CN1266268A - Glass-like body solidifying material for treating radioactive wastes and solidifying method - Google Patents

Glass-like body solidifying material for treating radioactive wastes and solidifying method Download PDF

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CN1266268A
CN1266268A CN 00105281 CN00105281A CN1266268A CN 1266268 A CN1266268 A CN 1266268A CN 00105281 CN00105281 CN 00105281 CN 00105281 A CN00105281 A CN 00105281A CN 1266268 A CN1266268 A CN 1266268A
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glass
curing materials
active
inorganic
powder
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CN1119820C (en
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李永德
胥胜利
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Tsinghua University
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Tsinghua University
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Abstract

The present invention belongs to the field of radioactive waste treatment technology, and is characterized by that it adopts active powder body material made up by combining several organic materials and inorganic materials, in which the organic materials include surfactant and water-soluble polymer, and its inorganic materials include calcium aluminosilicate compound, special hydraulic binding material and inorganic mineral powder material with special adsorption activity. Said invention possesses amorphous glasslike body structure, high strength good durability, firm structure, good impermeabiity and leaching rate when the solidified radioactive nuclide is soaked with water is low, so that it is a safe and reliable new type material and treatment method for treating radioactive wastes.

Description

A kind of glass-like body curing materials and curing process method of handling radioactive waste
The invention belongs to the radioactive waste process field, particularly a kind of can be at room temperature can with the active powder body material with radioactive liquid waste generation curing reaction that different chemical forms, and by the process of this class material cured radioactive liquid waste.
The radioactive waste that is produced by devices such as all kinds of nuclear reactors, nuclear power stations has suitable harmfulness, can not be directly to environmental emission, must be cured with suitable method and by the proper device compartmentalized storage, up to wherein radioelement decay to environment do not produced harm till.The glass solidification method is often adopted in processing for the high radioactivity waste liquid, is about to mix airtight storage in the storage field of special use again after high temperature sintering becomes the glass solid with the mineral powder material with suitable composition after waste liquid concentrates evaporate to dryness.The characteristics of this curing are good, the Stability Analysis of Structures of intensity height, density of firming body, and the radioactive nuclide that is cured is very low in the leaching rate when water logging is steeped, thereby safe.Shortcoming is this method of disposal equipment complexity, cost height, and material in the processing procedure and energy-output ratio are also big, thereby total disposal processing cost height.For in, the processing of cold waste do not adopt the glass solidification method usually.The disposal route of centering, cold waste employing mainly contains bitumen solidification method and cement solidification method in the world at present.Bitumen solidification is the curing materials that adopts organic class, though corresponding firming body can reach lower nucleic leaching rate and higher volumetric efficiency, the permanance of these organic materials and security are very big problems.The fire that Germany caused when once bitumen solidification taking place, the on fire from explosion of bitumen solidification system also took place in Japan, caused very big accident.By contrast, cement solidification method is owing to adopt inorganic coagulation material, and the intensity of gained firming body and permanance are all fine.But also there are problems in cement solidification method, is a kind of porous inorganic crystal mosaic texture as solidified cement body, and density is poor, and the leaching rate of the radioactive nuclide that is cured when solidified cement body contacts with water is higher, thereby treatment effect is relatively poor.During with cement solidification when handling the refuse of same amount the increment of firming body big, thereby needed storage space is bigger, this has just increased total processing cost of disposal.In addition, bigger thermal value when the suitable time limit of cement, aquation, the especially strong slow setting when solidifying the boronic acid containing waste liquid also are the disadvantages that exists in the cement solidification method to such an extent as to be difficult to problem such as curing molding.
The objective of the invention is at the deficiencies in the prior art, a kind of novel curing materials and easy curing process be provided, with solution contain variable concentrations nitrate or boratory in, the curing of low-activity waste liquid handles handling problems.The firming body that is generated has unformed glass-like body structure, intensity height, good endurance, structure is closely knit, impermeability good, leaching rate was low when the radioactive nuclide that is cured steeped through water logging, thereby was to handle a kind of safe and reliable new material of radioactive waste and handle method of disposal.
The present invention proposes a kind of glass-like body curing materials of handling radioactive waste, it is characterized in that the active powder body material that adopts multiple organic material and inorganic active material to be composited.
Said organic material can comprise: the inorganic powder material in the aqueous solution is had the surfactant of dispersed activity, and aqueous solution is had tackify, firming body had the water-soluble polymers that increases packing; Said inorganic active material can comprise the ca aluminosilicate compound through high temperature desulfurizing, deferrization and carbonization treatment, has the high temperature experience and extraordinary hydraulic cementing materials that forms and the inorganic mineral powder with special adsorption activity.
