CN115159917A - Formula and method for curing radioactive waste resin by cement - Google Patents
Formula and method for curing radioactive waste resin by cement Download PDFInfo
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- CN115159917A CN115159917A CN202210784457.0A CN202210784457A CN115159917A CN 115159917 A CN115159917 A CN 115159917A CN 202210784457 A CN202210784457 A CN 202210784457A CN 115159917 A CN115159917 A CN 115159917A
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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
- C04B28/02—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 hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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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
- G21F9/28—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
- G21F9/304—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
- C04B2111/00017—Aspects relating to the protection of the environment
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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
- C04B2111/00025—Aspects relating to the protection of the health, e.g. materials containing special additives to afford skin protection
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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
- C04B2111/20—Resistance against chemical, physical or biological attack
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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
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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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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- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a formula of radioactive waste resin for cement solidification treatment, which comprises the following components in parts by weight: 1 part of ordinary Portland cement, 0.25-0.35 part of radioactive waste resin, 0.3-0.4 part of water, 0.002-0.005 part of water reducing agent, 0.05-0.08 part of waterproof agent, 0.05-0.08 part of admixture and 0.1-0.2 part of fly ash. The present disclosure also discloses a method for curing radioactive waste resin by cement. The cement mortar has proper fluidity and setting time, can solve the problems of difficult discharge and difficult cleaning and decontamination after stirring, and is particularly suitable for the cement curing process for stirring outside a radioactive waste resin barrel.
Description
Technical Field
The invention belongs to the technical field of radioactive waste solidification treatment, and particularly relates to a formula and a method for treating radioactive waste resin by cement solidification.
Background
The cement solidification is a radioactive waste resin solidification treatment technology widely used at home and abroad, radioactive nuclide is solidified by utilizing the material containing and adsorbing effects of cement, and the method has the advantages of simple process, mature process, less equipment consumption, low energy consumption, safety, reliability and the like.
The cement curing process by stirring outside the barrel is a common cement curing treatment mode, and has the advantages of high filling rate, high treatment capacity, convenience in inspection and maintenance and the like, but the requirements on the initial fluidity and the 30-minute fluidity of cement mortar obtained in the cement curing process are higher, the existing formula is difficult to meet the requirements on cement curing by stirring outside the barrel, the problems of bleeding of a cement cured body, difficulty in discharging after stirring and difficulty in cleaning and decontamination are easily caused, the volume containment rate of radioactive waste resin is low, and the level of radionuclide leaching rate of the cement cured body is high.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a formula and a method for treating radioactive waste resin by cement solidification, aiming at the defects in the prior art, the prepared cement mortar has proper fluidity and setting time, can solve the problems of difficult discharge, difficult cleaning and decontamination and the like after stirring, and is particularly suitable for the cement solidification process for stirring the radioactive waste resin outside a barrel.
The technical scheme for solving the technical problems is as follows:
according to one aspect of the invention, a formula for curing radioactive waste resin by cement is provided, which comprises the following components in parts by weight:
1 part of ordinary portland cement;
0.25-0.35 part of radioactive waste resin;
0.3-0.4 part of water;
0.002-0.005 part of water reducing agent;
0.05 to 0.08 portion of waterproof agent;
0.05 to 0.08 portion of an admixture;
0.1-0.2 part of fly ash.
Preferably, the type of the ordinary portland cement is p.o42.5; the water is demineralized water; the water reducing agent is a polycarboxylic acid compound; the waterproof agent is a modified siliceous material; the admixture is a metakaolin material.
Preferably, the polycarboxylic acid compound is one or a combination of two of polyester polycarboxylic acid and polyether polycarboxylic acid; the modified siliceous material is one or the combination of two of silica powder and siliceous waterproofing agent.
Preferably, the volume ratio of the strongly basic anion resin to the strongly acidic cation resin in the radioactive waste resin is 1:5 to 5:1.
