CN106967440A - Medicament and production and application method suitable for repairing Compound Heavy Metals soil - Google Patents
Medicament and production and application method suitable for repairing Compound Heavy Metals soil Download PDFInfo
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- CN106967440A CN106967440A CN201710243093.4A CN201710243093A CN106967440A CN 106967440 A CN106967440 A CN 106967440A CN 201710243093 A CN201710243093 A CN 201710243093A CN 106967440 A CN106967440 A CN 106967440A
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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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- 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
- C09K2101/00—Agricultural use
Abstract
The invention discloses a kind of medicament and production and application method for being applied to repair Compound Heavy Metals soil, the medicament is made up of the material of following mass percent：Steel-making slag powder 30 55%；Peroxophosphoric acid calcium powder 20 50%；Load phosphatic humic acid powder 5 30%.It is an advantage of the invention that：First, the medicament can significantly reduce heavy metals mobilization and toxicity leaching content in heavy metal polluted soil, be particularly suitable for use in content of beary metal height and the more acid pollution place of pollutant kind, Polluted Soil can significantly reduce the environmental risk in the second development and utilization of contaminated site after repairing as environmentally friendly material recycling；Meanwhile, the medicament raw material are easily obtained, it is with low cost, prepare simple, easy to use, effect stability, can be in large-scale application in the solidification and stabilization in combined pollution place is repaired.
Description
Technical field
The present invention relates to environmental geotechnical field, more particularly to a kind of medicine for being applied to repair Compound Heavy Metals soil
Agent and production and application method.
Background technology
With the adjustment of China's city function and city layout, original position is in the enterprise of downtown area, suburb, such as chemical industry
Factory, metallurgical works, Electroplate Factory etc. all progressively close down or Tui Chengjin gardens, but industry, the production process of enterprise for many years, are removed at it
A large amount of pollutants are have accumulated in the soil left after moving, is not only that efficient utilize for leaving soil brings resistance, is also surrounding
Environment brings serious potential safety hazard.In recent years, government promulgates《Soil Pollution Control action plan》(ten, soil) is also by dirt
Dye soil remediation work is considered as one of current important people's livelihood engineering, carries out the work of associated contamination repairing and treating extremely urgent.
The features such as industrial pollution place heavy metal pollution of soil is rendered as many heavy metal species, high content and big acidity.
In the reparation in heavy metal pollution place, solidification stabilization technique is widely adopted.Conventional curing agent mainly includes cement, lime
And the material such as phosphate, heavy metal solidification and stabilization has good effect, but there is also substantial amounts of shortcoming, for example, produces water
Mud energy consumption is big, greenhouse gas emission is more etc.；Lime, phosphate are non-renewable natural minerals, cost height etc.；And it is phosphatic
It is a large amount of to apply, it can seriously change soil texture and further trigger the phosphorus pollution of underground water, surface water.
In summary, there is many defects in conventional curing agents, it is desirable to reduce the use of cement and phosphate material, find one
Stabilizing heavy metal can be solidified by planting, while solidifying, stabilization efficiency is high, with low cost, performance is stable, material source is extensive and environment is friendly
Good Novel curing agent turns into environmentally friendly scientific worker's focus of attention.
The content of the invention
Goal of the invention：The first object of the present invention is to provide a kind of heavy metal that can be significantly reduced in heavy metal polluted soil
Migration and toxicity leaching content, repair the medicament of Compound Heavy Metals soil；The second object of the present invention is to provide the reparation weight
The production method of metallic pollution local medicine agent；The third object of the present invention is to provide the user of the repairing heavy metal pollution local medicine agent
Method.
Technical scheme：The medicament of the present invention for being applied to repair Compound Heavy Metals soil, by following mass percent
Material composition：Steel-making slag powder 30-55%；Peroxophosphoric acid calcium powder 20-50%；Load phosphatic humic acid powder 5-30%.
The component material of the medicament is preferably：Steel-making slag powder 35-50%；Peroxophosphoric acid calcium powder 25-45%；Load phosphatic corruption
Phytic acid powder 10-25%.
The steel-making slag powder is activated steel slag powder, is prepared from by following methods：
(1) by the one or more in the vessel slag after magnetic separation, open hearth slag and the contour active slag of lectric furnace slag
By broken sieving；
(2) drying materials to its moisture content for taking particle diameter to be less than 2mm in the product obtained is less than 2%, it is preferred to use 100-
105 DEG C of airflow drying；
(3) product obtained is ground and crosses after the sieve of 150-200 mesh and (can for example use ball milling), then through 500 DEG C-
700 DEG C of calcining 1-2h (preferentially can for example be calcined using electric furnace, energy-saving practical), obtain activated steel slag powder.
The phosphatic humic acid powder of load is prepared from by following methods：
(1) prepare concentration for 0.01-0.05mol/L phosphate solution (phosphate is preferred to use potassium dihydrogen phosphate, its
The aqueous solution is acidity, more preferable to activity of steel slag effect)；
(2) by humic acid powder and aluminum sulfate according to mass ratio 20-30:1 mixing, obtains humic acid powder powder compound；
(3) gained humic acid powder compound is impregnated into phosphate solution, stirring 10-15min is (equal to mixture
It is even), 36-48h is stood after vibration stirring 10-15h at 20-30 DEG C, gelatinous precipitate is obtained, wherein, the mesh stirred twice
Difference, stirring is to allow solid-liquid fully to contact for the first time, is quick to produce gel precipitate for the second time；
(4) gelatinous precipitate is less than 2% using 45-55 DEG C airflow drying to its moisture content, products therefrom is levigate
150-200 mesh sieves are crossed, obtain loading phosphatic humic acid powder, wherein, preferential quick using airflow drying, medicament is difficult knot
Block, facilitates subsequent cure agent to produce.