The percentage by weight of each component can be in the said active powder:
Surfactant, 0.3%~1.2%;
Water-soluble polymers, 0.1%~1.0%;
The ca aluminosilicate compound, 50%~80%;
Hydraulic cementing materials, 10%~30%;
The inorganic mineral powder, 5%~20%.
Said surfactant can comprise one or more of naphthalene sulfonic acid-formaldehyde condensation product, sulfonated melamine compound condensation product or sulfamate formaldehyde condensation products, and said water-soluble polymers can comprise one or more of polyvinyl alcohol (PVA), polyacrylamide, hydroxyethyl cellulose and polyvinyl pyrrolidone.
Active SiO in the said ca aluminosilicate compound 2Content can be 30%~40%, active A l 2O 3Content can be 10~30%, the content of active CaO can be 30%~50%, surplus MgO, TiO 2, Fe 2O 3, K 2O, Na 2The total content of O etc. can be 0%~10%.
Said extraordinary hydraulic cementing materials comprises one or more of silicates, aluminate class and volcanic debris, shale ashes, flyash, blast furnace or open hearth slag and ultra-fine silicon ash.
Said inorganic mineral powder with special adsorption activity comprise zeyssatite, bentonitic clay, zeolite powder and kaolinic one or more.
The composition of powder body material of the present invention can be adjusted in above-mentioned scope according to the chemical composition of solidifying waste liquid, to guarantee that suitable condensation cure time and necessary performances such as firming body intensity are arranged.
The present invention proposes a kind of curing process method that adopts above-mentioned glass-like body curing materials, it is characterized in that, with said curing materials in liquid-solid ratio is 0.5~0.8 scope by mixing and become to have mobile slurry with containing nitrate or boratory radioactive liquid waste, be solidified into solid through injection molding and airtight maintenance with glass-like body structure.
According to method of the present invention, at room temperature will have the above-mentioned active powder body material of suitable composition and a certain amount ofly contain the radioactivity salt or the acids waste liquid mixes, become slurry, inject in metal bucket, concrete bucket or the Plastic Drum that to store then, add a cover the back sealed maintenance with flowability.Formed firming body has closely knit glass-like body structure.The compressive strength of firming body after 28 days is greater than 40MPa, and rupture strength is greater than 5MPa, and is impervious greater than B30, and the loss of strength rate of firming body after 30 freeze thawing circulation is less than 5%.When original radioelement mixes by the medium-activity metering in solidifying waste liquid, be with the 42nd day leaching rate of distilled water immersion firming body: 90Sr is 10 -5The cm/d order of magnitude, 137Cs is 10 -6The cm/d order of magnitude.According to the regulation of GB14569.1-93, should be not less than 7MPa to the compressive strength of solidified cement body, the requirement of antagonism leachability is: 137Sr is less than 4 * 10 -3Cm/d, 90Cs is less than 1 * 10 -3Cm/d, the loss of strength after the freeze thawing circulation is no more than 25%.Then the firming body performance of the inventive method all reaches and surpasses the requirement of index.
Contain in the chemical composition of the handled radioactive liquid waste of the present invention nitrate or boratory one or more, concentration is 0~30% (Wt).
Because selected curing materials is mainly inorganic coagulation material among the present invention, has unformed cancellated glass-like body with being mainly during the firming body after the radioactive liquid waste reaction that contains different salts or acids is solidified is formed, compare with the Portland cement solidification method, intensity height, the density leaching rate good, corresponding radioactive nuclide that not only shows firming body is low, and have good permanance, overcome heating in the cement solidification process, slow setting or do not coagulated and many disadvantages such as working life is short.
Method of disposal facility of the present invention is simplified, expense reduces, security increases, thus be in a kind of safe, reliable and easy disposal, the curing of cold waste.
Embodiment 1:
Adopt NaNO 3Content is that the solution of 30% (Wt) is the simulated emission waste liquid, and the active powder body material that is adopted consists of; Ca aluminosilicate compound (SiO wherein 2Content is 36.4%, Al 2O 3Content is 12%, and CaO content is 31.5%): 79.3%; Flyash (loss on ignition 4.78%): 10%; Zeyssatite (SiO 2Content 82.5%): 5%, zeolite powder (SiO 2Content 67.2%): 5%; Naphthalene sulfonic acid-formaldehyde condensation product: 0.5%; Hydroxyethyl cellulose powder: 0.2%; The liquid-solid ratio that is adopted during mixing is 0.65.Above-mentioned material is being starched the mould of plastics that injects φ 50mm * 50mm in the stirring machine behind the stirring 3min, sealed maintenance 28 days only.The compressive strength of measuring firming body is 45MPa, and after 30 freeze thawing circulation (15 ℃~20 ℃), the loss of strength rate is 4.5%, and impervious index is B30.
Embodiment 2:
Adopt as the formula for raw stock of example 1 and mixing, curing process, in the solution composition of concentration equally, add radioelement 90Sr and 137Cs, mix radioelement metering be 4 * 10 9Bg/L, firming body soaks in distilled water after solidifying in 28 days, measures 42 days leaching rate of radioelement respectively and is: 137Sr is 2.5 * 10 -6Cm/d, 90Cs is 3.4 * 10 -5Cm/d.
Embodiment 3:
Adopt a kind of H 3BO 3Content is that 11% solution is the chemical composition of simulated emission waste liquid, and the active powder body material that is adopted is composed as follows: ca aluminosilicate compound (SiO wherein 2Content is 33.5%, Al 2O 3Content is 13.6%, and CaO content is 38.6%): 74.25%; Active calcium aluminate: 20%; Bentonitic clay: 5%; Polyacrylamide: 0.25%; Sulfonated melamine compound condensation product: 0.5%; The liquid-solid ratio that is adopted during mixing is 0.60, at room temperature stir the mould of plastics that injects φ 50mm * 50mm behind the 3min, sealed maintenance is measured firming body after 28 days compressive strength is 41MPa, and after 30 freeze thawing circulation (15 ℃~20 ℃), the loss of strength rate is 5.0%.

