CN116535172A - Treatment method of high-specific-activity rare earth slag and solidified body - Google Patents
Treatment method of high-specific-activity rare earth slag and solidified body Download PDFInfo
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- CN116535172A CN116535172A CN202310824307.2A CN202310824307A CN116535172A CN 116535172 A CN116535172 A CN 116535172A CN 202310824307 A CN202310824307 A CN 202310824307A CN 116535172 A CN116535172 A CN 116535172A
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- earth slag
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- 239000002893 slag Substances 0.000 title claims abstract description 181
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 110
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 109
- 230000000694 effects Effects 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 52
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052788 barium Inorganic materials 0.000 claims abstract description 77
- 238000003756 stirring Methods 0.000 claims abstract description 60
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 52
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000011398 Portland cement Substances 0.000 claims description 16
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 15
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 12
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 9
- 230000002285 radioactive effect Effects 0.000 abstract description 8
- 238000000748 compression moulding Methods 0.000 abstract description 5
- 239000002901 radioactive waste Substances 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 abstract description 2
- 239000003469 silicate cement Substances 0.000 abstract description 2
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 13
- 238000002386 leaching Methods 0.000 description 11
- 238000012423 maintenance Methods 0.000 description 11
- 229910001422 barium ion Inorganic materials 0.000 description 10
- 230000001988 toxicity Effects 0.000 description 10
- 231100000419 toxicity Toxicity 0.000 description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000004568 cement Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- GJEZFXDASHZTRO-UHFFFAOYSA-N iron thorium Chemical compound [Fe].[Fe].[Fe].[Fe].[Fe].[Th] GJEZFXDASHZTRO-UHFFFAOYSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012857 radioactive material Substances 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- -1 sulfide ions Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- 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
-
- 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
- C04B2111/00784—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes for disposal only
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The application belongs to the field of solid waste treatment and disposal, and relates to a disposal method of high-specific-activity rare earth slag, which comprises the following steps: the pretreatment step of barium slag: adding hydrogen peroxide solution into the barium slag, uniformly stirring, and standing for reaction; then adding sulfuric acid, and fully and uniformly stirring until no bubbles are generated; rare earth slag treatment: adding rare earth slag into the barium slag obtained by the pretreatment of the barium slag, and continuously and uniformly stirring; and (3) forming and curing: and adding ordinary silicate cement into the material treated by the rare earth slag treatment step, continuously stirring uniformly, then carrying out compression molding treatment, and carrying out moisture preservation at normal temperature to obtain a solidified body. The barium slag is used for treating the high-specific-activity rare earth slag, and the barium element in the barium slag can be fully utilized through a simple process, so that the treatment effect of the high-specific-activity radioactive slag is better, and the specific activity of a solidified body is effectively reduced; not only realizes the reclamation of barium element in the barium slag, but also realizes the cooperative treatment of dangerous waste and radioactive waste.
Description
Technical Field
The application belongs to the field of solid waste treatment and disposal, and particularly relates to a high-efficiency treatment method of high-specific-activity rare earth slag and a solidified body.
Background
The rare earth resources in China are rich, the market share of rare earth products reaches 70 percent in the world, and great contribution is made to the economic construction of China. Rare earth primary ores in China generally contain radionuclides (such as U, th, ra and the like), which are mostly higher than natural background, and belong to associated radioactive ores. Along with the processes of exploitation, smelting, processing and the like, radioactive substances can be enriched in rare earth products or waste residues. In the smelting process of rare earth production, some harmful substances with radioactivity are transferred into waste residues to form rare earth residues with high specific activity. The piling up of the rare earth slag can cause serious pollution to the surrounding environment.
The rare earth smelting is mainly performed by a wet method, and according to different processes and production links of the rare earth industry, the rare earth metallurgical slag can be divided into water leaching slag in acid method production, acid dissolving slag in alkali method production, iron thorium slag and the like. The rare earth slag has the following characteristics: (1) the activity concentration range is large. Investigation shows that the radioactivity specific activity of the rare earth waste residue is large in range, and the difference is several orders of magnitude. The thorium content in the superior slag and the acid slag is high, 0.78% and 0.42% respectively, and the specific activity of the radioactive material reaches 8.6X10 4 Bq/kg and 1.4X10 5 Bq/kg. And (2) the amount of waste residues is large.