One or more progress in the poor quality fossil fuel such as the peat, lignite and weathered coal crushed 100-150 mesh
After sieve, added with solid-to-liquid ratio 0.05-0.025g/mL in sodium hydroxide solution, stirring 10-15min is uniform to mixture, in 20-
36-48h is stood after vibration stirring 10-15h at 30 DEG C, filtering obtains supernatant, adds 0.05-0.1mol/L hydrochloric acid, obtains
It is less than 2% using 45-55 DEG C airflow drying to its moisture content after precipitation, adds starch and granulated, selection obtains particle diameter and is
2-3mm humic acid powder.
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content uses 100- for 14-20% calcium superphosphate
250 DEG C of airflow drying to its moisture content is less than 2%, ground 150-200 mesh sieves.P2O5Content is technical grade calcium superphosphate
One of value parameter, content is too low of poor quality, and the too high price of content is high.
The production method for being applied to repair the medicament of Compound Heavy Metals soil comprises the following steps：Percentage by weight
Than steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic humic acid powder of load are mixed, using dry stirring 0.5-1h extremely
150-200 mesh sieves are crossed after well mixed.
It is described be applied to repair Compound Heavy Metals soil the application method of medicament be：By the medicament with it is heavy metal-polluted
Dye soil is mixed, wherein, the dosing is the 5-15% of heavy metal polluted soil dry weight, and the heavy metal polluted soil
Moisture content is 16-30%.
The granule content that particle diameter is less than 0.075mm in the heavy metal polluted soil is 65-100%, and wherein heavy metal lead contains
Amount is more than 2000mg/kg, and heavy metal zinc content is more than 2000mg/kg, and heavy metal copper content is more than 2000mg/kg, heavy metal nickel
Content is more than 2000mg/kg.
Beneficial effect：Compared with prior art, significant advantage of the invention is：
(1) heavy metals immobilization repairing effect is good.First, the suction that the slag heavy metal ion being related in the present invention has
Attached effect；Secondly, calcium sulfate is contained in agriculture level calcium superphosphate, slag is under the excitation of calcium sulfate, its potential gelling
Characteristic is showed, and calcium phosphate precipitation and the hydroxide precipitation of heavy metal have carried out effective package action, greatly enhance
The simple solidification effect using phosphatic heavy metal；Again, the calcium oxide aquation generation Ca being dissolved out in slag
(OH)2, and the main component of calcium superphosphate is Ca (H2PO4)2, it is a large amount of that both occur acid-base reaction generation under aqueous environment
Hydroxyapatite crystal.Hydroxyapatite can the efficient absorption complexing heavy metal such as Pb, Zn, Cu and Ni, itself and heavy metal are generated
Hydroxyapatite heavy metallic salt solubility tens orders of magnitude low compared with heavy metal hydroxide, while it is in acid and alkaline bar
Dissolve relatively low under part, solidification effect is more preferably stablized.
(2) excellent in durability.Conventional curing agents are easily corroded by carbon dioxide and acid-rain corrosion is influenceed, and produce solidification pollution
Native environmental safety and engineering characteristic deteriorate relaxation phenomenon.The solidification medicament being related in the present invention can effectively overcome above-mentioned lack
Point, because the heavy phosphates class precipitation of generation is reunited around humic acid powder, its solubility under a variety of pH environment is equal
It is relatively low, and under the package action of the hydrated product C-S-H gels of slag, heavy metal precipitation can be effectively reduced molten with acidity
The contact of liquid；Slag has the ability of extremely strong acid buffer capacity and absorbing carbon dioxide in itself simultaneously, and carbon dioxide, which corrodes, to be made
Under, CaCO is generated3Crystal further fills the hole of firming body, effectively reduction acid solution infiltration capacity, and further increase is solid
Change the stability of body in the presence of a harsh environment；Acid-rain corrosion also will be buffered preferably in addition, loading phosphatic humic acid powder
Effect, the phosphate of load can effectively suppress the desorption of Adsorption of Heavy Metals, further the durability of increase firming body.
(3) waste material, environmentally friendly solidification medicament are effectively utilized.First, slag is used as a kind of industrial residue, big face
Product accumulation, has had resulted in serious environmental pollution, by the activation to slag, has effectively increased the value of slag, becomes
Waste be changed into values.Secondly, slag is directly used in the solidification and stabilization of heavy metal polluted soil as a kind of overbased material, solidified earth
PH is higher, can be utilized to the later development in soil and bring many problems, by activation modification, is effectively increasing slag to a huge sum of money
While the solidification effect of category, the pH of solidified earth is also effectively reduced, and by the addition of calcium superphosphate, makes its heavy metal
Solidification and stabilization effect reach most preferably.Again, the common bulk deposition of the fossil fuel inferior such as peat, lignite and weathered coal, difficult
To utilize, it is prepared into after humic acid, is further modified, the solidification effect to metal can be effectively increased in load after phosphate
It can also be realized while fruit and slag is excited, increase the hydration activity of slag and the solidification and stabilization effect of heavy metal.
Embodiment
Embodiment 1
The present invention is applied to repair the medicament of Compound Heavy Metals soil, is made up of the material of following mass parts：Steel-making slag powder
45%；Peroxophosphoric acid calcium powder 35%；Load phosphatic humic acid powder 20%.
