CN109453493A - Stabilization agent and its preparation method and application for handling the waste residue containing beryllium - Google Patents
Stabilization agent and its preparation method and application for handling the waste residue containing beryllium Download PDFInfo
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- CN109453493A CN109453493A CN201811516140.9A CN201811516140A CN109453493A CN 109453493 A CN109453493 A CN 109453493A CN 201811516140 A CN201811516140 A CN 201811516140A CN 109453493 A CN109453493 A CN 109453493A
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- Prior art keywords
- waste residue
- residue containing
- beryllium
- containing beryllium
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/33—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by chemical fixing the harmful substance, e.g. by chelation or complexation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/10—Destroying solid waste or transforming solid waste into something useful or harmless involving an adsorption step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/49—Inorganic substances containing halogen
Abstract
The present invention relates to a kind of stabilization agents and its preparation method and application for handling the waste residue containing beryllium, belong to hazardous waste processing technology field.The stabilization agent for being used to handle the waste residue containing beryllium of the invention, including the following component according to mass fraction meter: 15 ~ 25 parts of conditioner, 5 ~ 15 parts of additive, 60 ~ 80 parts of curing agent, the conditioner is flyash, sepiolite or the residual mud of water supply plant, and the additive is potassium dihydrogen phosphate, calcium superphosphate, vulcanized sodium or calcium oxide.Of the invention can significantly stabilize beryllium, the fluorine solidified in waste residue containing beryllium for the stabilization processes of waste residue containing beryllium medicament, the leaching concentration for reducing beryllium, fluorine in waste residue containing beryllium of high degree, the rate of being cured reaches 99% or more, the leaching concentration of beryllium is lower than leaching characteristic identification standard value, realizes transformation of the waste residue containing beryllium from hazardous waste to Ordinary solid waste；The stabilization agent is at low cost, preparation method and application method are simple, is conducive to promote and apply.
Description
Technical field
The invention belongs to hazardous waste processing technology fields, and in particular to a kind of for handling the stabilization chemical drug of the waste residue containing beryllium
Agent and its preparation method and application.
Background technique
Beryllium is a kind of rare strategic resource, is mainly manifested in that reserves are few, and demand is big.Mainly have in the world the U.S.,
Several a few countries such as Japan, the Commonwealth of Independent States (CIS), China, India produce beryllium.Moreover, in the world the demand of beryllium with annual 5%~
6% speed increases, and beryllium metal, beryllium compound and beryllium alloy are widely used in aerospace, nuclear industry, electronics industry
In.The production technology of beryllium metal product is usually beryllium raw ore-ore dressing-beryllium concentrate-pretreatment-leaching-waste residue containing beryllium mistake
How journey since fluorinated volume is high in beryllium raw ore, therefore effectively reduces the leaching concentration of beryllium, fluorine in waste residue containing beryllium, so that useless containing beryllium
Slag is converted into Ordinary solid waste as present urgent problem to be solved by hazardous waste.
Curing/stabilizing method is will to contain beryllium waste residue by curing/stabilizing medicament directly to fix to reach and stablize containing beryllium
The purpose of beryllium in waste residue.It is a kind of for repairing consolidating for beryllium pollution soils and sediments as disclosed in Chinese patent CN107903903A
To change stabilization agent, is 25~40% comprising modified metakaolin, activated magnesia is 20~35%, and cement is 25~40%,
And the quality sum of each component is 100 parts, and each raw material is stirred and evenly mixed by 5~10% soil containing beryllium, adds water curing 2~7 days i.e.
It can.However, by current, the nationwide interior improvement case for an example not yet occur and being directed to the waste residue containing beryllium, at the same it is also not any
Special stabilization agent about the waste residue containing beryllium.Therefore, it is badly in need of a kind of stabilization agent that can be used for the waste residue containing beryllium at present.
Summary of the invention
It is provided the purpose of the present invention is overcome the deficiencies in the prior art a kind of for handling the stabilization chemical drug of the waste residue containing beryllium
Agent and its preparation method and application, the stabilization agent are good to beryllium, the stabilization effect of fluorine in waste residue containing beryllium, especially to high-content
Waste residue containing beryllium has preferable stabilization effect.The application method of the stabilization agent provided by the invention simultaneously has operation
Simply, the advantages that regulation effect is good.
The present invention adopts the following technical scheme:
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: conditioner 15~
25 parts, 75~85 parts of curing agent, the conditioner are flyash, sepiolite or the residual mud of water supply plant.