Generally, for safe storage, the radioactive slag is subjected to solidification treatment to reduce the pollution of the radioactive rare earth smelting slag to the environment. Different curing methods such as cement curing, asphalt curing, plastic curing, glass curing and the like can be adopted for different types of wastes, and the methods have the defects of higher cost, large curing material consumption (more than 5 times of radioactive slag is generally needed) and poor radioactive shielding effect, so that the problems of more effectively and lower cost for placing the rare earth mining smelting slag of the radioactive ore, protecting the ecological environment and becoming urgent are solved.
Disclosure of Invention
The invention aims to provide a treatment method of high-specific-activity rare earth slag and a solidified body, so as to solve the problems of high cost, large capacity-increasing ratio and poor radioactive shielding of the existing solidification method.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a method of disposing of high specific activity rare earth slag comprising:
the pretreatment step of barium slag: adding hydrogen peroxide solution into the barium slag, uniformly stirring, and standing for reaction; then adding sulfuric acid solution, and fully and uniformly stirring until no bubbles are generated;
rare earth slag treatment: adding rare earth slag into the barium slag obtained by the pretreatment of the barium slag, and continuously and uniformly stirring;
and (3) forming and curing: and adding ordinary silicate cement into the material treated by the rare earth slag treatment step, continuously stirring uniformly, then carrying out compression molding treatment, and carrying out moisture preservation at normal temperature to obtain a rare earth slag solidified body.
Preferably, in the barium residue pretreatment step, the standing reaction time is 10-60min (such as 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, etc.) to oxidize sulfide ions.
Preferably, in the barium residue pretreatment step, the hydrogen peroxide solution is added in an amount of H 2 O 2 Meter, said H 2 O 2 The mass ratio of the barium sulfide to the barium sulfide in the barium slag is 0.2:1-0.3:1 (such as 0.22:1, 0.25:1, 0.28:1, etc.). If the addition amount of the hydrogen peroxide is too large, the reagent is easy to waste; the addition amount of hydrogen peroxide is too small, barium sulfide in the barium slag cannot be fully oxidized, residual sulfide is easy to produce hydrogen sulfide gas in the subsequent rare earth slag treatment step, and the working environment is deteriorated.
Preferably, in the step of preprocessing the barium slag, the mass ratio of the hydrogen peroxide solution to the barium slag is 0.1:1-0.2:1, and if the first liquid-solid ratio is too large, the system is easy to contain too much water, which is not beneficial to subsequent solidification; if the first liquid-solid ratio is too small, the mixture is not likely to react sufficiently, and the effect of oxidizing barium sulfide sufficiently cannot be achieved.
Preferably, in the barium residue pretreatment step, the sulfuric acid solution is added in a molar amount of H 2 SO 4 Meter, said H 2 SO 4 The molar amounts of barium sulfide (BaS) and barium carbonate (BaCO) in the barium slag 3 ) 1.0 to 1.1 times the sum of the molar amounts of (a).
Preferably, the mass concentration of the sulfuric acid solution is 20-40% (such as 22%, 25%, 30%, 35%, 38%, etc.), if the sulfuric acid concentration is too high, the safety is easily affected by excessive heating, uneven stirring is easily caused, and if the concentration is too low, excessive system water can be caused; the second liquid-solid ratio, namely the mass ratio of the sulfuric acid solution to the barium slag is 1:2-1:4 (such as 1:2.5, 1:3, 1:3.5, etc.), if the second liquid-solid ratio is too large, the system is easy to contain too much water, which is not beneficial to subsequent solidification; if the second liquid-solid ratio is too small, the mixture is not likely to sufficiently contact and react.
