CN107162549A - The curing agent and application method of heavy metal pollution site remediation based on entringite - Google Patents
The curing agent and application method of heavy metal pollution site remediation based on entringite Download PDFInfo
- Publication number
- CN107162549A CN107162549A CN201710413337.9A CN201710413337A CN107162549A CN 107162549 A CN107162549 A CN 107162549A CN 201710413337 A CN201710413337 A CN 201710413337A CN 107162549 A CN107162549 A CN 107162549A
- Authority
- CN
- China
- Prior art keywords
- curing agent
- heavy metal
- entringite
- soil
- site remediation
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/143—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00767—Uses not provided for elsewhere in C04B2111/00 for waste stabilisation purposes
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The curing agent and application method of a kind of heavy metal pollution site remediation based on entringite, including alumina cement, quick lime, ardealite, its match (mass ratio) be：Alumina cement 20%~50%, quick lime 10~40%, ardealite 30%~60%.Heavy metal polluted soil through curing agent curing/stabilizing of the present invention has preferable heavy metals immobilization/stabilization effect, and curing/stabilizing stability is superior.28 days Leaching of Heavy Metals concentration is less than 0.2mg/L after curing agent curing/stabilizing processing of the present invention, and far below discarded danger standard (5mg/L), and it is smaller when Leaching of Heavy Metals concentration is compared with 28 within 90 days.Compared with curing heavy metal Polluted Soil of the same amount using Portland cement as curing agent, the solidified earth Leaching of Heavy Metals concentration reduction by more than 50% of Novel curing agent solidification.In addition, the present invention has the advantages that with low cost by the use of trade waste ardealite as raw material.
Description
Technical field
The invention belongs to technical field of civil engineering, be it is a kind of be used for solidify, stabilize the new solid of heavy metal polluted soil
Agent.
Background technology
U.S.'s super fund site remediation project statistics shows that solidification, stabilization technology are heavy metal pollution site remediations
Topmost technology.The solidification in traditional heavy metal pollution place, stabilize it is main by the cementing materials such as cement, the soil body and again
The Various Complex physical-chemical reaction effect recurred between metal ion reduces heavy metal ion dissolution, raising so as to reach
The purposes such as soil strength.The most frequently used curing agent is Portland cement during soil remediation.Portland cement is consolidated
Change, stabilisation heavy metal contaminants mainly have following four mechanism：1. package action of the hydrated product to pollutant；2. cement is molten
Insoluble hydroxide etc. is formed in the alkaline environment promotion heavy metal ion formed after water and is precipitated；3. all kinds of hydrated products
And soil body particle surface is to the physisorption of pollutant；4. by the interaction of hydrated product and pollutant (such as from
Sub- replacement, complexing etc.), chemistry is carried out to pollutant fixed.Around cement solidification/stabilisation heavy metal polluted soil is vulnerable to
The long term physical of environment and chemical erosion, such as carbon dioxide carbonization, drying and watering cycle, Frozen-thawed cycled and extraneous chemical attacks
Deng.Porosity, porosity distribution and the change of microcosmic cementing status of solidfied material, pH value and acid neutralization capacity reduction, heavy metal
Occurrence patterns conversion and the change etc. of solubility, can all cause the change of the stability of the physics, mechanics and chemistry of solidified earth,
The leaching concentration of heavy metal is higher than security restriction.
The molecular formula of entringite is 3CaAl2O3·3CaSO4·32H2O, it can make lead zinc by ion exchange effect
Turn into the part of ettringite structure Deng heavy metal so as to solidification and stabilization heavy metal, chemically angle is seen, trivalent ion
Such as Fe3+、Cr3+And Mn3+Etc. the Al that can replace in entringite3+Ion, divalent ion such as Mg2+、Zn2+、Fe2+、Co2+And Ni2+Can be with
Replace Ca2+, and SO4 2-Can be by CO3 2-、NO3 -、SeO4 2-、CrO4 2-Or B (OH)4 -Replaced.In addition, the surface negative electricity of entringite
Property can accommodate or adsorb more more exogenous metal ions.Entringite has dilatancy, and soil is the association of a discrete particles,
Itself has hole, using the difference of curing condition (temperature, humidity, pH value etc.), controls and using the dilatancy of entringite, can
With the effective porosity for reducing soil, the leaching concentration of heavy metal is reduced.