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: additive 5~15
Part, 85~95 parts of curing agent, the additive are potassium dihydrogen phosphate, calcium superphosphate, vulcanized sodium or calcium oxide.
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: conditioner 15~
25 parts, 5~15 parts of additive, 60~80 parts of curing agent, the conditioner be flyash, sepiolite or the residual mud of water supply plant, it is described
Additive is potassium dihydrogen phosphate, calcium superphosphate, vulcanized sodium or calcium oxide.
Further, the curing agent is portland cement.
The present invention also provides a kind of for handling the preparation method of the stabilization agent of the waste residue containing beryllium, step are as follows: according to institute
State quality proportioning, the conditioner is uniformly mixed with curing agent to get.
The present invention also provides a kind of for handling the preparation method of the stabilization agent of the waste residue containing beryllium, step are as follows: according to institute
State quality proportioning, the additive is uniformly mixed with curing agent to get.
The present invention also provides a kind of for handling the preparation method of the stabilization agent of the waste residue containing beryllium, step are as follows: will improve
It is broken into granularity≤0.3mm after agent is dry, according to the quality proportioning, conditioner, additive and curing agent are uniformly mixed, i.e.,
?.
The present invention also provides the stabilization agents for handling the waste residue containing beryllium in the stabilization processes of waste residue containing beryllium
Application, steps are as follows: will waste particle containing beryllium it is dry after be broken into granularity≤0.3mm waste particle containing beryllium, in mass ratio
The ratio of 0.8:1 mixes stabilization agent with waste residue containing beryllium, after evenly mixing, in solid-to-liquid ratio 1:(0.5~0.8) ratio add
Enter water, conserves 7~14d, the leaching concentration of measurement beryllium, fluorine after 5~10min of stirring under room temperature.
The medicaments such as potassium dihydrogen phosphate, calcium superphosphate, vulcanized sodium or the calcium oxide that technical solution of the present invention uses are purchased from state
Medicine group, it is pure to analyze.Flyash is derived from changde, hunan province power plant, and the residual mud of water supply plant is derived from Changsha, Hunan tap water
Factory, sepiolite are derived from Xiang Tan sepiolite production company, and cement is to buy ordinary portland cement by oneself.
Total content >=3500mg/kg of beryllium in waste residue containing beryllium of the invention, fluorine total content >=40400mg/kg, according to " Gu
Body waste Leaching leaching method hac buffer method (HJ/T300-2007) ", the leaching concentration of beryllium is 140~150mg/
L, the leaching concentration of fluorine are 260~280mg/L, pH > 9.
Technical solution of the present invention uses the agent of stable composition chemical drug, including additive, conditioner and curing agent.Additive is
Potassium dihydrogen phosphate, calcium superphosphate, vulcanized sodium or calcium oxide, this kind of phosphate substances of potassium dihydrogen phosphate, calcium superphosphate, it cannot change
Become the total amount of heavy metal, but reduces the biological effectiveness and poison of heavy metal by changing the form of heavy metal in systems
Property；Vulcanized sodium is because having many advantages, such as stronger reproducibility, good stablizing effect and more longlasting recovery time to various heavy
Metal has preferable stabilization effect；The meeting of adding of calcium oxide is so that the pH of system also rises with it, under the conditions of pH appropriate,
The absorption that the adding of quick lime can reduce hydrogen ion and heavy metal ion is striven unexpectedly, while generating in system and have to heavy metal ion
The carbonate of suction-operated, so that heavy metal ion in waste residue be promoted to shift to precipitating.Conditioner is flyash, sepiolite or gives
The residual mud of water factory, flyash have biggish specific surface area, thus can have to heavy metal and generate stronger adsorption capacity, and in flyash
Containing a large amount of Al, the oxides such as Si and the oxides such as a small amount of Fe, Ca have exclusive adsorptivity to heavy metal in waste residue containing beryllium；
Sepiolite is a kind of layer of chain threadiness alumina magnesia silicate, due to its huge specific surface area and special layer structure,
Sepiolite has good passivation repairing effect to heavy metal.The residual mud of water supply plant is the by-product of drinking water treatment process, mainly
It is made of the colloid carried in iron aluminum salt flocculant and raw water.Amorphous state iron aluminium content height, specific surface area in the residual mud of water supply plant
Greatly, there is preferable static stabilization, can be used as absorption heavy metal, improve effective material of heavy metal waste slag；Curing agent is
Portland cement, portland cement is as a kind of common solidification and stabilization material, since cement generates gelling object after aquation
The materializations such as large-scale encapsulated, physical absorption, isomorphous substitution, chemical reaction precipitating may occur to heavy metal and act on for matter, hydrated product,
It converts poisonous and harmful substances to the substance of low-solubility, low migration and hypotoxicity, is obtained in the mechanical strength for making the waste residue containing beryllium
Stablize the pollutant of the beryllium in waste residue containing beryllium.Synergistic function is generated between each component, to containing
Beryllium waste residue stabilization effect further consolidates promotion.