Preferably, in the rare earth slag treatment step, the addition amount of the rare earth slag is 1.2-1.5 times (such as 1.25 times, 1.3 times, 1.35 times, 1.4 times, 1.45 times, etc.) the mass of the barium slag. If the addition amount of the rare earth slag is too large, the radioactivity of the rare earth slag is reduced to a limited extent; if rare earth slag is added too little, the solidified capacity-increasing ratio is increased, and the subsequent treatment cost is increased.
Preferably, in the rare earth slag treatment step, stirring is continued for 3-5min, so that the materials can reach a uniform state.
Preferably, in the molding and curing step, the addition amount of the ordinary Portland cement (see general Portland cement GB 175-2007) is 5-8% (such as 5.5%, 6%, 6.5%, 7%, 7.5% and the like) of the total mass of the barium slag and the rare earth slag. If the addition amount of cement is too small, the strength of a solidified body is easily affected; if the cement is added in an excessive amount, curing increases the cost.
Preferably, in the molding and curing step, stirring is continued for 3-5min, so that the materials can reach a uniform state.
Preferably, in the molding and curing step, the molding pressure of the press molding process is 10 to 15MPa (e.g., 10.5MPa, 11MPa, 12MPa, 13MPa, 14MPa, 14.5MPa, etc.), and a hydraulic molding machine may be used. The compression molding can increase the density of the solidified body by about 20 percent, and effectively reduce the volume of the solidified body.
The application also provides a high specific activity rare earth slag solidified body prepared by adopting the method. The specific activity and strength properties of the cured body are more satisfactory.
The technical principle of the application comprises: firstly, oxidizing barium sulfide in barium slag into barium hydroxide and sulfur simple substances by using hydrogen peroxide, then adding sulfuric acid to convert the barium hydroxide and the barium carbonate in the barium slag into barium sulfate, wherein the barium sulfate has stable performance, the quality of a barium element kernel is large, and energy carried by rays is easily absorbed by the kernel in the collision process of the kernel, so that the rays cannot penetrate through the kernel and are ejected, and the effect of blocking the rays is achieved.
Compared with the prior art, the scheme of the application has the following beneficial effects:
1) The method uses the solid waste barium slag to treat the rare earth slag with high specific activity, and the barium element in the barium slag can be fully utilized through a simple process, so that the treatment effect of the radioactive waste slag with high specific activity is better, and the specific activity of a solidified body is effectively reduced;
2) The method can realize the reclamation of barium element in the barium slag and the cooperative treatment of dangerous waste (barium slag) and radioactive waste;
3) Unlike barite aggregate (namely barium sulfate ore), the granularity of the barium slag is finer, and the barium slag can be more uniformly wrapped by the rare earth slag after being mixed with the rare earth slag, so that the operation is simple;
4) By adopting the treatment method provided by the application, the cured body can have better strength performance by using less cement.
Drawings
Fig. 1 is a process flow diagram of a method for disposing of high specific activity rare earth slag provided herein.
Detailed Description
Fig. 1 is a flowchart of a method for disposing high specific activity rare earth slag according to a preferred embodiment of the present application, which basically includes the following steps:
s1, pretreatment of barium residues: adding hydrogen peroxide solution into the barium slag, uniformly stirring, and standing for 0.2-1h; then adding sulfuric acid solution, and fully and uniformly stirring until no bubbles are generated;
s2, rare earth slag treatment: adding rare earth slag into the barium slag obtained in the step S1, and continuously stirring for 3-5 minutes;
s3, curing and forming: and (2) adding ordinary Portland cement into the sample obtained in the step (S2), continuously stirring for 3-5 minutes, performing compression molding, and performing moisture-preserving maintenance at normal temperature to obtain a rare earth slag solidified body.
Preferably, in step S1, a hydrogen peroxide solution (in the form of H 2 O 2 Calculated by weight) and the mass ratio of the added amount to the barium sulfide in the barium slag is 0.2:1-0.3:1. If the adding amount of the hydrogen peroxide solution is too large, the reagent is easy to waste; if the addition amount is too small, barium sulfide in the barium slag cannot be oxidized sufficiently, and residual sulfide is liable to produce hydrogen sulfide gas in step S2, resulting in deterioration of the working environment.