Preferably, the particle size of the radioactive resin is in the range of 0.40 to 1.20mm.
Preferably, the wet apparent density of the radioactive resin is in the range of 0.65 to 0.85g/mL, and the moisture content of the radioactive resin is in the range of 45 to 55% on a wet basis.
According to another aspect of the present invention, there is provided a method of cement curing treatment of radioactive waste resin, comprising:
s11, respectively weighing the water reducing agent, the waterproof agent, the admixture and the fly ash according to the formula, uniformly mixing, and preparing into an additive;
s12, respectively weighing ordinary Portland cement, radioactive waste resin and water according to the formula, adding the water and the radioactive waste resin into a stirring device for stirring, adding the ordinary Portland cement and the additive in batches, and uniformly stirring to obtain cement mortar;
and S13, filling the cement mortar into a steel barrel, covering the steel barrel, and curing to obtain the cement solidified body of the radioactive waste resin.
Preferably, the method further comprises:
before weighing the radioactive waste resin, carrying out dehydration pretreatment on the radioactive waste resin
The invention relates to a formula and a method for treating radioactive waste resin by cement solidification, which can enable cement mortar to have proper fluidity and setting time by adding proper amounts of water reducing agent, waterproofing agent, admixture and fly ash, specifically, the initial fluidity of the cement mortar is 250-350mm, the fluidity of 30 minutes is 220-340 mm, the initial setting time is 31-49 h, and the initial setting time of complete final setting time is 32-58 h, the formula is especially suitable for a cement solidification process by stirring outside a radioactive waste resin barrel, can solve the problems of difficult discharging, cleaning and decontamination after stirring in the prior art, can meet the requirements of GB14569.1-2011 performance requirements of low and medium water flat radioactive waste solidified body-cement solidified body, can reduce the leaching rate level of the cement solidified body in 42 days by 1-2 orders of magnitude compared with the standard requirements, and can reduce the nuclide leaching fraction of the cement solidified body in 42 days by more than 50% compared with the standard requirements. Moreover, the formula has good compatibility with the components in the radioactive waste resin, the fluctuation range of the volume ratio (yin-yang ratio) of the strongly basic negative resin to the strongly acidic positive resin in the radioactive waste resin is 1:5-5:1, the influences of the fluctuation of the components of the radioactive waste resin, the errors of a metering system and the like can be overcome, the fluidity and the setting time of the cement mortar are ensured to be in a reasonable range, the situations of floating and uneven distribution of the resin in a cement solidified body are avoided, and the formula is suitable for cement solidification of most radioactive waste resins. In addition, the raw materials of the formula are easy to obtain, and especially, the ordinary portland cement can be locally produced and supplied, so that the cost is greatly reduced; the formula has high volumetric capacity of curing radioactive waste resin which can reach 35-40 percent and is higher than or at least not lower than the volumetric capacity of curing the radioactive waste resin which is commonly about 30 percent in the conventional formula for curing the cement by stirring outside a barrel.
Drawings
FIG. 1 is a formulation of a radioactive waste resin for cement curing treatment in an embodiment of the present invention;
FIG. 2 is a flow chart of a method of cement curing radioactive waste resin in an embodiment of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is obvious that the described embodiments are a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As shown in fig. 1, this embodiment discloses a formulation of radioactive waste resin for cement curing treatment, which comprises the following components in parts by weight:
1 part of ordinary portland cement;
0.25-0.35 part of radioactive waste resin;
0.3-0.4 part of water;
0.002-0.005 part of water reducing agent;
0.05 to 0.08 portion of waterproof agent;
0.05 to 0.08 portion of admixture;
0.1 to 0.2 portion of fly ash.
Specifically, the model of the ordinary portland cement is P.O42.5, and various performance parameters of the ordinary portland cement meet the requirements of GB175-2007 general portland cement, the cement is easy to produce, can be directly produced and supplied by local cement plants, and can reduce the cost;
the water is demineralized water, deionized water, tap water, etc., and in this embodiment, demineralized water is preferred.