The steel-making slag powder is the activated steel slag powder being prepared from by following methods：Vessel slag is crushed after magnetic separation
Sieving；Taking particle diameter to be less than 2mm material and place in obtained product uses temperature to contain for 105 DEG C of airflow drying to it in baking oven
Water rate is 1%；Obtained product is ground and crossed after the sieve of 200 mesh, then is obtained through 700 DEG C of electric furnaces calcining 2h.The steel-making slag powder
Basicity value is 2.07.
The main component and content of the slag are shown in Table 1, what deserves to be explained is, it is adaptable to slag of the invention is not limited to
Data in table 1, it is only the slag that the present embodiment is used：
The slag main component of table 1 and content
| Main chemical compositions | CaO | SiO2 | Al2O3 | Fe2O3 | MgO | P2O5 |
| Content (%) | 36.30 | 16.26 | 3.32 | 18.66 | 8.35 | 1.26 |
The phosphatic humic acid powder of load is prepared from by following methods：Prepare the phosphorus that concentration is 0.05mol/L
Acid dihydride potassium solution；By the ratio 30 of humic acid powder and aluminum sulfate according to quality:1 is sufficiently mixed, and obtains humic acid powder
Compound；Gained compound is impregnated into potassium dihydrogen phosphate obtained above, stirring 15min is to well mixed, 25
At DEG C, 48h is stood after vibration stirring 15h, gelatinous precipitate is obtained；Gelatinous precipitate is used into 50 DEG C of airflow drying extremely
Its moisture content is 1%, ground 200 mesh sieve of products therefrom, obtains loading the humic acid powder of potassium dihydrogen phosphate.
The humic acid powder is that peat crushed after 100 mesh sieves, and sodium hydroxide is added with solid-to-liquid ratio 0.04g/mL
In solution, stirring 13min is uniform to mixture, stands 42h after vibration stirring 13h at 25 DEG C, filtering obtains supernatant, adds
0.075mol/L hydrochloric acid, uses 50 DEG C of airflow drying to its moisture content for 1% after being precipitated, add starch and made
Grain, chooses the humic acid powder for obtaining that particle diameter is 2mm, its physicochemical characteristics and main chemical compositions are shown in Table 2.
The humic acid basic chemical property of table 2 and essential element content
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 18% calcium superphosphate uses 200 DEG C
Stream drying to its moisture content is 1%, ground 200 mesh sieve.
The medicament for being applied to reparation Compound Heavy Metals soil, which is comprised the following steps that, to be prepared from：By above-mentioned matter
Activated steel slag powder, peroxophosphoric acid calcium powder and the phosphatic humic acid powder of load for measuring part are mixed, using dry stirring 1h
200 mesh sieves are crossed to after being well mixed.
It is described be applied to repair Compound Heavy Metals soil the application method of medicament be specially：By medicament with it is heavy metal-polluted
Dye soil carries out original place mixing, wherein, the dosing (accounts for composition metal dirty for the 5% of heavy metal polluted soil dry weight
The native dry weight of dye).Heavy metal contaminants have two kinds：Polluted Soil a, is derived from lead, the zinc combined pollution soil in a certain industrial pollution place；It is dirty
Soil b is contaminated, copper, the nickel combined pollution soil in certain two industrial pollution place is derived from.Other main physicochemical properties are as shown in table 3.
The Polluted Soil Main physical chemical property of table 3
Embodiment 2
It is identical with the preparation process and maintenance processes of embodiment 1, except that, the volume of medicament is 10% (curing agent
Account for heavy metal and organic compound contaminated native dry weight).
Embodiment 3
It is identical with the preparation process and maintenance processes of embodiment 1, except that, the volume of medicament is 15% (curing agent
Account for heavy metal and organic compound contaminated native dry weight).
Comparative example 1
Without any medicament, only the Compound Heavy Metals soil sample in Example 1.
Comparative example 2
Medicament is prepared without overactivation using the slag in embodiment 1, other preparation processes are constant, volume and embodiment 3
It is all mutually 15%.
Embodiment 4
The present invention is applied to repair the medicament of Compound Heavy Metals soil, is made up of the material of following mass parts：Steel-making slag powder
50%；Peroxophosphoric acid calcium powder 25%；Load phosphatic humic acid powder 25%.
The steel-making slag powder is the activated steel slag powder being prepared from by following methods：Open hearth slag is crushed after magnetic separation
Sieving；The material for taking particle diameter to be less than 2mm in obtained product uses the temperature to be for 100 DEG C airflow drying to its moisture content
1.5%；Obtained product is ground and crossed after the sieve of 150 mesh, then is obtained through 500 DEG C of electric furnaces calcining 1h.The steel-making slag powder basicity
It is worth for 1.8.
The phosphatic humic acid powder of load is prepared from by following methods：Prepare the phosphorus that concentration is 0.01mol/L
Acid dihydride potassium solution；By humic acid powder and aluminum sulfate according to 20:The ratio of 1 mass is sufficiently mixed, and obtains humic acid powder
Compound；Gained compound is impregnated into potassium dihydrogen phosphate obtained above, stirring 10min is to well mixed, 20
At DEG C, 36h is stood after vibration stirring 10h, gelatinous precipitate is obtained；Gelatinous precipitate is used into 45 DEG C of airflow drying extremely
Its moisture content is 1.5%, ground 150 mesh sieve of products therefrom, obtains loading the humic acid powder of potassium dihydrogen phosphate.