Preferably, in the step S1, the mass ratio of the first liquid-solid ratio, namely the hydrogen peroxide solution to the barium slag is 0.1:1-0.2:1, and the excessive liquid-solid ratio causes excessive water content in the system, which is unfavorable for subsequent solidification; if the liquid-solid ratio is too small, the mixture cannot sufficiently react, and the effect of oxidizing barium sulfide cannot be achieved.
Preferably, in step S1, the sulfuric acid solution is added in a molar amount of 1.0 to 1.1 times the sum of the molar amounts of barium sulfide and barium carbonate in the barium slag.
Preferably, in the step S1, the mass concentration of the sulfuric acid solution is 20-40%, and the mass ratio of the second liquid-solid ratio, namely the sulfuric acid solution to the barium slag is 1:2-1:4.
Preferably, in the step S2, the addition amount of the rare earth slag is 1.2-1.5 times of the mass of the barium slag. If the addition amount of the rare earth slag is too large, the radioactivity of the rare earth slag is reduced to a limited extent; if rare earth slag is added too little, the solidified capacity-increasing ratio is increased, and the subsequent treatment cost is increased.
Preferably, in the step S3, the addition amount of the ordinary Portland cement is 5-8% of the total mass of the barium slag and the rare earth slag. If the addition amount of cement is too small, the strength of a cured body is affected; if the cement is added in an excessive amount, curing increases the cost.
Preferably, in the step S3, a hydraulic forming machine is adopted for compression forming, and the forming pressure is 10-15MPa. The compression molding can increase the density of the solidified body by about 20 percent, and effectively reduce the volume of the solidified body.
The following examples are set forth in further detail to illustrate the present application, and the scope of protection of the present application includes, but is not limited to, the following examples. The examples do not identify specific experimental procedures or conditions, which may be followed by procedures or conditions that are routine procedures described in the literature in this field. The various reagents and raw materials used in the examples are all commercial products, and some medicaments with different concentrations are prepared by diluting the commercial products. The raw material barium slag used in the examples was taken from Guizhou Tianzhu chemical Co., ltd, and its main composition was determined to be 16.34% of barium sulfate, 2.60% of barium sulfide, and 16.17% of barium carbonate. The raw material rare earth slag used in the examples was obtained from New resource rare earth Co.Ltd in Quannan county of Ganz, and the specific activity of the material was 1.2X10 7 Bq/kg, belonging to the low level of radioactive waste.
Example 1
The treatment method of the high specific activity rare earth slag in the embodiment comprises the following steps:
(1) Adding 0.5kg of hydrogen peroxide solution with the mass concentration of 5.2% into 5.0kg of barium slag, uniformly stirring, and standing for 0.5h; then adding 2.5kg of sulfuric acid with the concentration of 20%, and fully and uniformly stirring until no bubbles are generated;
(2) Rare earth slag treatment: adding 6.0kg of rare earth slag into the barium slag in the step (1), and continuously stirring for 3 minutes;
(3) And (3) forming: and (3) adding 0.55kg of ordinary Portland cement into the sample obtained in the step (2), continuously stirring for 3 minutes, pressurizing by a hydraulic forming machine for 10MPa for forming, and performing moisture-preserving maintenance at normal temperature to obtain a rare earth slag solidified body.
The cured bulk strength was determined to be 10.52MPa and the specific activity was determined to be 2.2X10 3 Bq/kg, barium ion leaching toxicity is 12.3mg/L.
Example 2
The treatment method of the high specific activity rare earth slag in the embodiment comprises the following steps:
(1) Adding 0.75kg of hydrogen peroxide solution with the mass concentration of 5.2% into 5.0kg of barium slag, uniformly stirring, and standing for 0.5h; then adding 2.5kg of sulfuric acid with the concentration of 20%, and fully and uniformly stirring until no bubbles are generated;
(2) Rare earth slag treatment: adding 6.5kg of rare earth slag into the barium slag in the step (1), and continuously stirring for 5 minutes;
(3) And (3) forming: and (3) adding 0.70kg of ordinary Portland cement into the sample obtained in the step (2), continuously stirring for 5 minutes, pressurizing by a hydraulic forming machine for 10MPa for forming, and performing moisture-preserving maintenance at normal temperature to obtain a rare earth slag solidified body.
