CN108865168A - A kind of heavy-metal contaminated soil renovation agent and preparation method thereof - Google Patents
A kind of heavy-metal contaminated soil renovation agent and preparation method thereof Download PDFInfo
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- CN108865168A CN108865168A CN201810979984.0A CN201810979984A CN108865168A CN 108865168 A CN108865168 A CN 108865168A CN 201810979984 A CN201810979984 A CN 201810979984A CN 108865168 A CN108865168 A CN 108865168A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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Abstract
The present invention provides a kind of heavy-metal contaminated soil renovation agent and preparation method thereof, is related to soil remediation field.The preparation method of heavy-metal contaminated soil renovation agent, including：Mixed solution is mixed to get after the tri-thiol s-triazine of the polyvinylpyrrolidone of 5~15 parts by weight and its salt and 5~15 parts by weight is prepared into the solution that mass fraction is 1~5% respectively, the mixed solution is added in the sulfate filler of the montmorillonite of 15~35 parts by weight, the attapulgite of 10~30 parts by weight, the diatomite of 10~15 parts by weight and 15~30 parts by weight, and 50~80 DEG C at a temperature of stirring 3~5h after be dried to obtain pre-product, the stabilizer of 5~10 parts by weight is mixed with the pre-product.Heavy-metal contaminated soil renovation agent can be realized to the heavy metal inactivation in heavy-metal contaminated soil, realize the reparation to soil.Have the advantages that high treating effect, processing cost are low etc..
Description
Technical field
The present invention relates to soil remediation fields, and in particular to a kind of heavy-metal contaminated soil renovation agent and its preparation side
Method.
Background technique
Heavy metal pollution of soil refers to that due to mankind's activity, the content of the minor metallic element in soil in the soil is more than
Background value, too high levels caused by excess deposition, is referred to as heavy metal pollution of soil.
Existing heavy-metal contaminated soil renovation agent is mainly mixed by contaminated soil to realize to its inside
Heavy metal realization processing, in this way, absorb heavy metal soil-repairing agent still mix in the soil, can not thoroughly solve soil
The problem of reparation.
Summary of the invention
The first object of the present invention is to provide a kind of heavy-metal contaminated soil renovation agent, is that a kind of effect is good, drug effect is long
Heavy-metal contaminated soil renovation agent.
The second object of the present invention is to provide a kind of preparation method of heavy-metal contaminated soil renovation agent, can quickly make
Standby above-mentioned heavy-metal contaminated soil renovation agent.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The present invention proposes a kind of heavy-metal contaminated soil renovation agent, in parts by weight, including：
15~35 parts of montmorillonite, 10~30 parts of attapulgite, 10~15 parts of diatomite, 15~30 parts of sulfate filler,
Polyvinylpyrrolidone and its 5~15 parts of salt, tri-thiol Strinoline~15 part and 5~10 parts of stabilizer.
In preferred embodiments of the present invention, above-mentioned heavy-metal contaminated soil renovation agent, in parts by weight, packet
It includes：
18~28 parts of montmorillonite, 15~25 parts of attapulgite, 10~15 parts of diatomite, 16~26 parts of sulfate filler,
Polyvinylpyrrolidone and its 8~12 parts of salt, tri-thiol Strinoline~10 part and 5~8 parts of stabilizer.
In preferred embodiments of the present invention, above-mentioned heavy-metal contaminated soil renovation agent, in parts by weight, packet
It includes：
0~25 part of montmorillonite 2,18~24 parts of attapulgite, 12~15 parts of diatomite, 18~20 parts of sulfate filler,
Polyvinylpyrrolidone and its 8~10 parts of salt, 6~9 parts of tri-thiol s-triazine and 6~7 parts of stabilizer.
In preferred embodiments of the present invention, above-mentioned sulfate filler includes at least one in sodium sulphate and ferric sulfate
Kind.
In preferred embodiments of the present invention, above-mentioned stabilizer include calcium carbonate, hydroxyapatite and cement at least
It is a kind of.
In preferred embodiments of the present invention, above-mentioned stabilizer selects calcium carbonate and hydroxyapatite according to 1~2:1 ratio
The mixture of example.
The present invention also provides a kind of preparation methods of heavy-metal contaminated soil renovation agent, including：
The tri-thiol s-triazine of the polyvinylpyrrolidone of 5~15 parts by weight and its salt and 5~15 parts by weight is made respectively
It is mixed to get mixed solution after the standby solution for being 1~5% at mass fraction, by the montmorillonite of 15~35 parts by weight, 10~30 weights
The sulfate filler addition mixing for measuring the attapulgite of part, the diatomite of 10~15 parts by weight and 15~30 parts by weight is molten
Liquid, and 50~80 DEG C at a temperature of stirring 3~5h after be dried to obtain pre-product, by the stabilizer of 5~10 parts by weight with it is described
Pre-product mixing.