The humic acid powder to choose lignite crushed after 150 mesh sieves, and hydrogen-oxygen is added with solid-to-liquid ratio 0.025g/mL
Change in sodium solution, stirring 10min is uniform to mixture, stand 36h after vibration stirring 10h at 20 DEG C, filtering obtains supernatant,
0.05mol/L hydrochloric acid is added, uses 45 DEG C of airflow drying to its moisture content for 1.5% after precipitate, addition starch enters
Row granulation, chooses the humic acid powder for obtaining that particle diameter is 3mm.
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 14% calcium superphosphate uses 100 DEG C
Stream drying to its moisture content is 1.5%, and ground 150 mesh sieve obtains peroxophosphoric acid calcium powder.
The medicament for being applied to reparation Compound Heavy Metals soil, which is comprised the following steps that, to be prepared from：By above-mentioned matter
Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic humic acid powder of load for measuring part are mixed, using dry stirring 0.5h extremely
150 mesh sieves are crossed after well mixed.
It is described be applied to repair Compound Heavy Metals soil the construction of medicament be specially：By medicament and heavy metal polluted soil
Original place mixing is carried out, wherein, the dosing (accounts for composition metal Polluted Soil for the 5% of heavy metal polluted soil dry weight
Dry weight), and the moisture content of the heavy metal polluted soil is 16%, heavy metal polluted soil is identical with the Polluted Soil selected in embodiment 1,
The granule content that particle diameter is less than 0.075mm wherein in the heavy metal polluted soil is 65%.
Embodiment 5
The present invention is applied to repair the medicament of Compound Heavy Metals soil, is made up of the material of following mass parts：Steel-making slag powder
35%；Peroxophosphoric acid calcium powder 45%；Load phosphatic humic acid powder 20%.
The steel-making slag powder is to be prepared from activated steel slag powder by following methods：Open hearth slag is carried out after magnetic separation to crush
Sieve；It is absolutely dry that the material for taking particle diameter to be less than 2mm in obtained product uses temperature to be dried to for 150 DEG C of air-flow；Obtained product enters
Row grinds and crossed after the sieve of 180 mesh, then is obtained through 600 DEG C of electric furnaces calcining 1.5h.The steel-making slag powder basicity value is 2.2.
The phosphatic humic acid powder of load is prepared from by following methods：Preparing concentration with phosphate is
0.03mol/L potassium dihydrogen phosphate；By humic acid powder and aluminum sulfate according to 25:The ratio of 1 mass is sufficiently mixed, and is obtained
To humic acid powder powder compound；Gained compound is impregnated into potassium dihydrogen phosphate obtained above, stirring 13min is extremely
It is well mixed, at 25 DEG C, 42h is stood after vibration stirring 12.5h, gelatinous precipitate is obtained；Gelatinous precipitate is used
55 DEG C of air-flow is dried to absolutely dry, ground 160 mesh sieve of products therefrom, obtains loading the humic acid powder of potassium dihydrogen phosphate.
The humic acid powder to choose weathered coal crushed after 120 mesh sieves, and hydrogen is added with solid-to-liquid ratio 0.05g/mL
In sodium hydroxide solution, stirring 15min is uniform to mixture, stands 48h after vibration stirring 15h at 30 DEG C, filtering obtains supernatant
Liquid, adds 0.1mol/L hydrochloric acid, is dried to using 55 DEG C of air-flow absolutely dry after precipitate, adds starch and is granulated, selection
Obtain the humic acid powder that particle diameter is 2.5mm
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 20% calcium superphosphate uses 175 DEG C
Stream dries, ground 160 mesh sieve absolutely dry to its, obtains peroxophosphoric acid calcium powder.
The medicament for being applied to reparation Compound Heavy Metals soil, which is comprised the following steps that, to be prepared from：By above-mentioned matter
Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic humic acid powder of load for measuring part are mixed, using dry stirring 0.75h extremely
160 mesh sieves are crossed after well mixed.
It is described be applied to repair Compound Heavy Metals soil the application method of medicament be specially：By medicament with it is heavy metal-polluted
Dye soil carries out original place mixing, wherein, the dosing (accounts for composition metal dirty for the 10% of heavy metal polluted soil dry weight
The native dry weight of dye), and the moisture content of the heavy metal polluted soil is 23%, heavy metal polluted soil and the Polluted Soil selected in embodiment 1
It is identical, wherein, the granule content that particle diameter is less than 0.075mm in the heavy metal polluted soil is 82.5%.
Embodiment 6
The present invention is applied to repair the medicament of Compound Heavy Metals soil, is made up of the material of following mass parts：Steel-making slag powder
40%；Peroxophosphoric acid calcium powder 50%；Load phosphatic humic acid powder 10%.
The steel-making slag powder is the activation being prepared from by following methods：Open hearth slag is carried out to broken sieving after magnetic separation；
The material for taking particle diameter to be less than 2mm in obtained product uses temperature to be 0.5% for 125 DEG C airflow drying to its moisture content；
To product be ground and cross after the sieve of 200 mesh, then calcine 2h through 700 DEG C of electric furnaces and obtain.The steel-making slag powder basicity value is 2.6.
The phosphatic humic acid powder of load is prepared from by following methods：Prepare the phosphorus that concentration is 0.05mol/L
Acid dihydride potassium solution；By humic acid powder and aluminum sulfate according to 30:The ratio of 1 mass is sufficiently mixed, and obtains humic acid powder
Compound；Gained compound is impregnated into phosphate solution obtained above, stirring 15min is to well mixed, at 30 DEG C,
48h is stood after vibration stirring 15h, gelatinous precipitate is obtained；Gelatinous precipitate is contained to it using 52 DEG C of airflow drying
Water rate is 0.5%, ground 170 mesh sieve of products therefrom, obtains loading the humic acid powder of potassium dihydrogen phosphate.