The strength of the cured product was determined to be 12.45MPa and the specific activity was determined to be 2.7X10 3 Bq/kg, the barium ion leaching toxicity is 10.4mg/L.
Example 3
The treatment method of the high specific activity rare earth slag in the embodiment comprises the following steps:
(1) Adding 1.0kg of hydrogen peroxide solution with the mass concentration of 2.6% into 5.0kg of barium slag, uniformly stirring, and standing for 0.5h; then adding 2.5kg of sulfuric acid with the concentration of 20%, and fully and uniformly stirring until no bubbles are generated;
(2) Rare earth slag treatment: adding 6.5kg of rare earth slag into the barium slag in the step (1), and continuously stirring for 4 minutes;
(3) And (3) forming: and (3) adding 0.80kg of ordinary Portland cement into the sample obtained in the step (2), continuously stirring for 4 minutes, pressurizing by a hydraulic forming machine for 10MPa for forming, and performing moisture-preserving maintenance at normal temperature to obtain a rare earth slag solidified body.
The strength of the cured product was 15.23MPa and the specific activity was 3.1×10 3 Bq/kg, barium ion leaching toxicity is 8.7mg/L.
Example 4
The treatment method of the high specific activity rare earth slag in the embodiment comprises the following steps:
(1) Adding 1.0kg of hydrogen peroxide solution with the mass concentration of 2.6% into 5.0kg of barium slag, uniformly stirring, and standing for 0.5h; then adding 1.67kg of sulfuric acid with the concentration of 30%, and fully and uniformly stirring until no bubbles are generated;
(2) Rare earth slag treatment: adding 7.5kg of rare earth slag into the barium slag in the step (1), and continuously stirring for 4 minutes;
(3) And (3) forming: adding 1.0kg of ordinary Portland cement into the sample obtained in the step (2), continuously stirring for 4 minutes, pressurizing by a hydraulic forming machine for 10MPa for forming, and performing moisture-preserving maintenance at normal temperature to obtain a rare earth slag solidified body.
The strength of the cured product was measured to be 20.58MPa, and the specific activity was measured to be 3.3X10 3 Bq/kg, barium ion leaching toxicity is 5.8mg/L.
Example 5
The treatment method of the high specific activity rare earth slag in the embodiment comprises the following steps:
(1) Adding 0.75-kg of hydrogen peroxide solution with the mass concentration of 5.2% into 5.0kg of barium slag, uniformly stirring, and standing for 0.5h; then adding 1.25kg of sulfuric acid with the concentration of 40%, and fully and uniformly stirring until no bubbles are generated;
(2) Rare earth slag treatment: adding 7.0. 7.0 kg of rare earth slag into the barium slag in the step (1), and continuously stirring for 4 minutes;
(3) And (3) forming: and (3) adding ordinary Portland cement 0.90 and kg into the sample obtained in the step (2), continuously stirring for 4 minutes, pressurizing by a hydraulic forming machine for 15MPa for forming, and performing moisture-preserving maintenance at normal temperature to obtain a rare earth slag solidified body.
The strength of the cured product was 19.67MPa and the specific activity was 2.9X10 3 Bq/kg, barium ion leaching toxicity is 7.8mg/L.
Example 6
The treatment method of the high specific activity rare earth slag in the embodiment comprises the following steps:
(1) Adding 1.0kg of hydrogen peroxide solution with the mass concentration of 2.6% into 5.0kg of barium slag, uniformly stirring, and standing for 0.5h; then adding 2.5kg of sulfuric acid with the concentration of 20%, and fully and uniformly stirring until no bubbles are generated;
(2) Rare earth slag treatment: adding 6.5kg of rare earth slag into the barium slag in the step (1), and continuously stirring for 5 minutes;
(3) And (3) forming: and (3) adding 0.70kg of ordinary Portland cement into the sample obtained in the step (2), continuously stirring for 4 minutes, pressurizing by a hydraulic forming machine for 15MPa for forming, and performing moisture-preserving maintenance at normal temperature to obtain a rare earth slag solidified body.