Compared with the prior art, the present invention has the following beneficial effects:
A kind of can significantly stabilize for the stabilization processes of waste residue containing beryllium medicament provided by the invention solidifies waste residue containing beryllium
In beryllium, fluorine, the leaching concentration for reducing beryllium, fluorine in waste residue containing beryllium of high degree, the rate of being cured reaches 99% or more, especially
Using the resulting stabilization agent of embodiment 4 to 10, the leaching concentration of beryllium is lower than " hazardous waste judging standard leaching characteristic identification
(GB5085.3-2007) " transformation of the waste residue containing beryllium from hazardous waste to Ordinary solid waste, is realized；The stabilization agent
At low cost, preparation method and application method are simple, are conducive to promote and apply.
Specific embodiment
Below by specific embodiment, invention is further described in detail, but those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.
Embodiment 1
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: 15 parts of flyash,
85 parts of portland cement.
For handle the waste residue containing beryllium stabilization agent the preparation method comprises the following steps: according to the quality proportioning, by the fine coal
Ash be uniformly mixed with portland cement to get.
Embodiment 2
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: 25 parts of sepiolite,
75 parts of portland cement.
For handle the waste residue containing beryllium stabilization agent the preparation method comprises the following steps: according to the quality proportioning, by the Hai Pao
Stone be uniformly mixed with portland cement to get.
Embodiment 3
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: the residual mud of water supply plant
20 parts, 80 parts of portland cement.
For handle the waste residue containing beryllium stabilization agent the preparation method comprises the following steps: according to the quality proportioning, by the water supply
The residual mud of factory be uniformly mixed with portland cement to get.
The stabilization agent being respectively adopted in embodiment 1 to 3 carries out the stabilization processes of waste residue containing beryllium.It is broken into after taking drying
Granularity≤0.3mm waste particle containing beryllium, wherein beryllium content 3500mg/kg, fluorine content 40400mg/kg.0.8:1 in mass ratio
Ratio the obtained stabilization agent in embodiment 1 to 3 is mixed with waste residue containing beryllium respectively, after evenly mixing, by solid-to-liquid ratio
1:(0.5~0.8) ratio water is added, 7~14d, the leaching concentration of measurement beryllium, fluorine are conserved under room temperature after stirring 5~10min.
According to " solid waste Leaching leaching method hac buffer method (HJ/T300-2007) " to stabilisation after
Waste residue is tested, then according to Leaching in " hazardous waste judging standard leaching characteristic identification (GB5085.3-2007) "
Judging standard value determines whether the waste residue containing beryllium after stabilizing is the hazardous waste with Leaching feature, the results are shown in Table 1.
Stabilization effect of 1 embodiment of table, 1 to the 3 gained stabilization agent to the waste residue containing beryllium
As can be seen from Table 1, conditioner flyash, sepiolite, the residual mud of water supply plant are used in embodiment 1 to 3 respectively
With curing agent portland cement it is compound after waste residue containing beryllium is stabilized after, this contains beryllium in beryllium waste residue, the curing degree of fluorine exists
99% or more, stabilization effect is significant, but the leaching concentration of beryllium is not up to " hazardous waste judging standard leaching poison in waste residue containing beryllium
Property identify (GB5085.3-2007) " in leaching characteristic identification standard value.
Embodiment 4
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: potassium dihydrogen phosphate 5
Part, 95 parts of portland cement.
For handling the preparation method of the stabilization agent of the waste residue containing beryllium, step are as follows:, will be described according to the quality proportioning
Potassium dihydrogen phosphate be uniformly mixed with portland cement to get.
Embodiment 5
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: calcium superphosphate 10
Part, 90 parts of portland cement.