The humic acid powder is that peat in choosing and lignite crushed after 130 mesh sieves, with solid-to-liquid ratio 0.035g/mL
Add in sodium hydroxide solution, stirring 12min is uniform to mixture, stand 40h after vibration stirring 14h at 26 DEG C, filtering is obtained
Take supernatant, add 0.08mol/L hydrochloric acid, use 48 DEG C of airflow drying to its moisture content for 0.5% after being precipitated, plus
Enter starch to be granulated, choose the humic acid powder for obtaining that particle diameter is 2mm.
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content uses 250 DEG C for 15% calcium superphosphate
Airflow drying to its moisture content is 0.5%, and ground 170 mesh sieve obtains peroxophosphoric acid calcium powder.
The curing agent suitable for Compound Heavy Metals soil, which comprises the following steps, to be prepared from：By above-mentioned mass parts
Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic humic acid powder of load are mixed, equal to mixing using dry stirring 0.75h
170 mesh sieves are crossed after even.
It is described be applied to repair Compound Heavy Metals soil the application method of medicament be specially：By medicament with it is heavy metal-polluted
Dye soil carries out original place mixing.Wherein, the dosing (accounts for composition metal dirty for the 15% of heavy metal polluted soil dry weight
The native dry weight of dye), and the moisture content of the heavy metal polluted soil is 30%.Particle diameter is less than 0.075mm's in heavy metal polluted soil used
Granule content is 83%, and heavy metal polluted soil is identical with the Polluted Soil selected in embodiment 1, wherein, the heavy metal polluted soil
The granule content that middle particle diameter is less than 0.075mm is 100%.
Embodiment 7
The present invention is applied to repair the medicament of Compound Heavy Metals soil, is made up of the material of following mass parts：Steel-making slag powder
30%；Peroxophosphoric acid calcium powder 40%；Load phosphatic humic acid powder 30%.
The steel-making slag powder is the activated steel slag powder being prepared from by following methods：Lectric furnace slag is carried out after magnetic separation
Broken sieving；It is absolutely dry that the material for taking particle diameter to be less than 2mm in obtained product uses temperature to be dried to for 150 DEG C of air-flow；Obtain
Product is ground and crossed after the sieve of 180 mesh, then is obtained through 600 DEG C of electric furnaces calcining 1.5h.The steel-making slag powder basicity value is 2.2.
The phosphatic humic acid powder of load is prepared from by following methods：Preparing concentration with phosphate is
0.03mol/L potassium dihydrogen phosphate；By humic acid powder and aluminum sulfate according to 25:The ratio of 1 mass is sufficiently mixed, and is obtained
To humic acid powder compound；Gained compound is impregnated into potassium dihydrogen phosphate obtained above, stirring 13min is to mixed
Close uniform, at 25 DEG C, stand 42h after vibration stirring 12.5h, obtain gelatinous precipitate；Gelatinous precipitate is used 51
DEG C air-flow be dried to absolutely dry, ground 200 mesh sieve of products therefrom, obtain load potassium dihydrogen phosphate humic acid powder.
The humic acid powder is that lignite and weathered coal crushed after 100 mesh sieves, is added with solid-to-liquid ratio 0.03g/mL
In sodium hydroxide solution, stirring 11min is uniform to mixture, stands 41h after vibration stirring 14h at 27 DEG C, filters on obtaining
Clear liquid, adds 0.065mol/L hydrochloric acid, is dried to using 50 DEG C of air-flow absolutely dry after precipitate, and addition starch is granulated,
Choose the humic acid powder for obtaining that particle diameter is 3mm
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 16% calcium superphosphate uses 175 DEG C
Stream dries, ground 200 mesh sieve absolutely dry to its, obtains peroxophosphoric acid calcium powder.
The medicament for being applied to reparation Compound Heavy Metals soil, which is comprised the following steps that, to be prepared from：By above-mentioned matter
Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic humic acid powder of load for measuring part are mixed, using dry stirring 0.75h extremely
200 mesh sieves are crossed after well mixed.
It is described be applied to repair Compound Heavy Metals soil the application method of medicament be specially：By medicament with it is heavy metal-polluted
Dye soil carries out original place mixing, wherein, the dosing (accounts for composition metal dirty for the 5% of heavy metal polluted soil dry weight
The native dry weight of dye), and the moisture content of the heavy metal polluted soil is 25%, heavy metal polluted soil and the Polluted Soil selected in embodiment 1
It is identical, wherein, the granule content that particle diameter is less than 0.075mm in the heavy metal polluted soil is 90%.
Embodiment 8
The present invention is applied to repair the medicament of Compound Heavy Metals soil, is made up of the material of following mass parts：Steel-making slag powder
55%；Peroxophosphoric acid calcium powder 20%；Load phosphatic humic acid powder 25%.
The steel-making slag powder is the activated steel slag powder being prepared from by following methods：Lectric furnace slag is carried out after magnetic separation
Broken sieving；It is absolutely dry that the material for taking particle diameter to be less than 2mm in obtained product uses temperature to be dried to for 150 DEG C of air-flow；Obtain
Product is ground and crossed after the sieve of 180 mesh, then is obtained through 600 DEG C of electric furnaces calcining 1.5h.The steel-making slag powder basicity value is 2.2.