The strength of the cured product was 15.61MPa and the specific activity was 2.8X10 3 Bq/kg, the barium ion leaching toxicity is 10.7mg/L.
Example 7
The treatment method of the high specific activity rare earth slag in the embodiment comprises the following steps:
(1) Adding 1.0kg of hydrogen peroxide solution with the mass concentration of 2.60% into 5.0kg of barium slag, uniformly stirring, and standing for 0.5h; then adding 1.67kg of sulfuric acid with the concentration of 30%, and fully and uniformly stirring until no bubbles are generated;
(2) Rare earth slag treatment: adding 6.5kg of rare earth slag into the barium slag in the step (1), and continuously stirring for 5 minutes;
(3) And (3) forming: and (3) adding 0.60kg of ordinary Portland cement into the sample obtained in the step (2), continuously stirring for 4 minutes, pressurizing by a hydraulic forming machine for 12.5MPa for forming, and performing moisture-preserving maintenance at normal temperature to obtain a rare earth slag solidified body.
The strength of the cured product was measured to be 14.36MPa, and the specific activity was measured to be 2.8X10 3 Bq/kg, barium ion leaching toxicity is 12.5mg/L.
Comparative example 1
The treatment method of the high specific activity rare earth slag of the present comparative example, which is different from example 1 only in the amount of the rare earth slag added in step (2), specifically comprises the steps of:
(1) Adding 0.5kg of hydrogen peroxide solution with the mass concentration of 5.2% into 5.0kg of barium slag, uniformly stirring, and standing for 0.5h; then adding 2.5kg of sulfuric acid with the concentration of 20%, and fully and uniformly stirring until no bubbles are generated;
(2) Rare earth slag treatment: adding 10.0kg of rare earth slag into the barium slag in the step (1), and continuously stirring for 3 minutes;
(3) And (3) forming: and (3) adding 0.55kg of ordinary Portland cement into the sample obtained in the step (2), continuously stirring for 3 minutes, pressurizing by a hydraulic forming machine for 10MPa for forming, and performing moisture-preserving maintenance at normal temperature to obtain a rare earth slag solidified body.
The strength of the cured product was measured to be 5.36MPa, and the specific activity was measured to be 7.9X10 5 Bq/kg, barium ion leaching toxicity is 19.8mg/L.
Comparative example 2
The treatment method of the high specific activity rare earth slag of the present comparative example, which is different from example 1 only in the amount of sulfuric acid added in step (1), specifically comprises the following steps:
(1) Adding 0.5kg of hydrogen peroxide solution with the mass concentration of 5.2% into 5.0kg of barium slag, uniformly stirring, and standing for 0.5h; then adding 1.25kg of sulfuric acid with the concentration of 20%, and fully and uniformly stirring until no bubbles are generated;
(2) Rare earth slag treatment: adding 6.0kg of rare earth slag into the barium slag in the step (1), and continuously stirring for 3 minutes;
(3) And (3) forming: and (3) adding 0.55kg of ordinary Portland cement into the sample obtained in the step (2), continuously stirring for 3 minutes, pressurizing by a hydraulic forming machine for 10MPa for forming, and performing moisture-preserving maintenance at normal temperature to obtain a rare earth slag solidified body.
The strength of the cured product was measured to be 4.36MPa, and the specific activity was measured to be 1.4X10 5 Bq/kg, barium ion leaching toxicity is 135.6 mg/L.