The water reducing agent is a polycarboxylic acid compound, and specifically can be one or a combination of two of polyester polycarboxylic acid and polyether polycarboxylic acid.
The waterproof agent is a modified siliceous material, and specifically can be one or a combination of silicon powder and an organic silicon waterproof agent.
The admixture is a metakaolin-based material, such as metakaolin.
The radioactive waste resin is a radioactive waste resin produced by a post-treatment plant in a nuclear facility, and can contain strong-base anion resin and/or strong-acid cation resin, the volume ratio (anion-cation ratio) fluctuation range of the strong-base anion resin and the strong-acid cation resin is preferably 1:5-5:1, the particle size range is preferably 0.40-1.20 mm, the wet apparent density (wet resin bulk density) is preferably 0.65-0.85 g/mL, the moisture content of the radioactive resin is preferably less than 55%, the moisture content of the radioactive resin can be controlled to be generally 45-55%, wherein the radioactive nuclide mainly comprises radionuclide 90 Sr、 137 Cr and 60 Co。
according to the formula for treating the radioactive waste resin by cement solidification, a proper amount of water reducing agent, waterproofing agent, admixture and fly ash are added, so that the cement mortar has proper fluidity and setting time, specifically, the initial fluidity of the cement mortar is 275-340mm, the fluidity in 30 minutes is 240-340 mm, the initial setting time is 31-49 h, and the complete final setting time is 32-58 h, so that the application requirement of stirring outside a barrel can be completely met, the formula is particularly suitable for the cement solidification process by stirring the radioactive waste resin outside the barrel, the problems of difficult discharging and difficult cleaning and decontamination after stirring in the prior art can be solved, various performance indexes of the cement solidified body can meet the requirement of GB14569.1-2011 < performance requirement of low and medium-level radioactive waste solidified body performance requirement-cement solidified body >, the leaching rate level of the cement solidified body in 42 days can be reduced by 1-2 quantity levels compared with the standard requirement, and the accumulated leaching fraction of the cement solidified body in 42 days can be reduced by more than 50%. Moreover, the formula has good compatibility with the components in the radioactive waste resin, the fluctuation range of the volume ratio (yin-yang ratio) of the strongly basic negative resin and the strongly acidic positive resin in the radioactive waste resin is 1:5-5:1, the influences of the fluctuation of the material components of the radioactive waste resin, the errors of a metering system and the like can be overcome, the fluidity and the setting time of the cement mortar are ensured to be in reasonable ranges, the situations of floating and uneven distribution of the resin in a cement solidified body are avoided, and the formula can be suitable for cement solidification of most of the radioactive waste resin. In addition, the raw materials of the formula are easy to obtain, and especially, the common Portland cement can be locally produced and supplied, so that the cost is greatly reduced; the formula has high curing volume containment rate of the radioactive waste resin, which can reach 35 to 40 percent and is higher than or at least not lower than the curing volume containment rate of the prior cement curing formula which is commonly about 30 percent.
Example 2
As shown in fig. 2, the present embodiment discloses a method for curing radioactive waste resin by cement, which comprises:
s11, respectively weighing a water reducing agent, a waterproof agent, an admixture and fly ash according to the formula of the radioactive waste resin for cement solidification treatment in the embodiment 1, uniformly mixing, and preparing into an additive;
s12, weighing ordinary portland cement, radioactive waste resin and water respectively according to the formula of the radioactive waste resin for cement curing treatment in the embodiment 1, adding the radioactive waste resin and the water into a stirring device (such as an out-of-bucket stirring mixer), starting the stirring device, stirring, adding the ordinary portland cement and additives in batches, and stirring for a period of time (for example, 5-40 min) until the mixture is uniformly stirred to obtain cement mortar;
and S13, discharging the cement mortar prepared in the step S12 into a steel drum, covering the steel drum, and curing to obtain the cement solidified body of the radioactive waste resin. In this embodiment, the curing time is preferably 28 days or more to ensure the structural stability of the cement cured body.