Entringite is that substep is formed, and each ion for participating in being formed entringite reaction is followed successively by AlO2 -、Ca2+、SO4 2-。
AlO2 -Content is not only the prerequisite to form entringite, and determines the formation speed of entringite.Ca2+Concentration is influence calcium
The principal element of aluminite formation, and the generation form of entringite can be influenceed.The sulfate of sulfate ion is provided solely for calcium alum
The no facilitation of formation of stone, but a certain amount of SO is maintained in liquid phase4 2-It is the essential condition that entringite is stabilized.When molten
SO in liquid4 2-When content is not enough, entringite will be to single sulfur type calcium sulphoaluminate (3CaAl2O3·CaSO4·12H2O) convert, but calcium
The speed that aluminite changes to single sulfur type calcium sulphoaluminate is very slow, therefore entringite has preferable long-time stability.Curing agent
((iron) phase content is to influence one of key factor of entringite long-time stability to middle aluminium, as SO in system4 2-Mutually rubbed with aluminium (iron)
You are than being less than when 0.42, and its stability is decreased obviously.
Alumina cement, quick lime and ardealite can provide corresponding ionic reaction generation entringite.Wherein ardealite is raw
The solid waste given off when production phosphate fertilizer, phosphoric acid, often produces 1t phosphoric acid and about produces 4.5-5t ardealites.Ardealite main component
For dihydrate gypsum (CaSO4·2H2O), also containing a small amount of phosphoric acid, silicon, magnesium, iron, aluminium, organic impurities etc..Ardealite is stacked not only take up
A large amount of soils, and cause environmental pollution.It is therefore desirable to seek the reasonable utilization ways of ardealite, to realize Phosphate Fertilizer Industry
Sustainable development and ardealite height utilize.
The content of the invention
Technical problem：It is an object of the invention to provide a kind of curing agent of the heavy metal pollution site remediation based on entringite
And application method, for solidifying the heavy metal ion in contaminated site.The present invention can improve the curing degree of heavy metal, and reduction is outer
Influence of boundary's environment to solidified earth, and using the intumescent filler effect of entringite, improve the physico mechanical characteristic of solidified earth.
Technical scheme：The present invention a kind of heavy metal pollution site remediation based on entringite curing agent by quick lime,
Alumina cement and ardealite are constituted, and its proportioning (mass ratio) is：Alumina cement 20%~50%, quick lime 10~40%, phosphorus stone
Cream 30%~60%.
Inventor is found by experiment that, proportioning (mass ratio) exist an optimum range, i.e. alumina cement account for 20%~
50%, quick lime accounts for 10~40%, when ardealite accounts for 30%~60%, and curing/stabilizing effect is optimal, and leaching ability of heavy metal is most
It is few.In the ratio range, leaching ability of heavy metal is less than using silicate cement solidification/stabilized solidified earth.
Construction method in situ：Original position construction can use stir in situ method.According to geological conditions, heavy metal pollution place is repaiied
The curing agent used again is stirred it with live soil in-situ using professional equipment, forms pile body, and then realize heavy metal pollution
The solidification punishment in place.Deep Mixing Method is divided into grout deep mixing method (abbreviation wet method) and stir powder spray method is (referred to as dry
Method), using the curing agent of heavy metal pollution site remediation as slurries or powder material, goed deep into using the deep mixer of specialty
Ground stirs foundation soil and curing agent, and curing agent can chemically react with soil, solidify, stabilize heavy metal.Powder
Body gunite is compared with grout deep mixing method, in soil property whipping process, and curing agent can absorb the large quantity of moisture in the soil body, subtract
Low soil moisture content knot, therefore different treating methods may be selected in different moisture content and the ground of requirement for bearing capacity.
Dystopy construction method：The soil layer repaired will be needed to excavate, the curing agent stirring with heavy metal pollution site remediation is equal
Even, then compacting backfills the soil in-situ, it can also be used to which other aspects, such as construction material increases dykes and dams in civil engineering
Deng.
Beneficial effect：Inventor has found through overtesting, and appropriate aluminium, calcium, sulfur content reaction can generate a large amount of entringite,
Entringite heavy metal has good solidification, stabilization effect.Appropriate entringite can not only have by effects such as displacement, absorption
Effect solidification, stabilisation heavy metal ion, and the dilatancy that entringite has can reduce soil body hole, further reduce a huge sum of money
Belong to dissolution.
Embodiment
Curing agent of the present invention is made up of quick lime, alumina cement and ardealite, and proportioning (mass ratio) is：High alumina water
Mud accounts for 20%~50%, and quick lime accounts for 10~40%, and ardealite accounts for 30%~60%.Carried out using the required soil body to be processed several
Group test of Proportional Ratio, determines optimal proportion.It is heavy metal-polluted according to concrete engineering during with curing heavy metal Polluted Soil of the present invention
Contaminating concentration and processing target needs, curing agent incorporation (ratio of curing agent quality and dry ground quality) desirable 5%~30%.
