CN117801826B - Environment-friendly curing agent and method for repairing polluted soil by using same - Google Patents
Environment-friendly curing agent and method for repairing polluted soil by using same Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
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- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
-
- 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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses an environment-friendly curing agent which is characterized by comprising, by mass, 75% -90% of an alkaline inorganic composite material, 5% -20% of an organic composite material and 5% of plant fibers; the alkaline inorganic composite material consists of 10 parts of plant ash, 16 parts of boron-magnesium mud, 1 part of phosphogypsum and 9 parts of coal gangue by mass, and the organic composite material consists of 2 parts of swill-cooked dirty oil and 1 part of cassava starch residues by mass. Meanwhile, the preparation and application methods of the curing agent are also provided. The curing agent disclosed by the invention is mainly composed of industrial or biological waste, and is wide in material source, simple and convenient to prepare and environment-friendly; the method can replace the traditional cement material, synchronously and efficiently treat heavy metals and organic pollutants, remarkably reduce the leaching toxicity of soil pollutants, and realize waste treatment; the environmental safety of the polluted soil is improved, the engineering characteristics of the soil body can be improved, and the economic and environmental benefits are obvious.
Description
Technical Field
The invention belongs to the technical field of environmental rock soil and foundation treatment, and particularly relates to an environment-friendly curing agent and a method for repairing polluted soil by using the same.
Background
In the running process of industrial enterprises, due to the problems of three wastes discharge and the like, toxic heavy metals, organic pollutants and the like often enter the surrounding soil and groundwater, and the toxic heavy metals, the organic pollutants and the like can enter human bodies through various ways such as food, drinking water and the like, and the strength of foundations can be reduced, so that the toxic heavy metals, the organic pollutants and the like can cause environmental pollution and unsafe harm to buildings if the toxic heavy metals, the organic pollutants and the like are not treated or are improperly treated before secondary construction. In addition, due to the repeated use of the construction land and other reasons, the residual pollutants in the soil are accumulated, and heavy metals and organic pollutants coexist.
The conventional curing/stabilizing technology mostly adopts cement and other conventional high-alkaline curing agents, has obvious defects in the aspects of repairing effect, environmental safety, engineering performance, ecological friendliness and the like, and is difficult to meet the requirement of repairing high-concentration composite polluted sites in the current stage of China. Firstly, the treatment effect on organic matters and high-concentration heavy metal polluted soil is poor. The existence of organic pollutants and high-concentration heavy metals can seriously inhibit hydration reaction of cement materials, so that the quantity of hydration products is reduced, and further the engineering characteristics of solidified soil and the environmental safety are affected; when heavy metal and organic matter pollution exist on the spot at the same time, the curing effect of the traditional cement curing agent is greatly reduced due to the influence of the organic pollutant. And secondly, the restored soil body is too high in alkalinity, so that the cement solidified soil is unfavorable for long-term stability of heavy metal sealing, the secondary pollution possibility is high, and alkaline leaching liquid is easy to generate. Thirdly, the traditional polluted site soil remediation uses cement as a curing agent in a large amount, and the cement is used as a material with high carbon emission and pollution emission in the production process, so that the method is unfavorable for realizing green low carbon in the whole soil remediation process.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the environment-friendly curing agent and the method for repairing the polluted soil are provided, and the curing agent can synchronously adsorb organic pollutants and fix heavy metals in the soil, so that the leaching toxicity of the polluted soil is reduced, and meanwhile, the engineering characteristics such as the strength and the like are improved. Meanwhile, the preparation and application methods of the curing agent are provided, so that the source of raw materials is wide, the preparation is simple and convenient, the environment is friendly, the waste is treated, the environmental safety and engineering performance of polluted soil are improved, and remarkable economic and environmental benefits are created.
In order to solve the technical problems, the invention adopts the following technical scheme:
an environment-friendly curing agent comprises the following components in percentage by mass:
Alkaline inorganic composite: 75% -90% of an organic composite material: 5% -20%, plant fiber: 5%; the alkaline inorganic composite material consists of 10 parts of plant ash, 16 parts of boron-magnesium mud, 1 part of phosphogypsum and 9 parts of coal gangue by mass, and the organic composite material consists of 2 parts of swill-cooked dirty oil and 1 part of cassava starch residues by mass.