In preferred embodiments of the present invention, above-mentioned montmorillonite, attapulgite and diatomite, will before mixed liquor is added
Montmorillonite, attapulgite and diatomite are ground to 1mm particle below.
In preferred embodiments of the present invention, above-mentioned drying is in the fluidized bed that control inlet air temperature is 110~140 DEG C
It carries out.
In preferred embodiments of the present invention, above-mentioned pre-product and the stabilizer are blended in 300~700r/min
4~10min of lower mixing.
The beneficial effect of the embodiment of the present invention is：
Heavy-metal contaminated soil renovation agent of the embodiment of the present invention, passes through montmorillonite powder, attapulgite, diatomite, sulfate
Synergistic effect between filler, polyvinylpyrrolidone and its salt, tri-thiol s-triazine and stabilizer, makes the huge sum of money in soil
Belong to inactivation to realize the reparation to heavy-metal contaminated soil.It is the heavy-metal contaminated soil reparation that a kind of effect is good, drug effect is long
Agent.
The preparation method of heavy-metal contaminated soil renovation agent of the embodiment of the present invention there is operation to do simple, easy to spread etc.
Advantage can prepare above-mentioned heavy-metal contaminated soil renovation agent at low cost.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Heavy-metal contaminated soil renovation agent of the embodiment of the present invention and preparation method thereof is specifically described below.
The embodiment of the present invention provides a kind of heavy-metal contaminated soil renovation agent, in parts by weight, including：Montmorillonite 15
~35 parts, 10~30 parts of attapulgite, 10~15 parts of diatomite, 15~30 parts of sulfate filler, polyvinylpyrrolidone and
5~15 parts of its salt, tri-thiol Strinoline~15 part and 5~10 parts of stabilizer.
As the preferred embodiment of above-mentioned heavy-metal contaminated soil renovation agent, in parts by weight, including：Montmorillonite 18
~28 parts, 15~25 parts of attapulgite, 10~15 parts of diatomite, 16~26 parts of sulfate filler, polyvinylpyrrolidone and
8~12 parts of its salt, tri-thiol Strinoline~10 part and 5~8 parts of stabilizer.
As the further preferred scheme of above-mentioned heavy-metal contaminated soil renovation agent, in parts by weight, including：It covers
De- 20~25 parts of stone, 18~24 parts of attapulgite, 12~15 parts of diatomite, 18~20 parts of sulfate filler, polyvinyl pyrrole
Alkanone and its 8~10 parts of salt, 6~9 parts of tri-thiol s-triazine and 6~7 parts of stabilizer.
The raw material of heavy metal pollution soil-repairing agent is illustrated below：
Wherein, montmorillonite powder can select commercially available montmorillonite powder.Montmorillonite powder can as minerals and microelement
Enough enhance the bacteria agent in compost, and the fixed inactivation realized to substances such as heavy metals that can act synergistically with other raw materials.
Wherein, attapulgite can select commercially available attapulgite.Attapulgite has preferable chelation, and other
Raw material synergistic effect, which is realized, inactivates the fixed of the substances such as heavy metal, plays the filling to heavy metal pollution soil-repairing agent and steady
Fixed effect.
Wherein, diatomite can select commercially available diatomite.Diatomite and other raw materials synergistic effect are realized to heavy metal
The fixed inactivation of equal substances, plays the filling and stable effect to heavy metal pollution soil-repairing agent.
Wherein, sulfate filler includes at least one of sodium sulphate and ferric sulfate.It is appreciated that sulfate filler
The mixture that can be sodium sulphate and ferric sulfate is also possible to the mixture of the arbitrary proportion of sodium sulphate and ferric sulfate.By
Sulfate filler is added in heavy-metal contaminated soil renovation agent, can either play stabilizer acts to keep heavy metal pollution
The effect of soil-repairing agent, and improvement can be played the role of to soil.
Wherein, polyvinylpyrrolidone (PVP) can select commercially available polyvinylpyrrolidone, specifically, with CAS：25
~28 and LDso>The grade products of 13.0g/kg are advisable.It, can be with montmorillonite, concave convex rod by using polyvinylpyrrolidone
Soil, diatomite part and sulfate filler etc. act synergistically, and accelerate deposition and inactivation to the heavy metal in soil, and energy
Enough keep the activity of heavy-metal contaminated soil renovation agent.