For handling the preparation method of the stabilization agent of the waste residue containing beryllium, step are as follows:, will be described according to the quality proportioning
Calcium superphosphate be uniformly mixed with portland cement to get.
Embodiment 6
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: 15 parts of vulcanized sodium,
85 parts of portland cement.
For handling the preparation method of the stabilization agent of the waste residue containing beryllium, step are as follows:, will be described according to the quality proportioning
Vulcanized sodium be uniformly mixed with portland cement to get.
Embodiment 7
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: 15 parts of calcium oxide,
85 parts of portland cement.
For handling the preparation method of the stabilization agent of the waste residue containing beryllium, step are as follows:, will be described according to the quality proportioning
Calcium oxide be uniformly mixed with portland cement to get.
The stabilization agent being respectively adopted in embodiment 4~7 carries out the stabilization processes of waste residue containing beryllium.It is broken into after taking drying
Granularity≤0.3mm waste particle containing beryllium, wherein beryllium content 3500mg/kg, fluorine content 40400mg/kg, in mass ratio 0.8:1
Ratio the stabilization agent in embodiment 4 to 7 is mixed with waste residue containing beryllium respectively, uniformly mix, by solid-to-liquid ratio 1:(0.5~
0.8) water is added in ratio, conserves 7~14d, the leaching concentration of measurement beryllium, fluorine after 5~10min of stirring under room temperature.According to " solid
Waste Leaching leaching method hac buffer method (HJ/T300-2007) " waste residue after stabilisation is tested, then
Determine to stablize according to leaching characteristic identification standard value in " hazardous waste judging standard leaching characteristic identification (GB5085.3-2007) "
Whether the waste residue containing beryllium after change is the hazardous waste with Leaching feature, the results are shown in Table 2.
2 embodiment of table, 4 to 7 gained stabilization agent is to the stabilization effect of waste residue containing beryllium
As can be seen from Table 2, stabilization agent calcium superphosphate+portland cement and implementation are used in embodiment 5
After being stabilized respectively to waste residue containing beryllium in example 7 using stabilization agent calcium oxide+portland cement, this contains in beryllium waste residue
Beryllium, fluorine curing degree 99.99% or more, stabilization effect is significant, this contains beryllium in beryllium waste residue, the leaching concentration of fluorine is below
Leaching characteristic identification standard value in " hazardous waste judging standard leaching characteristic identification (GB5085.3-2007) ", after stabilisation
Waste residue containing beryllium is changed into Ordinary solid waste by hazardous waste.
Embodiment 8
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: flyash 15~
25 parts, 5~15 parts of calcium oxide, 60~80 parts of portland cement.
For handling the preparation method of the stabilization agent of the waste residue containing beryllium, step are as follows: granulating will be crushed after conditioner drying
Degree≤0.3mm, according to the quality proportioning, by flyash, calcium oxide and portland cement be uniformly mixed to get.
Embodiment 9
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: sepiolite 15~
25 parts, 5~15 parts of calcium oxide, 60~80 parts of portland cement.
For handling the preparation method of the stabilization agent of the waste residue containing beryllium, step are as follows: granulating will be crushed after conditioner drying
Degree≤0.3mm, according to the quality proportioning, by sepiolite, calcium oxide and portland cement be uniformly mixed to get.
Embodiment 10
For handling the stabilization agent of the waste residue containing beryllium, including the following component according to mass fraction meter: the residual mud of water supply plant
15~25 parts, 5~15 parts of calcium oxide, 60~80 parts of portland cement.
For handling the preparation method of the stabilization agent of the waste residue containing beryllium, step are as follows: granulating will be crushed after conditioner drying
Degree≤0.3mm, according to the quality proportioning, by the residual mud of water supply plant, calcium oxide and portland cement be uniformly mixed to get.
The resulting stabilization agent of embodiment 8 to 10 is respectively adopted and carries out the stabilization processes of waste residue containing beryllium.It is broken after taking drying
It is broken into granularity≤0.3mm waste particle containing beryllium, wherein beryllium content 3500mg/kg, fluorine content 40400mg/kg, in mass ratio
The ratio of 0.8:1 respectively mixes the resulting stabilization agent of embodiment 8 to 10 with waste residue containing beryllium, after evenly mixing, by solid-liquid
Than 1:(0.5~0.8) ratio water is added, 7~14d is conserved under room temperature after stirring 5~10min, measurement beryllium, the leaching of fluorine are dense
Degree.