The phosphatic humic acid powder of load is prepared from by following methods：Preparing concentration with phosphate is
0.03mol/L potassium dihydrogen phosphate；By humic acid powder and aluminum sulfate according to 25:The ratio of 1 mass is sufficiently mixed, and is obtained
To humic acid powder compound；Gained compound is impregnated into potassium dihydrogen phosphate obtained above, stirring 13min is to mixed
Close uniform, at 25 DEG C, stand 42h after vibration stirring 12.5h, obtain gelatinous precipitate；Gelatinous precipitate is used 55
DEG C air-flow be dried to absolutely dry, ground 200 mesh sieve of products therefrom, obtain load potassium dihydrogen phosphate humic acid powder.
The humic acid powder to choose peat and weathered coal crushed after 100 mesh sieves, with solid-to-liquid ratio 0.025g/mL
Add in sodium hydroxide solution, stirring 15min is uniform to mixture, stand 36h after vibration stirring 10h at 30 DEG C, filtering is obtained
Take supernatant, add 0.05mol/L hydrochloric acid, be dried to using 45 DEG C of air-flow absolutely dry after precipitate, addition starch is made
Grain, chooses the humic acid powder for obtaining that particle diameter is 3mm.
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 20% calcium superphosphate uses 175 DEG C
Stream dries, ground 200 mesh sieve absolutely dry to its, obtains peroxophosphoric acid calcium powder.
The medicament for being applied to reparation Compound Heavy Metals soil, which is comprised the following steps that, to be prepared from：By above-mentioned matter
Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic humic acid powder of load for measuring part are mixed, using dry stirring 0.75h extremely
200 mesh sieves are crossed after well mixed.
It is described be applied to repair Compound Heavy Metals soil the application method of medicament be specially：By curing agent and heavy metal
Polluted Soil carries out original place mixing, wherein, the hardener dose (accounts for compound gold for the 10% of heavy metal polluted soil dry weight
Belong to Polluted Soil dry weight), and the moisture content of the heavy metal polluted soil is 23%, heavy metal polluted soil and the dirt selected in embodiment 1
Dye soil is identical, wherein, the granule content that particle diameter is less than 0.075mm in the heavy metal polluted soil is 75%.
Embodiment 9
The present invention is applied to repair the medicament of Compound Heavy Metals soil, is made up of the material of following mass parts：Steel-making slag powder
55%；Peroxophosphoric acid calcium powder 40%；Load phosphatic humic acid powder 5%.
The steel-making slag powder is the activated steel slag powder being prepared from by following methods：Lectric furnace slag is carried out after magnetic separation
Broken sieving；It is absolutely dry that the material for taking particle diameter to be less than 2mm in obtained product uses temperature to be dried to for 150 DEG C of air-flow；Obtain
Product is ground and crossed after the sieve of 180 mesh, then is obtained through 600 DEG C of electric furnaces calcining 1.5h.The steel-making slag powder basicity value is 2.2.
The phosphatic humic acid powder of load is prepared from by following methods：Preparing concentration with phosphate is
0.03mol/L potassium dihydrogen phosphate；By humic acid powder and aluminum sulfate according to 25:The ratio of 1 mass is sufficiently mixed, and is obtained
To humic acid powder compound；Gained compound is impregnated into potassium dihydrogen phosphate obtained above, stirring 13min is to mixed
Close uniform, at 25 DEG C, stand 42h after vibration stirring 12.5h, obtain gelatinous precipitate；Gelatinous precipitate is used 45
DEG C air-flow be dried to absolutely dry, ground 200 mesh sieve of products therefrom, obtain load potassium dihydrogen phosphate humic acid powder.
The humic acid powder was crushed after 100 mesh sieves to choose peat, lignite and weathered coal mixing progress, with solid-to-liquid ratio
0.05g/mL is added in sodium hydroxide solution, and stirring 10min is uniform to mixture, is stood at 20 DEG C after vibration stirring 10h
48h, filtering obtains supernatant, adds 1mol/L hydrochloric acid, is dried to absolutely dry, addition starch after being precipitated using 55 DEG C of air-flow
Granulated, choose the humic acid powder for obtaining that particle diameter is 2mm.
The peroxophosphoric acid calcium powder is prepared from by following methods：By P2O5Content is the gas that 14% calcium superphosphate uses 175 DEG C
Stream dries, ground 200 mesh sieve absolutely dry to its, obtains peroxophosphoric acid calcium powder.
The medicament for being applied to reparation Compound Heavy Metals soil, which is comprised the following steps that, to be prepared from：By above-mentioned matter
Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic humic acid powder of load for measuring part are mixed, using dry stirring 0.75h extremely
200 mesh sieves are crossed after well mixed.
It is described be applied to repair Compound Heavy Metals soil the application method of medicament be specially：By curing agent and heavy metal
Polluted Soil carries out original place mixing, wherein, the hardener dose (accounts for compound gold for the 15% of heavy metal polluted soil dry weight
Belong to Polluted Soil dry weight), and the moisture content of the heavy metal polluted soil is 23%, heavy metal polluted soil and the dirt selected in embodiment 1
Dye soil is identical, wherein, the granule content that particle diameter is less than 0.075mm in the heavy metal polluted soil is 82.5%
Embodiment 10
To embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, embodiment 4, embodiment 5, embodiment 6, reality
Apply the soil of the sample after implementing in example 7, embodiment 8 and embodiment 9 and sealing is wrapped with freshness protection package, be more than 95% condition in 20 DEG C, humidity
It is lower maintenance 28 days after solidification Polluted Soil do toxicity characteristic leaching procedure：
Testing standard：National environmental protection professional standard《Solid waste Leaching leaching method sulfonitric method》(HJ/
T 299-2007)。
Process of the test：By the solidification Polluted Soil after maintenance, weigh wherein 50g samples and be placed in drying, constant weight to two at 105 DEG C
The error of secondary weighing value is less than ± 1%, and calculating obtains sample moisture content.Calculated according to moisture content and repair native dry weight, weigh butt
Quality is 10g reparation soil sample, and according to《Solid waste Leaching leaching method sulfonitric method》(HJ/T299-2007)
Defined method and step are tested.Result of the test is as shown in table 4.