Test example 1
In the present embodiment, certain representative heavy metal contaminated site soil, soil sample liquid limit is 37.2%, and plasticity index is 11.8, according to
According to《The engineering classification standard of soil》(GB/T 50145-2007), the soil sample is named as silty clay, heavy metal concentration (Pb mass
With dry ground mass ratio) it is about 5000mg/kg, sample moisture content is 24%.Curing agent takes the alumina cement of different ratio, raw stone
Ash, ardealite are combined, and the total volume of curing agent is the 15% of dry ground quality.According to different ratio, different curing agent are prepared, will
In the solidification Polluted Soil press-in diameter 50mm stirred, height 100mm mould.The demoulding, sealing after sample makes, feeding mark
Quasi- fog room, is conserved 28 days and 90 days in 20 ± 2 DEG C of temperature, environment of the relative humidity more than 95%.According to specification HJ/
T300-2007 methods, the Leaching of Heavy Metals concentration of test sample.Same proportioning makes three parallel samples, takes its concentration to be averaged
Value is used as test result.
Embodiment 1
A kind of curing agent of the heavy metal pollution site remediation based on entringite, curing agent is by alumina cement, quick lime, phosphorus
Gypsum is constituted, and wherein alumina cement mass change scope is 0%~70%, and Lime Quality excursion is 0%~50%, phosphorus
Gypsum quality excursion is 20%~70%, and curing agent incorporation accounts for the 15% of dry ground quality.After punishment, testing result table
Bright, 28 days Leaching of Heavy Metals concentration is less than 0.2mg/L after processing, far below discarded danger standard (5mg/L), and weighs for its 90 days
It is smaller when metal leaching concentration is compared with 28.Curing heavy metal Polluted Soil phase with same amount using Portland cement as curing agent
Than the solidified earth Leaching of Heavy Metals concentration reduction by more than 50% of Novel curing agent solidification.The leaching concentration of heavy metal and high alumina water
Mud, quick lime, ardealite mass ratio it is relevant, when quick lime and alumina cement mass ratio increase to 70% by 35%, a huge sum of money
Category leaching concentration reduction amplitude, which is presented, first significantly reduces the trend being gradually reduced afterwards.When the mass ratio of ardealite and alumina cement is big
When 75%, the leaching concentration of heavy metal, shows that entringite has when the leaching concentration of heavy metal is less than 28 days during 90 day age
Preferable stability.
Claims (5)
1. a kind of curing agent of the heavy metal pollution site remediation based on entringite, it is characterised in that the curing agent includes high alumina water
Mud, quick lime, ardealite, be according to the composition of mass ratio：
Alumina cement 20%~50%,
Quick lime 10~40%,
Ardealite 30%~60%.
2. a kind of application method of the curing agent of the heavy metal pollution site remediation as claimed in claim 1 based on entringite,
It is characterized in that using construction method in situ or dystopy construction method, according to geological conditions, heavy metal pollution site remediation is made
Curing agent is stirred with live soil in-situ, forms pile body, and then realize the solidification punishment in heavy metal pollution place, the original
Position construction method step be：Pile position is determined, the curing agent prepared is sprayed into the soil body using deep-mixed pile machinery,
And it is by stirring vane that the curing agent and soil shear failure is uniform, until design punishment depth.
3. the application method of the curing agent of the heavy metal pollution site remediation as claimed in claim 2 based on entringite, it is special
Levy and be that the stir in situ is divided into grout deep mixing method abbreviation wet method and stir powder spray method abbreviation dry method, using heavy metal-polluted
The curing agent of site remediation is contaminated as slurries, gos deep into ground using deep mixer and foundation soil stirs with curing agent, institute
Stating curing agent can chemically react with soil, solidify, stabilize heavy metal.
4. the application method of the curing agent of the heavy metal pollution site remediation as claimed in claim 2 based on entringite, it is special
Levy and be that the stir in situ is divided into grout deep mixing method abbreviation wet method and stir powder spray method abbreviation dry method, using heavy metal-polluted
The curing agent of site remediation is contaminated as powder material, is goed deep into ground using deep mixer and is stirred foundation soil and curing agent
Even, the curing agent can chemically react with soil, solidify, stabilize heavy metal.