Comparative example 3
In the treatment method of the high specific activity rare earth slag of the comparative example, compared with example 1, H of the hydrogen peroxide solution in the step (1) 2 O 2 The rare earth slag in the step (2) is slightly excessive compared with barium slag, and the cement in the step (3) is different in concentration, and specifically comprises the following steps:
(1) Adding 0.5kg of hydrogen peroxide solution with the mass concentration of 2.6% into 5.0kg of barium slag, uniformly stirring, and standing for 0.5h; then adding sulfuric acid with the concentration of 20 percent of 2.5, fully and uniformly stirring until no bubbles are generated any more, and observing overflow of hydrogen sulfide during the period;
(2) Rare earth slag treatment: adding 8.0kg of rare earth slag into the barium slag in the step (1), and continuously stirring for 3 minutes;
(3) And (3) forming: and (3) adding 0.55kg of ordinary Portland cement into the sample obtained in the step (2), continuously stirring for 3 minutes, pressurizing by a hydraulic forming machine for 10MPa for forming, and performing moisture-preserving maintenance at normal temperature to obtain a rare earth slag solidified body.
The strength of the cured product was 8.53MPa, and the specific activity was 5.6X10 5 Bq/kg, the barium ion leaching toxicity is 20.5mg/L.
Finally, it is further noted that in this application, relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
While the application has been disclosed in the context of specific embodiments thereof, it will be appreciated that those skilled in the art may devise various modifications, adaptations, or equivalents of the application within the spirit and scope of the appended claims. Such modifications, improvements, or equivalents are intended to be included within the scope of the present application.
Claims (9)
1. The method for disposing the high-specific-activity rare earth slag is characterized by comprising the following steps of:
the pretreatment step of barium slag: adding hydrogen peroxide solution into the barium slag, uniformly stirring, and standing for reaction; then adding sulfuric acid, and fully and uniformly stirring until no bubbles are generated;
rare earth slag treatment: adding rare earth slag into the barium slag obtained by the pretreatment of the barium slag, and continuously and uniformly stirring;
and (3) forming and curing: adding ordinary Portland cement into the material treated by the rare earth slag treatment step, continuously stirring uniformly, and then forming and curing to obtain a rare earth slag solidified body;
in the barium slag pretreatment step, the hydrogen peroxide solution is added in an amount of H 2 O 2 Meter, said H 2 O 2 The mass ratio of the barium sulfide to the barium sulfide in the barium slag is 0.2:1-0.3:1; the molar amount of the sulfuric acid solution added is H 2 SO 4 Meter, said H 2 SO 4 The molar amount of the catalyst is 1.0 to 1.1 times of the sum of the molar amounts of barium sulfide and barium carbonate in the barium slag.
2. The method for disposing high-specific-activity rare earth slag according to claim 1, wherein in the barium slag pretreatment step, the mass ratio of the hydrogen peroxide solution to the barium slag is 0.1:1-0.2:1.
3. The method for disposing of high specific activity rare earth slag according to claim 1 or 2, characterized in that the mass concentration of the sulfuric acid solution is 20-40%; the mass ratio of the sulfuric acid solution to the barium slag is 1:2-1:4.
4. The method for disposing of high-specific-activity rare earth slag as set forth in claim 3, wherein in said rare earth slag disposing step, the addition amount of said rare earth slag is 1.2 to 1.5 times the mass of said barium slag.
5. The method for disposing high-specific-activity rare earth slag according to any one of claims 1, 2 and 4, wherein in the molding and curing step, the addition amount of the ordinary portland cement is 5 to 8% of the total mass of the barium slag and the rare earth slag.
6. The method for treating high specific activity rare earth slag according to any one of claims 1, 2 and 4, wherein the time for the standing reaction in the barium slag pretreatment step is 10 to 60 minutes.
7. The method according to claim 5, wherein in the barium slag pretreatment step, the stirring is continued for 3 to 5 minutes in the rare earth slag treatment step and/or the molding solidification step.
8. The method for treating high-specific-activity rare earth slag according to claim 5, wherein in the molding and solidifying step, the molding treatment is performed by press molding, and the molding pressure is 10-15MPa.
9. A high specific activity rare earth slag solidified body prepared by the method of any one of claims 1-8.
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| CN115159882A (en) * | 2022-08-01 | 2022-10-11 | 江西理工大学 | Preparation process of rare earth waste residue geopolymer |
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| US20130171047A1 (en) * | 2011-12-07 | 2013-07-04 | Nicholas H. Burlingame | Method for recycling of rare earth and zirconium oxide materials |
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