Claims (8)

1, a kind of glass-like body curing materials of handling radioactive waste is characterized in that, the active powder body material that adopts multiple organic material and inorganic active material to be composited.
2, the glass-like body curing materials of processing radioactive waste as claimed in claim 1, it is characterized in that, said organic material comprises: the inorganic powder material in the aqueous solution is had the surfactant of dispersed activity, and aqueous solution is had tackify, firming body had the water-soluble polymers that increases packing; Said inorganic active material comprises the ca aluminosilicate compound through high temperature desulfurizing, deferrization and carbonization treatment, has the high temperature experience and extraordinary hydraulic cementing materials that forms and the inorganic mineral powder with special adsorption activity.
3, glass-like body curing materials as claimed in claim 2 is characterized in that, the percentage by weight of each component is in the said active powder: surfactant, 0.3%~1.2%;
Water-soluble polymers, 0.1%~1.0%;
The ca aluminosilicate compound, 50%~80%;
Hydraulic cementing materials, 10%~30%;
The inorganic mineral powder, 5%~20%.
4, glass-like body curing materials as claimed in claim 2, it is characterized in that, said surfactant comprises one or more of naphthalene sulfonic acid-formaldehyde condensation product, sulfonated melamine compound condensation product or sulfamate formaldehyde condensation products, and said water-soluble polymers comprises one or more of polyvinyl alcohol (PVA), polyacrylamide, hydroxyethyl cellulose and polyvinyl pyrrolidone.
5, glass-like body curing materials as claimed in claim 2 is characterized in that, active SiO in the said ca aluminosilicate compound 2Content be 30%~40%, active A l 2O 3Content be 10~30%, the content of active CaO is 30%~50%, surplus MgO, TiO 2, Fe 2O 3, K 2O, Na 2The total content 0%~10% of O etc.
6, glass-like body curing materials as claimed in claim 4, it is characterized in that said extraordinary hydraulic cementing materials comprises one or more of silicates, aluminate class and volcanic debris, shale ashes, flyash, blast furnace or open hearth slag and ultra-fine silicon ash.
7, glass-like body curing materials as claimed in claim 4 is characterized in that, said inorganic mineral powder with special adsorption activity comprise zeyssatite, bentonitic clay, zeolite powder and kaolinic one or more.
8, a kind of curing process method that adopts glass-like body curing materials as claimed in claim 1, it is characterized in that, with said curing materials in liquid-solid ratio is 0.5~0.8 scope by mixing and become to have mobile slurry with containing nitrate or boratory radioactive liquid waste, be solidified into solid through injection molding and airtight maintenance with glass-like body structure.
CN 00105281 2000-04-07 2000-04-07 Glass-like body solidifying material for treating radioactive wastes and solidifying method Expired - Fee Related CN1119820C (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
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CN102446569A (en) * 2010-09-30 2012-05-09 索列丹斯-弗莱西奈公司 Method for curing nuclear waste
CN102105944B (en) * 2008-10-24 2013-07-24 株式会社召命特殊建业 Method and apparatus for vitrification of radioactive waste
CN103641304A (en) * 2013-10-26 2014-03-19 溧阳市浙大产学研服务中心有限公司 Beryllium silicate glass containing CeO2 and method for treating radioactive waste liquid
CN103886926A (en) * 2012-12-21 2014-06-25 中核核电运行管理有限公司 Radioactive concentrated liquor solidifying formula
CN104464867A (en) * 2014-12-03 2015-03-25 中国工程物理研究院材料研究所 Preparation method of high-strength cement solidifying body for radioactive used oil
CN104658627A (en) * 2015-02-02 2015-05-27 中科华核电技术研究院有限公司 Solidified body used for performing glass curing process on low-medium radioactive waste and method
CN105741899A (en) * 2016-02-25 2016-07-06 中国核动力研究设计院 Solidification treatment additive, solidification formula and solidification process for radioactive boron-containing waste liquor
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
CN105814000A (en) * 2013-12-04 2016-07-27 韩国水力原子力株式会社 Glass composition for vitrifying mixed waste product and method for vitrifying mixed waste product using same
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
CN111056789A (en) * 2019-12-11 2020-04-24 南华大学 Method for solidifying radioactive waste residues

