-02-25 | 2023-05-26 | 武汉理工大学 | Geopolymer-based multi-phase ceramic high-level radioactive waste liquid curing material and curing method thereof |
CN116161948B (en) * | 2023-02-25 | 2023-11-28 | 武汉理工大学 | Geopolymer-based multi-phase ceramic high-level radioactive waste liquid curing material and curing method thereof |
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