Wherein, tri-thiol s-triazine and its salt are to select commercially available polyvinylpyrrolidone and its salt, wherein tri-thiol is equal
Triazine salt can be tri-thiol s-triazine mono-sodium salt or tri-thiol s-triazine trisodium salt.It is appreciated that tri-thiol s-triazine and its
Salt when in use, can be used alone tri-thiol s-triazine, also can be used alone triazine mono-sodium salt or tri-thiol s-triazine three
Sodium salt can also use at least two in tri-thiol s-triazine, tri-thiol s-triazine mono-sodium salt and tri-thiol s-triazine trisodium salt
Arbitrary proportion mixture.By using tri-thiol s-triazine and its salt, on the one hand itself has and energy is complexed with heavy metal
Power guarantees the repair ability of heavy metal soil-repairing agent, and on the other hand the above montmorillonite of energy, attapulgite and diatomite etc. are
It relies on, the metal for avoiding inactivation from depositing discharges again.
Wherein, stabilizer includes at least one of calcium carbonate, hydroxyapatite and cement.Likewise, it is understood that stablizing
Agent can be one of above-mentioned calcium carbonate, hydroxyapatite and cement, be also possible to two kinds or two kinds in above-mentioned raw materials with
On arbitrary proportion mixture.
Preferably, stabilizer selects calcium carbonate and hydroxyapatite according to 1~2:The mixture of 1 ratio.Pass through control
On the one hand the use ratio of stabilizer reduces cost of material, on the other hand guarantees the drug effect of renovation agent.
Hold above-mentioned, the heavy-metal contaminated soil renovation agent of the embodiment of the present invention passes through montmorillonite powder, attapulgite, diatom
Synergistic effect between soil, sulfate filler, polyvinylpyrrolidone and its salt, tri-thiol s-triazine and stabilizer, makes soil
Heavy metal inactivation in earth is to realize the reparation to heavy-metal contaminated soil.It is that a kind of effect is good, drug effect length heavy metal-polluted
Contaminate soil-repairing agent.
The embodiment of the present invention also provides a kind of preparation method of heavy-metal contaminated soil renovation agent, including：
It is on the waiting list raw material, montmorillonite, attapulgite and diatomite are ground to 1mm particle below.Specifically, it can will cover
De- stone, attapulgite and diatomite are added separately to crush in grinder；Montmorillonite, attapulgite and diatomite can also be mixed
It is added in grinder and crushes after conjunction.Preferably, the partial size of montmorillonite, attapulgite and diatomite is with 500~1000 μm
Preferably.
The tri-thiol s-triazine of the polyvinylpyrrolidone of 5~15 parts by weight and 5~15 parts by weight is prepared into matter respectively
Mixed solution is mixed to get after the solution that amount score is 1~5%.The illiteracy of smashed 15~35 parts by weight is added into mixed liquor
De- stone, the attapulgite of smashed 10~30 parts by weight, smashed 10~15 parts by weight diatomite and smashed 15
The sulfate filler of~30 parts by weight, and 50~80 DEG C at a temperature of stirring 3~5h obtain stirring product；Later, it will stir
The inlet air temperature mixed product to be added in fluidized bed, and control fluidized bed is 110~140 DEG C and is dried, and obtains pre-product；It will
The stabilizer and pre-product of 5~10 parts by weight are added in high-speed mixer, and 4~10min is mixed at 300~700r/min,
Obtain soil pollution by heavy metal renovation agent.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
Montmorillonite, attapulgite and diatomite are added separately to be crushed in grinder 500~700 μm of particle.
The tri-thiol s-triazine of the polyvinylpyrrolidone of 7.5 parts by weight and 6 parts by weight is prepared into mass fraction respectively
After 3% solution, it is mixed to get mixed solution.
The montmorillonite of smashed 18 parts by weight, attapulgite, the powder of smashed 13 parts by weight are added into mixed liquor
The sodium sulphate of the diatomite of 115 parts by weight after broken and smashed 17 parts by weight, and 50~80 DEG C at a temperature of stir
3.5h obtains stirring product；Later, will stirring product be added in fluidized bed, and control fluidized bed inlet air temperature be 110~
140 DEG C are dried, and obtain pre-product；The stabilizer of 7 parts by weight and pre-product are added in high-speed mixer, in 600r/
5min is mixed under min, obtains soil pollution by heavy metal renovation agent.
Embodiment 2
Montmorillonite, attapulgite and diatomite are added separately to be crushed in grinder 500~600 μm of particle.