In some embodiments, the method further comprises: before the radioactive waste resin is weighed, the radioactive waste resin is subjected to dehydration pretreatment, so that the moisture content of the wet basis of the radioactive waste resin is controlled below 55 percent and generally controlled to be 45-55 percent. In practice, the pump can be used to dehydrate the radioactive waste resin until the weight of the radioactive waste resin does not decrease.
Several sets of preparation examples are provided below to perform verification tests on the method for curing radioactive waste resin by cement of this embodiment, wherein the amounts of water reducing agent, water repellent, admixture, and fly ash are shown in table 1, and the radioactive waste resin is replaced by the simulated waste resin prepared by the components shown in table 2.
Table 1 formula raw material amounts
TABLE 2 composition table of simulated liquid of radioactive waste resin
Preparation example 1
As shown in table 1, 0.003 part of polyether polycarboxylic acid, 0.068 part of a composition of silicon powder and a siliceous waterproofing agent (wherein, the mass ratio of silicon powder to siliceous waterproofing agent =1: 10), 0.06 part of metakaolin, and 0.14 part of class II fly ash are weighed respectively in parts by weight, mixed and stirred uniformly to prepare an additive;
as shown in table 2, according to 5:1 volume ratio of the quaternary ammonium group [ -N (CH) on the strongly basic anion resin (such as styrene-divinylbenzene copolymer with gel crosslinking structure) 3 ) 3 OH]The anion exchange resin) and a strongly acidic cation resin (e.g., a styrene-divinylbenzene copolymer having a gel-type crosslinked structure and having a sulfonic acid group (-SO) 3 H) The cation exchange resin of (4) to obtain an initial simulated waste resin, and adding a non-radioactive CsCl crystal and a non-radioactive SrCl crystal to the initial simulated waste resin in an amount of 0.004% by mass based on the mass of the initial simulated waste resin, respectively 2 Crystal and nonradioactive CoCl 2 Mixing and stirring the crystals uniformly to prepare final simulated waste resin so as to simulate radioactive waste resin;
as shown in table 1, 1 part of portland cement p.o42.5, 0.32 part of simulated waste resin, 0.38 part of demineralized water, and 0.271 part of the additive prepared above were weighed in parts by weight, and 0.32 part of simulated waste resin and 0.38 part of demineralized water were added together to a 400L external stirring mixer, stirring was started, and then 1 part of portland cement and 0.27 part of additive were sequentially added in batches and stirred for 10min until they were uniformly stirred, to obtain cement mortar;
discharging the cement mortar in the out-of-barrel stirring mixer into a special steel barrel required by the radioactive waste resin curing treatment, covering the steel barrel, curing for 28 days, and completely curing the cement mortar to obtain a cement cured body of the radioactive waste resin, wherein the curing volume inclusion rate is 35 percent and is higher than or at least not lower than the curing volume inclusion rate which is about 30 percent commonly used in the existing out-of-barrel stirring cement curing formula.
The cement mortar and the cement cured product of preparation example 1 were subjected to performance tests in accordance with standards such as GB14569.1, GB/T7023, and GB 1346, and the results of the performance tests are shown in Table 3.
Table 3 results of performance test of preparation example 1
As can be seen from Table 3, the cement mortar and the cement cured body meet the corresponding national standard requirements in terms of various performance indexes, and can meet the requirements of the out-of-bucket stirring cement curing process on fluidity and setting time.