The toxicity characteristic leaching procedure result (mg/L) of table 4
Sulfonitric method leaching method be used to evaluate solid waste whether be hazardous waste standard, be also analysis solid
The common method of pollutant Leaching feature of the waste under acid precipitation effect.From the toxicity characteristic leaching procedure result of table 4, lead to
Comparing embodiment 1-3, embodiment 4-6 and embodiment 7-9 is crossed to can be seen that：Mixed with the reparation soil of medicament of the present invention, its leachate
Middle Zn, Pb, Ni and Cu leaching concentration are untreated by comparative example 1 as the addition content of medicament increases and reduces
Heavy metals mobilization in the Polluted Soil of source is extremely strong, and heavy metal Zn, Pb, Ni and Cu leaching content are far above《Hazardous waste differentiates mark
Quasi- leaching characteristic identification》Boundary value in (GB 5085.3-2007), in conjunction with the embodiments 1-9 can be found that the addition of medicament can
The stripping quantity of heavy metal is significantly reduced, increases environmental safety.It was found from embodiment 3 and comparative example 2 are contrasted, in the addition present invention
Medicament and conserve 28 days after, the stability of heavy metal all increases, and the stablizing effect in embodiment 3 becomes apparent, its soak
Output is far below《Hazardous waste judging standard leaching characteristic identification》Boundary value in (GB 5085.3-2007), and comparative example 2
In medicament in steel-making slag powder it is not activated only prepared by loading phosphatic charcoal, it can be reduced in a ground degree
The migration characteristic of heavy metal Zn, Pb, Ni and Cu in soil, reduces the harm of its environmentally safe property, can still meet this hair
Bright basic demand, it follows that carrying out activation modification processing to slag used, can effectively strengthen and medicament heavy metal is consolidated
Change stablizing effect, if slag can also realize the technique effect of the present invention to a certain extent without activation process.
Embodiment 11
To embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, embodiment 4, embodiment 5, embodiment 6, reality
Apply the solidification Polluted Soil after example 7, embodiment 8 and embodiment 9 are conserved as described in Example 10 and do reparation mud acid alkalinity test：
Testing standard：The method of testing 4972-01 of the pH value of soil.
Process of the test：By the solidification Polluted Soil after maintenance, weigh wherein 50g samples and be placed in drying, constant weight to two at 105 DEG C
The error of secondary weighing value is less than ± 1%, and calculating obtains sample moisture content.Calculated according to moisture content and repair native dry weight, cross 1mm sieves simultaneously
The reparation soil sample that butt quality is 10g is weighed, is mixed with the stirring of 10g distilled water, solution ph is tested after standing 1h.Result of the test
As shown in table 5.
The acid-base value result of the test of table 5
The acid-base value of the solidification soil body is to evaluate an important indicator of medicament curing heavy metal effect, and it is to repairing place
The influence of the secondary development scheme and degree utilized is great.By the acid-base value result of the test of table 5, pass through embodiment 1-3 and comparative example 1
Comparison understand that after addition medicament, the pH of the solidification soil body is significantly improved, after maintenance 28 days, for Polluted Soil pH value 6~
Between 9, close to neutrality, be conducive to repairing the utilization in place, while the pH for solidifying the soil body in embodiment 4-9 is also significantly improved, support
Shield is after 28 days, for Polluted Soil pH value also between 6~9, close to neutral；Comparative example 2 is relative to embodiment 3 due to not having
Activation process is carried out to slag, causes pH value slightly higher, but can also realize technical scheme substantially, if pH is persistently raised
It can be utilized to soil later development and bring many problems.
Embodiment 12
To embodiment 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, embodiment 4, embodiment 5, embodiment 6, reality
Apply the Polluted Soil of example 7, embodiment 8 and embodiment 9 as described in Example 10 and carry out phytotoxicity experiment (percentage of seedgermination examination
Test)：
Process of the test：Percentage of seedgermination experiment uses the soya bean to heavy metal in soil pollutant load more sensitivity, with
Its germination percentage carries out oxicity analysis as ecological index heavy metal and organic compound contaminated soil, is more conventional from life
State toxicological point weighs the important method of soil environment quality and soil pollution.Element after should conserving 28 days first is native and repaiies
Earth backing, it is standby that natural wind dry doubling crosses 2mm sieves.Each sample takes 4kg soil (element soil or each repair soil) dress basin, and (back cut diameter is
25cm, base diameter is 20cm, a height of 20cm), ridging height is 18cm；Soil in basin is irrigated to specific retention with distilled water and is
60%, keep specific retention constant thereafter and infiltration indoors is placed 2 days；Soya bean is finally sowed, soya bean sowing is left in depth 0.3cm
The right side, 100 are sowed per basin；Suitable soil moisture is periodically after planting kept using spray pattern, make seed indoors area without shade,
Germinateed under the conditions of 18-22 DEG C of room temperature, natural lighting.Germination percentage=(seed number is planted experimentally in chitting piece grain number/confession) × 100%.Examination
Test result as shown in table 6.