The polyvinylpyrrolidone of 10 parts by weight is prepared into the solution that mass fraction is 2%, by the tri-thiol of 8 parts by weight
S-triazine is prepared into the solution that mass fraction is 4% respectively, and two kinds of solution are mixed to get mixed solution.
The montmorillonite of smashed 21 parts by weight, attapulgite, the powder of smashed 18 parts by weight are added into mixed liquor
The ferric sulfate of the diatomite of 14 parts by weight after broken and smashed 18 parts by weight, and 50~80 DEG C at a temperature of stirring 4h obtain
To stirring product；Later, will stirring product be added in fluidized bed, and control fluidized bed inlet air temperature be 110~140 DEG C into
Row drying, obtains pre-product；The stabilizer of 7 parts by weight and pre-product are added in high-speed mixer, mixed at 550r/min
8min is closed, soil pollution by heavy metal renovation agent is obtained.
Embodiment 3
Montmorillonite, attapulgite and diatomite are added separately to be crushed in grinder 700~800 μm of particle.
The polyvinylpyrrolidone of 10 parts by weight is prepared into the solution that mass fraction is 5%, by the tri-thiol of 7 parts by weight
S-triazine is prepared into the solution that mass fraction is 3% respectively, and two kinds of solution are mixed to get mixed solution.
The montmorillonite of smashed 22 parts by weight, attapulgite, the powder of smashed 22 parts by weight are added into mixed liquor
The ferric sulfate of the diatomite of 16 parts by weight after broken and smashed 22 parts by weight, and 50~80 DEG C at a temperature of stir 4.5h
Obtain stirring product；Later, the inlet air temperature for stirring product being added in fluidized bed, and controlling fluidized bed is 110~140 DEG C
It is dried, obtains pre-product；The stabilizer of 9 parts by weight and pre-product are added in high-speed mixer, at 600r/min
5min is mixed, soil pollution by heavy metal renovation agent is obtained.
Embodiment 4
Montmorillonite, attapulgite and diatomite are added separately to be crushed in grinder 400~600 μm of particle.
The polyvinylpyrrolidone of 13 parts by weight is prepared into the solution that mass fraction is 1%, by three mercaptos of 14 parts by weight
Base s-triazine is prepared into the solution that mass fraction is 3% respectively, and two kinds of solution are mixed to get mixed solution.
The montmorillonite of smashed 30 parts by weight, attapulgite, the powder of smashed 26 parts by weight are added into mixed liquor
The ferric sulfate of the diatomite of 10 parts by weight after broken and smashed 25 parts by weight, and 50~80 DEG C at a temperature of stir 3.5h
Obtain stirring product；Later, the inlet air temperature for stirring product being added in fluidized bed, and controlling fluidized bed is 110~140 DEG C
It is dried, obtains pre-product；The stabilizer of 10 parts by weight and pre-product are added in high-speed mixer, at 650r/min
10min is mixed, soil pollution by heavy metal renovation agent is obtained.
Embodiment 5
Montmorillonite, attapulgite and diatomite are added separately to be crushed in grinder 500~600 μm of particle.
The tri-thiol s-triazine of the polyvinylpyrrolidone of 12 parts by weight and 12 parts by weight is prepared into mass fraction respectively
After 3.5% solution, it is mixed to get mixed solution.
The montmorillonite of smashed 25 parts by weight, attapulgite, the powder of smashed 20 parts by weight are added into mixed liquor
The ferric sulfate of the diatomite of 12.5 parts by weight after broken and smashed 20 parts by weight, and 50~80 DEG C at a temperature of stir 5h
Obtain stirring product；Later, the inlet air temperature for stirring product being added in fluidized bed, and controlling fluidized bed is 110~140 DEG C
It is dried, obtains pre-product；The stabilizer of 7.5 parts by weight and pre-product are added in high-speed mixer, in 350r/min
Lower mixing 10min, obtains soil pollution by heavy metal renovation agent.
Comparative example
By the montmorillonite powder of 17 parts by weight, the attapulgite of 17 parts by weight, the diatomite of 10 parts by weight, 15 parts by weight sulphur
Hydrochlorate filler and the adsorbent of 5 parts by weight, which are uniformly mixed, obtains heavy-metal contaminated soil renovation agent.
Effect assessment
300~500mm depth location below cadmium pollution soil surface layer, the soil remediation of tiling Examples 1 to 5 preparation
Agent forms the soil remediation oxidant layer with a thickness of 5~30mm.Later, in soil remediation oxidant layer tiling cadmium pollution soil layer, to cadmium dirt
Dye soil horizon irrigate or using natural precipitation, realizes migration of the cadmium element in soil to soil remediation oxidant layer.Work as soil
After earth reparation oxidant layer top heavy metal content in soil is reduced to required value, by soil remediation oxidant layer and its soil of upper and lower 10~30mm
Earth layer takes out, the soil after being repaired.Test result is shown in Table 1.