Preparation example 2
As shown in table 1, 0.004 parts of polyether polycarboxylic acid, 0.055 part of a composition of silicon powder and a siliceous waterproofing agent (wherein the mass ratio of silicon powder to siliceous waterproofing agent = 1:1), 0.065 parts of metakaolin, and 0.127 parts of class I fly ash are weighed respectively in parts by weight, mixed and stirred uniformly to prepare an additive;
as shown in table 2, the following ratios were 1:5 volume ratio of strongly basic anion resin (such as styrene-divinylbenzene copolymer with gel crosslinking structure having quaternary ammonium group [ -N (CH) ] 3 ) 3 OH]The anion exchange resin) and a strongly acidic cation resin (e.g., a styrene-divinylbenzene copolymer having a gel-type crosslinked structure and having a sulfonic acid group (-SO) 3 H) The cation exchange resin of (4) to obtain an initial simulated waste resin, and adding a non-radioactive CsCl crystal and a non-radioactive SrCl crystal to the initial simulated waste resin in an amount of 0.004% by mass based on the mass of the initial simulated waste resin, respectively 2 Crystal and nonradioactive CoCl 2 Mixing and stirring the crystals uniformly to prepare simulated waste resin so as to simulate radioactive waste resin;
as shown in table 1, 1 part of portland cement p.o42.5, 0.32 part of simulated waste resin, 0.35 part of demineralized water, and 0.251 part of the additive prepared above were weighed, respectively, 0.32 part of simulated waste resin and 0.35 part of demineralized water were added together to a 400L external stirring mixer, stirring was started, 1 part of portland cement and 0.25 part of additive were sequentially added in batches, and stirred for 10min until uniform stirring was achieved, to obtain cement mortar;
and discharging the cement mortar in the out-of-barrel stirring mixer into a special steel barrel required by the radioactive waste resin for cement curing treatment, covering the steel barrel, curing for 28 days, and completely curing the cement mortar to obtain a cement cured body, wherein the curing volume inclusion rate is 40 percent and is higher than or at least not lower than the curing volume inclusion rate which is commonly about 30 percent in the existing out-of-barrel stirring cement curing formula.
The cement mortar and the cement cured product of preparation example 2 were subjected to performance tests in accordance with standards such as GB14569.1, GB/T7023, and GB 1346, and the results of the performance tests are shown in Table 4.
Table 4 results of performance test of preparation example 2
As can be seen from Table 4, the cement mortar and the cement cured body meet the corresponding national standard requirements in terms of various performance indexes, and can meet the requirements of the out-of-bucket stirring cement curing process on fluidity and setting time.
Preparation example 3
As shown in table 1, 0.004 parts of polyester polycarboxylic acid, 0.075 part of a composition of silicon powder and a siliceous waterproofing agent (wherein the mass ratio of the silicon powder to the siliceous waterproofing agent = 1:8), 0.075 part of metakaolin and 0.166 part of class I fly ash are weighed respectively, mixed and stirred uniformly to prepare an additive;
as shown in table 2, the following ratios were 1:2.5 the volume ratio of the resin is measured to obtain strong basic anion resin (e.g. styrene-divinylbenzene copolymer with gel crosslinking structure having quaternary ammonium group [ -N (CH) 3 ) 3 OH]The anion exchange resin) and a strongly acidic cation resin (e.g., a styrene-divinylbenzene copolymer having a gel-type crosslinked structure and having a sulfonic acid group (-SO) 3 H) The cation exchange resin of (4) to obtain an initial simulated waste resin, and adding a non-radioactive CsCl crystal and a non-radioactive SrCl crystal to the initial simulated waste resin in an amount of 0.004% by mass based on the mass of the initial simulated waste resin, respectively 2 Crystal and nonradioactive CoCl 2 Mixing and stirring the crystals uniformly to prepare simulated waste resin so as to simulate radioactive waste resin;
as shown in table 1, 1 part of portland cement p.o42.5, 0.35 part of simulated waste resin, 0.34 part of demineralized water, and 0.32 part of the additive prepared above were weighed, respectively, and 0.35 part of simulated waste resin and 0.34 part of demineralized water were added together to a 400L external stirring mixer, stirring was started, 1 part of portland cement and 0.32 part of additive were sequentially added in batches, and stirred for 10min until uniform stirring was achieved, to obtain cement mortar;
and discharging the cement mortar in the out-of-barrel stirring mixer into a special steel barrel required by the radioactive waste resin for cement curing treatment, covering the steel barrel, curing for 28 days, and completely curing the cement mortar to obtain a cement cured body, wherein the curing volume inclusion rate is 40 percent and is higher than or at least not lower than the curing volume inclusion rate which is commonly about 30 percent in the existing out-of-barrel stirring cement curing formula.