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CN101448752B (en) * 2006-03-20 2012-05-30 地理矩阵解决方案公司 Process and composition for the immobilization of high alkaline radioactive and hazardous wastes in silicate-based glasses

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102105944B (en) * 2008-10-24 2013-07-24 株式会社召命特殊建业 Method and apparatus for vitrification of radioactive waste
CN102446569A (en) * 2010-09-30 2012-05-09 索列丹斯-弗莱西奈公司 Method for curing nuclear waste
CN102446569B (en) * 2010-09-30 2017-03-01 索列丹斯-弗莱西奈公司 The method of solidification nuke rubbish
CN103886926A (en) * 2012-12-21 2014-06-25 中核核电运行管理有限公司 Radioactive concentrated liquor solidifying formula
CN103641304A (en) * 2013-10-26 2014-03-19 溧阳市浙大产学研服务中心有限公司 Beryllium silicate glass containing CeO2 and method for treating radioactive waste liquid
CN103641304B (en) * 2013-10-26 2016-08-17 溧阳市浙大产学研服务中心有限公司 Beryllium silicate glass and the method for process radioactive liquid waste including CeO2
CN105814000A (en) * 2013-12-04 2016-07-27 韩国水力原子力株式会社 Glass composition for vitrifying mixed waste product and method for vitrifying mixed waste product using same
CN105814000B (en) * 2013-12-04 2018-09-14 韩国水力原子力株式会社 Method for vitrification for its mixed waste of the vitrified glass composition of mixed waste and utilization
CN104464867A (en) * 2014-12-03 2015-03-25 中国工程物理研究院材料研究所 Preparation method of high-strength cement solidifying body for radioactive used oil
CN104464867B (en) * 2014-12-03 2017-03-15 中国工程物理研究院材料研究所 A kind of preparation method of Spent Radioactive machine oil high strength cement firming body
CN104658627A (en) * 2015-02-02 2015-05-27 中科华核电技术研究院有限公司 Solidified body used for performing glass curing process on low-medium radioactive waste and method
CN105741899A (en) * 2016-02-25 2016-07-06 中国核动力研究设计院 Solidification treatment additive, solidification formula and solidification process for radioactive boron-containing waste liquor
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
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
CN111056789A (en) * 2019-12-11 2020-04-24 南华大学 Method for solidifying radioactive waste residues
CN111056789B (en) * 2019-12-11 2021-10-22 南华大学 Method for solidifying radioactive waste residues

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