1 test result of table
As it can be seen from table 1 the heavy-metal contaminated soil renovation agent of Examples 1 to 5 preferably repairs cadmium metal
Multiple effect, also, my notable difference between the treatment effect of said ratio, are a kind of excellent renovation agents.
In conclusion heavy-metal contaminated soil renovation agent of the embodiment of the present invention, passes through montmorillonite powder, attapulgite, diatom
Synergistic effect between soil, sulfate filler, polyvinylpyrrolidone and its salt, tri-thiol s-triazine and stabilizer, makes soil
Heavy metal inactivation in earth is to realize the reparation to heavy-metal contaminated soil.It is that a kind of effect is good, drug effect length heavy metal-polluted
Contaminate soil-repairing agent.
The preparation method of heavy-metal contaminated soil renovation agent of the embodiment of the present invention there is operation to do simple, easy to spread etc.
Advantage can prepare above-mentioned heavy-metal contaminated soil renovation agent at low cost.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of heavy-metal contaminated soil renovation agent, which is characterized in that in parts by weight, including：
15~35 parts of montmorillonite, 10~30 parts of attapulgite, 10~15 parts of diatomite, 15~30 parts of sulfate filler, poly- second
Alkene pyrrolidone and its 5~15 parts of salt, tri-thiol Strinoline~15 part and 5~10 parts of stabilizer.
2. heavy-metal contaminated soil renovation agent according to claim 1, which is characterized in that in parts by weight, including：
18~28 parts of montmorillonite, 15~25 parts of attapulgite, 10~15 parts of diatomite, 16~26 parts of sulfate filler, poly- second
Alkene pyrrolidone and its 8~12 parts of salt, tri-thiol Strinoline~10 part and 5~8 parts of stabilizer.
3. heavy-metal contaminated soil renovation agent according to claim 2, which is characterized in that in parts by weight, including：
0~25 part of montmorillonite 2,18~24 parts of attapulgite, 12~15 parts of diatomite, 18~20 parts of sulfate filler, poly- second
Alkene pyrrolidone and its 8~10 parts of salt, 6~9 parts of tri-thiol s-triazine and 6~7 parts of stabilizer.
4. described in any item heavy-metal contaminated soil renovation agents according to claim 1~3, which is characterized in that the sulfate
Filler includes at least one of sodium sulphate and ferric sulfate.
5. described in any item heavy-metal contaminated soil renovation agents according to claim 1~3, which is characterized in that the stabilizer
At least one including calcium carbonate, hydroxyapatite and cement.
6. heavy-metal contaminated soil renovation agent according to claim 5, which is characterized in that the stabilizer selects calcium carbonate
With hydroxyapatite according to 1~2:The mixture of 1 ratio.
7. a kind of preparation method of heavy-metal contaminated soil renovation agent, which is characterized in that including：
The tri-thiol s-triazine of the polyvinylpyrrolidone of 5~15 parts by weight and its salt and 5~15 parts by weight is prepared into respectively
It is mixed to get mixed solution after the solution that mass fraction is 1~5%, by the montmorillonite of 15~35 parts by weight, 10~30 parts by weight
Attapulgite, the diatomite of 10~15 parts by weight and the sulfate filler of 15~30 parts by weight the mixed solution is added,
And 50~80 DEG C at a temperature of stirring 3~5h after be dried to obtain pre-product, by the stabilizer of 5~10 parts by weight and the pre- production
Object mixing.
8. the preparation method of heavy-metal contaminated soil renovation agent according to claim 7, which is characterized in that described cover takes off
Stone, the attapulgite and the diatomite are before being added the mixed liquor, by the montmorillonite, the attapulgite and described
Diatomite is ground to 1mm particle below.
9. the preparation method of heavy-metal contaminated soil renovation agent according to claim 7, which is characterized in that the drying exists
It controls in the fluidized bed that inlet air temperature is 110~140 DEG C and carries out.
10. the preparation method of heavy-metal contaminated soil renovation agent according to claim 7, which is characterized in that the pre- production
Object and being blended under 300~700r/min for the stabilizer mix 4~10min.
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| CN110846044A (en) * | 2019-11-25 | 2020-02-28 | 连云港新江环保材料有限公司 | Efficient soil remediation agent and preparation method thereof |
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