The cement mortar and the cement cured product of preparation example 3 were subjected to performance tests in accordance with standards such as GB14569.1, GB/T7023, and GB 1346, and the results of the performance tests are shown in Table 5.
Table 5 results of performance test of preparation example 3
As can be seen from Table 5, the cement mortar and the cement cured body meet the corresponding national standard requirements in terms of various performance indexes, and can meet the requirements of the out-of-drum stirring cement curing process on fluidity and setting time.
Preparation example 4
As shown in table 1, 0.005 parts of polyester polycarboxylic acid, 0.08 parts of a composition of silicon powder and a siliceous waterproofing agent (wherein the mass ratio of silicon powder to siliceous waterproofing agent = 1:2), 0.08 parts of metakaolin, and 0.187 parts of class II fly ash were weighed, respectively, and mixed and stirred uniformly to prepare an additive;
taking strong alkaline anion resin (such as styrene-divinylbenzene copolymer with gel crosslinking structure and quaternary ammonium group [ -N (CH) 3 ) 3 OH]The anion exchange resin) and a strongly acidic cation resin (e.g., a styrene-divinylbenzene copolymer having a gel-type crosslinked structure and having a sulfonic acid group (-SO) 3 H) Cation exchange resin of) anddewatering was carried out until the weight no longer dropped and was stopped as shown in table 2 at a rate of 2.5:1, respectively weighing the dehydrated strong-base anion resin and strong-acid cation resin, mixing to obtain initial simulated waste resin, and respectively adding non-radioactive CsCl crystal and non-radioactive SrCl according to 0.004 percent of the mass of the initial simulated waste resin 2 Crystal and nonradioactive CoCl 2 Mixing and stirring the crystals uniformly to prepare simulated waste resin so as to simulate radioactive waste resin;
as shown in table 1, 1 part of portland cement p.o42.5, 0.34 part of simulated waste resin, 0.32 part of demineralized water, and 0.352 part of the additive prepared above were weighed, respectively, and 0.34 part of simulated waste resin and 0.32 part of demineralized water were added together to a 400L external stirring mixer, stirring was started, 1 part of portland cement and 0.35 part of additive were sequentially added in batches, and stirred for 10min until uniform stirring was achieved, to obtain cement mortar;
and discharging the cement mortar in the out-of-barrel stirring mixer into a special steel barrel required by the radioactive waste resin for cement curing treatment, covering the steel barrel, curing for 28 days, and completely curing the cement mortar to obtain a cement cured body, wherein the curing volume inclusion rate is 40 percent and is higher than or at least not lower than the curing volume inclusion rate which is commonly about 30 percent in the existing out-of-barrel stirring cement curing formula.
The cement mortar and the cement cured product of preparation example 4 were subjected to performance tests in accordance with standards such as GB14569.1, GB/T7023, and GB 1346, and the results of the performance tests are shown in Table 6.
Table 6 results of performance test of preparation example 4
As can be seen from Table 6, the cement mortar and the cement cured body meet the corresponding national standard requirements in terms of various performance indexes, and can meet the requirements of the out-of-drum stirring cement curing process on fluidity and setting time.
It will be understood that the above embodiments are merely exemplary embodiments adopted to illustrate the principles of the present invention, and the present invention is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (8)
1. The formula of the radioactive waste resin for curing cement is characterized by comprising the following components in parts by weight:
1 part of ordinary portland cement;
0.25-0.35 part of radioactive waste resin;
0.3-0.4 part of water;
0.002-0.005 part of water reducing agent;
0.05 to 0.08 portion of waterproof agent;
0.05 to 0.08 portion of an admixture;
0.1 to 0.2 portion of fly ash.