The percentage of seedgermination of table 6 (%)
Percentage of seedgermination experiment can reflect toxic action of the soil to plant.As can be seen from Table 6：Plain soil (contrast
Example 1, that is, be not added with the Polluted Soil of medicament) in content of beary metal it is very high, have a strong impact on the soya bean in the germination percentage of seed, Polluted Soil
Percentage of seedgermination is only 8% and 12%.And the medicament in comparative example 2 then improves germination percentage to a certain extent, but lift width
Degree is limited, is only capable of reaching 58% and 63% germination percentage, illustrates the present invention using in medicament made from not activated steel-making slag powder
There is certain stabilization to the heavy metal in Polluted Soil, act on limited at that time；On the contrary, the medicament in 1-9 of the embodiment of the present invention
The percentage of seedgermination for repairing soil is all higher than 85% in the case of a variety of volumes, and highest even can reach 99%.Embodiment 1,2,3
Show with the difference of comparative example 1, medicament of the present invention repairs the autochthonal state close friend of Compound Heavy Metals, is conducive to place week after repairing
The plant on side and development of microorganisms growth, what embodiment 3 and the comparative illustration of comparative example 2 can also be effectively to the activation process of slag
Toxic action of the soil to plant is reduced, the solidification stabilizing power of its heavy metal is reflected from side.
Claims (10)
1. a kind of medicament for being applied to repair Compound Heavy Metals soil, it is characterised in that：By the material of following mass percent
Composition：Steel-making slag powder 30-55%；Peroxophosphoric acid calcium powder 20-50%；Load phosphatic humic acid powder 5-30%.
2. the medicament according to claim 1 for being applied to repair Compound Heavy Metals soil, it is characterised in that：The slag
Powder 35-50%；Peroxophosphoric acid calcium powder 25-45%；Load phosphatic humic acid powder 10-25%.
3. the medicament according to claim 1 or 2 for being applied to repair Compound Heavy Metals soil, it is characterised in that：It is described
Steel-making slag powder is activated steel slag powder, is prepared from by following methods：
(1) will be one or more by broken sieving in the vessel slag after magnetic separation, open hearth slag and lectric furnace slag；
(2) drying materials to its moisture content for taking particle diameter to be less than 2mm in the product obtained is less than 2%；
(3) product obtained is ground and crossed after the sieve of 150-200 mesh, then through 500-700 DEG C of calcining 1-2h, obtains activating steel
Ground-slag.
4. the medicament according to claim 1 for being applied to repair Compound Heavy Metals soil, it is characterised in that：The load
Phosphatic humic acid powder is prepared from by following methods：
(1) phosphate solution that concentration is 0.01-0.05mol/L is prepared；
(2) by humic acid powder and aluminum sulfate according to mass ratio 20-30:1 mixing, obtains humic acid powder compound；
(3) gained humic acid powder compound is impregnated into phosphate solution, stirs 10-15min, vibrated at 20-30 DEG C
36-48h is stood after stirring 10-15h, gelatinous precipitate is obtained；
(4) gelatinous precipitate is less than 2%, mistake that products therefrom is levigate using 45-55 DEG C airflow drying to its moisture content
150-200 mesh sieves, obtain loading phosphatic humic acid powder.
5. being applied to according to claim 1 or 4 repairs the medicament of Compound Heavy Metals soil, it is characterised in that：It is described
Humic acid is to be obtained by one or more extracted as raw material in peat, lignite and weathered coal.
6. the medicament according to claim 5 for being applied to repair Compound Heavy Metals soil, it is characterised in that：The mud
One or more progress in charcoal, lignite and weathered coal were crushed after 100-150 mesh sieves, were added with solid-to-liquid ratio 0.05-0.025g/mL
Enter in sodium hydroxide solution, stirring 10-15min is uniform to mixture, 36- is stood after vibration stirring 10-15h at 20-30 DEG C
48h, filtering obtains supernatant, adds 0.05-0.1mol/L hydrochloric acid, and 45-55 DEG C of airflow drying is used extremely after being precipitated
Its moisture content is less than 2%, adds starch and is granulated, and chooses the humic acid powder for obtaining that particle diameter is 2-3mm.
7. the medicament according to claim 1 for being applied to repair Compound Heavy Metals soil, it is characterised in that：It is described to cross phosphorus
Sour calcium powder is prepared from by following methods：By P2O5Content is that 14-20% calcium superphosphate uses 100-250 DEG C of airflow drying extremely
Its moisture content is less than 2%, ground 150-200 mesh sieves.
8. being applied to described in claim 1 repairs the production method of the medicament of Compound Heavy Metals soil, it is characterised in that bag
Include following steps：Steel-making slag powder, peroxophosphoric acid calcium powder and the phosphatic humic acid powder of load are mixed by weight percentage,
150-200 mesh sieves are crossed to after being well mixed using dry stirring 0.5-1h.
9. being applied to described in claim 1 repairs the application method of the medicament of Compound Heavy Metals soil, it is characterised in that：Will
The medicament is mixed with heavy metal polluted soil, wherein, the dosing is the 5-15% of heavy metal polluted soil dry weight,
And the moisture content of the heavy metal polluted soil is 16-30%.
10. the application method according to claim 9 for being applied to repair the medicament of Compound Heavy Metals soil, its feature exists
In：The granule content that particle diameter is less than 0.075mm in the heavy metal polluted soil is 65-100%, and wherein content of heavy metal lead is more than
2000mg/kg, heavy metal zinc content is more than 2000mg/kg, and heavy metal copper content is more than 2000mg/kg, and heavy metal nickel content is big
In 2000mg/kg.
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