5. the application method of the curing agent of the heavy metal pollution site remediation as claimed in claim 2 based on entringite, it is special
Levy and be that the dystopy construction method is：The soil layer repaired will be needed to excavate, stirred with the curing agent of heavy metal pollution site remediation
Mix uniform, then backfill the soil in-situ, be compacted.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710413337.9A CN107162549A (en) | 2017-06-05 | 2017-06-05 | The curing agent and application method of heavy metal pollution site remediation based on entringite |
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| CN201710413337.9A CN107162549A (en) | 2017-06-05 | 2017-06-05 | The curing agent and application method of heavy metal pollution site remediation based on entringite |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558252A (en) * | 2017-12-27 | 2018-09-21 | 东南大学 | A kind of curing agent and its application for reinforcing high organic weak soil |
| CN109111927A (en) * | 2018-08-14 | 2019-01-01 | 东南大学 | A kind of heavy metal pollution sandy soil curing agent and its application method |
| CN110240456A (en) * | 2019-07-24 | 2019-09-17 | 西安建筑科技大学 | A kind of processing method and heavy metal ion-sulphate aluminium cement-bentonite composite material containing heavy metal ion industrial wastewater |
| CN110668748A (en) * | 2019-09-25 | 2020-01-10 | 上海市政工程设计研究总院（集团）有限公司 | Method suitable for curing sludge incineration ash for making bricks |
| CN112024586A (en) * | 2020-08-05 | 2020-12-04 | 江苏山水环境建设集团股份有限公司 | In-situ solidification and restoration method for contaminated site soil |
| CN114505339A (en) * | 2022-02-21 | 2022-05-17 | 江西挺进环保科技股份有限公司 | In-situ stabilization/solidification mine ecological restoration method |
| CN114621023A (en) * | 2022-04-28 | 2022-06-14 | 中交疏浚技术装备国家工程研究中心有限公司 | Method for preparing autoclaved aerated block by using phosphogypsum and dredged sediment and product |
| CN115611602A (en) * | 2022-11-08 | 2023-01-17 | 云南云天化环保科技有限公司 | Phosphogypsum-containing pit filling and ecological restoration material and preparation method thereof |
| CN115921515A (en) * | 2022-11-09 | 2023-04-07 | 武汉轻工大学 | Curing treatment method for heavy metal contaminated soil |
| CN117602859A (en) * | 2023-10-10 | 2024-02-27 | 江苏集萃功能材料研究所有限公司 | Sludge building material treatment system and treatment method |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558252A (en) * | 2017-12-27 | 2018-09-21 | 东南大学 | A kind of curing agent and its application for reinforcing high organic weak soil |
| CN109111927A (en) * | 2018-08-14 | 2019-01-01 | 东南大学 | A kind of heavy metal pollution sandy soil curing agent and its application method |
| CN109111927B (en) * | 2018-08-14 | 2020-07-31 | 东南大学 | Heavy metal polluted sandy soil curing agent and application method thereof |
| CN110240456A (en) * | 2019-07-24 | 2019-09-17 | 西安建筑科技大学 | A kind of processing method and heavy metal ion-sulphate aluminium cement-bentonite composite material containing heavy metal ion industrial wastewater |
| CN110668748A (en) * | 2019-09-25 | 2020-01-10 | 上海市政工程设计研究总院（集团）有限公司 | Method suitable for curing sludge incineration ash for making bricks |
| CN112024586A (en) * | 2020-08-05 | 2020-12-04 | 江苏山水环境建设集团股份有限公司 | In-situ solidification and restoration method for contaminated site soil |
| CN114505339A (en) * | 2022-02-21 | 2022-05-17 | 江西挺进环保科技股份有限公司 | In-situ stabilization/solidification mine ecological restoration method |
| CN114621023A (en) * | 2022-04-28 | 2022-06-14 | 中交疏浚技术装备国家工程研究中心有限公司 | Method for preparing autoclaved aerated block by using phosphogypsum and dredged sediment and product |
| CN114621023B (en) * | 2022-04-28 | 2023-11-03 | 中交疏浚技术装备国家工程研究中心有限公司 | Method for preparing autoclaved aerated block by using phosphogypsum and dredging sediment and product |
| CN115611602A (en) * | 2022-11-08 | 2023-01-17 | 云南云天化环保科技有限公司 | Phosphogypsum-containing pit filling and ecological restoration material and preparation method thereof |
| CN115921515A (en) * | 2022-11-09 | 2023-04-07 | 武汉轻工大学 | Curing treatment method for heavy metal contaminated soil |
| CN117602859A (en) * | 2023-10-10 | 2024-02-27 | 江苏集萃功能材料研究所有限公司 | Sludge building material treatment system and treatment method |
| CN117602859B (en) * | 2023-10-10 | 2024-04-23 | 江苏集萃功能材料研究所有限公司 | Sludge building material treatment system and treatment method |
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