2. The formulation for cement curing radioactive waste resin according to claim 1, wherein the portland cement has a model number of p.o42.5;
the water is demineralized water;
the water reducing agent is a polycarboxylic acid compound;
the waterproof agent is a modified siliceous material;
the admixture is a metakaolin material.
3. The formulation for the out-of-cask mixing cement setting of radioactive waste resin of claim 2 wherein the polycarboxylic acid type compound is one or a combination of two of polyester polycarboxylic acid and polyether polycarboxylic acid;
the modified siliceous material is one or the combination of two of silica powder and siliceous waterproofing agent.
4. The formulation of claim 1, wherein the volume ratio of the strongly basic anion resin to the strongly acidic cation resin in the radioactive waste resin is 1:5-5:1.
5. The formulation for cement curing radioactive waste resin according to claim 1, wherein the particle size of the radioactive waste resin is in the range of 0.40 to 1.20mm.
6. The formulation of claim 1, wherein the radioactive waste resin has a wet apparent density in the range of 0.65 to 0.85g/mL, and the radioactive waste resin has a moisture content of 45 to 55% on a wet basis.
7. A method of cement curing radioactive waste resin, comprising:
s11, respectively weighing a water reducing agent, a waterproof agent, an admixture and fly ash according to the formula of any one of claims 1 to 6, uniformly mixing, and preparing into an additive;
s12, respectively weighing ordinary portland cement, radioactive waste resin and water according to the formula of any one of claims 1 to 6, adding the water and the radioactive waste resin into a stirring device for stirring, adding the ordinary portland cement and the additive in batches, and uniformly stirring to obtain cement mortar;
and S13, filling the cement mortar into a steel barrel, covering the steel barrel, and curing to obtain the cement solidified body of the radioactive waste resin.
8. The method of cement curing radioactive waste resin according to claim 7, further comprising:
before weighing the radioactive waste resin, the radioactive waste resin is subjected to dehydration pretreatment.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102262910A (en) * | 2011-05-13 | 2011-11-30 | 清华大学 | Method for solidifying spent radioactive resin by blending sulphoaluminate cement and admixtures |
| CN106960692A (en) * | 2017-03-10 | 2017-07-18 | 清华大学 | Radioactive spent resin cement solidification is formulated and curing |
| CN111635168A (en) * | 2020-05-07 | 2020-09-08 | 中国工程物理研究院材料研究所 | High-stability composite geological cement for nuclide solidification and application method thereof |
| CN111662049A (en) * | 2019-03-07 | 2020-09-15 | 北京万之悦科技发展有限公司 | High-strength cement-based radioactive waste curing and fixing material |
| CN112479664A (en) * | 2020-11-20 | 2021-03-12 | 中核核电运行管理有限公司 | Boron-containing waste resin cement curing formula and curing method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102262910A (en) * | 2011-05-13 | 2011-11-30 | 清华大学 | Method for solidifying spent radioactive resin by blending sulphoaluminate cement and admixtures |
| CN106960692A (en) * | 2017-03-10 | 2017-07-18 | 清华大学 | Radioactive spent resin cement solidification is formulated and curing |
| CN111662049A (en) * | 2019-03-07 | 2020-09-15 | 北京万之悦科技发展有限公司 | High-strength cement-based radioactive waste curing and fixing material |
| CN111635168A (en) * | 2020-05-07 | 2020-09-08 | 中国工程物理研究院材料研究所 | High-stability composite geological cement for nuclide solidification and application method thereof |
| CN112479664A (en) * | 2020-11-20 | 2021-03-12 | 中核核电运行管理有限公司 | Boron-containing waste resin cement curing formula and curing method thereof |
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