3 embodiment of table, 8 to 10 gained stabilization agent is to the stabilization effect of waste residue containing beryllium
As can be seen from Table 3,8 to 10 gained stabilization agent of embodiment should after stabilizing to waste residue containing beryllium
The curing degree of beryllium, fluorine is 99.99% or more in waste residue containing beryllium, and stabilization effect is significant, this contains the leaching of beryllium, fluorine in beryllium waste residue
Concentration is below leaching characteristic identification standard value in " hazardous waste judging standard leaching characteristic identification (GB5085.3-2007) ",
Waste residue containing beryllium after stabilisation is changed into Ordinary solid waste by hazardous waste.
By Examples 1 to 10 it is found that a kind of stabilization processes of waste residue containing beryllium medicament that is used for provided by the invention can be shown
Beryllium, the fluorine for stabilizing and solidifying in waste residue containing beryllium are write, the leaching concentration for reducing beryllium, fluorine in waste residue containing beryllium of high degree is consolidated
Rate reaches 99% or more, and especially with the resulting stabilization agent of embodiment 4 to 10, the leaching concentration of beryllium is lower than " danger is useless
Object judging standard leaching characteristic identification (GB5085.3-2007) ", it realizes this and contains beryllium waste residue and given up from hazardous waste to general solid
The transformation of object；The stabilization agent is at low cost, preparation method and application method are simple, is conducive to promote and apply.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, and protection scope is unlimited
In this.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in protection of the invention
Within the scope of, protection scope of the present invention is subject to claims.
Claims (8)
1. the stabilization agent for handling the waste residue containing beryllium, which is characterized in that including the following component according to mass fraction meter: adjusting
15~25 parts of agent, 75~85 parts of curing agent are managed, the conditioner is flyash, sepiolite or the residual mud of water supply plant.
2. the stabilization agent for handling the waste residue containing beryllium, which is characterized in that including the following component according to mass fraction meter: adding
Add 5~15 parts of agent, 85~95 parts of curing agent, the additive is potassium dihydrogen phosphate, calcium superphosphate, vulcanized sodium or calcium oxide.
3. the stabilization agent for handling the waste residue containing beryllium, which is characterized in that including the following component according to mass fraction meter: adjusting
15~25 parts of agent, 5~15 parts of additive, 60~80 parts of curing agent are managed, the conditioner is that flyash, sepiolite or water supply plant are residual
Mud, the additive are potassium dihydrogen phosphate, calcium superphosphate, vulcanized sodium or calcium oxide.
4. according to claim 1 or 2 or 3 for handling the stabilization agent of the waste residue containing beryllium, which is characterized in that described solid
Agent is portland cement.
5. described in claim 1 for handling the preparation method of the stabilization agent of the waste residue containing beryllium, which is characterized in that step
Are as follows: according to the quality proportioning, the conditioner is uniformly mixed with curing agent to get.
6. as claimed in claim 2 for handling the preparation method of the stabilization agent of the waste residue containing beryllium, which is characterized in that step
Are as follows: according to the quality proportioning, the additive is uniformly mixed with curing agent to get.
7. as claimed in claim 3 for handling the preparation method of the stabilization agent of the waste residue containing beryllium, which is characterized in that step
Are as follows: it will be broken into granularity≤0.3mm after conditioner drying, according to the quality proportioning, conditioner, additive and curing agent are mixed
Close uniformly to get.
8. for handling the stabilization agent of the waste residue containing beryllium in the stabilization processes of waste residue containing beryllium described in claims 1 or 2 or 3
Application, which is characterized in that steps are as follows: will waste particle containing beryllium it is dry after be broken into granularity≤0.3mm waste residue containing beryllium
Grain, the ratio of 0.8:1 mixes the stabilization agent with waste residue containing beryllium in mass ratio, after evenly mixing, by solid-to-liquid ratio 1:
Water is added in the ratio of (0.5~0.8), conserves 7~14d, the leaching concentration of measurement beryllium, fluorine after 5~10min of stirring under room temperature.
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| CN112456957A (en) * | 2020-12-15 | 2021-03-09 | 扬州杰嘉工业固废处置有限公司 | Stabilized disposal method of beryllium-containing waste residue |
| CN113233865A (en) * | 2021-06-04 | 2021-08-10 | 肖剑波 | Novel high-tech environment-friendly wall coating and preparation method and application thereof |
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