Further, the alkaline inorganic composite material is prepared by the following steps:
(1) Pouring plant ash into a plastic container according to a solid-to-liquid ratio of 1:3 adding hot water, stirring uniformly, standing at room temperature for 3 days, and filtering out bottom sediment to prepare plant ash alkali liquor for later use;
(2) The boron-magnesium mud is placed in a 105 ℃ oven to be dried for 4 h so as to be fully dried, and is poured into plant ash alkali liquor after being screened, stirred evenly and kept stand for 6 h under the condition of room temperature;
(3) Drying the mixture alkali liquor in a drying oven at 105 ℃ until the liquid is completely evaporated, then placing the mixture alkali liquor in a muffle furnace at 600 ℃ for roasting 2h, cooling to room temperature, grinding and sieving to obtain activated boron-magnesium sludge;
(4) Placing the coal gangue in a muffle furnace, performing heat treatment at 600 ℃ for 3 h, cooling, grinding and sieving to obtain coal gangue dry powder;
(5) Drying phosphogypsum in a 105 ℃ oven to obtain 4 h, fully drying, grinding and sieving to obtain phosphogypsum dry powder;
(6) Mixing the phosphogypsum dry powder, the coal gangue dry powder and the activated boron magnesium sludge, and uniformly stirring for 15min to prepare the alkaline inorganic composite material.
Further, the organic composite material is prepared according to the following steps:
(1) Heating and stirring the collected waste swill-cooked dirty oil, and filtering out surface scum and bottom sediment to obtain crude swill-cooked dirty oil;
(2) Sieving the cassava starch residues with a 20-mesh sieve, and mixing the cassava starch residues with water according to a ratio of 1:6, uniformly stirring, and then placing in a microwave environment for heating treatment of 25 min, wherein the microwave frequency is 3.0 GHz, and the power density is 0.6 w/cm 2 to obtain cassava starch slurry;
(3) Taking out the cassava starch slurry, placing the cassava starch slurry in a water bath kettle at 80 ℃, and then pouring the weighed crude swill-cooked dirty oil into the slurry successively, and continuously stirring while chamfering to prepare the organic composite material.
Further, the plant fiber is one or more of sisal fiber, bamboo fiber, wood fiber and coconut fiber.
The method for restoring the polluted soil by using the environment-friendly curing agent comprises the following steps:
(1) Pretreating the polluted soil by using a crushing and screening hopper to remove sundries such as broken stones in the polluted soil, and primarily mixing the sundries uniformly;
(2) The inorganic composite material and plant fiber are paved on the surface of a polluted soil pile, and are mixed and stirred for more than 3 times by utilizing a crushing and screening hopper until the mixture is observed to be uniform by naked eyes;
(3) Placing the mixture into a stirring tank, adding an organic composite material and a proper amount of water, and uniformly stirring for 30 min;
(4) And (3) the stirred soil is compacted and buried in an ectopic way, and the compaction degree is more than or equal to 80%.
(5) And (5) finishing the repair.
Further, in the repairing method, the mass ratio of the curing agent to the polluted soil is 10: 100-25: between 100; and the concentration of heavy metal pollutants in the soil is less than or equal to 10000 mg/kg, and the concentration of organic pollutants is less than or equal to 3000 mg/kg.
The technical scheme of the invention has the following beneficial effects:
Strong cementing capability, high strength of solidified soil, low permeability and good stability. Plant ash in the curing agent can react with activated boron magnesium mud and phosphogypsum to generate strong cementing materials MgCO 3 and MgKPO 4, and the cementing strength of the plant ash is obviously higher than that of calcium compounds such as conventional CaCO 3; in addition, the phosphogypsum and the plant ash alkali excite the coal gangue to generate a large amount of strong gelling substances, so that the soil body structure is further bonded and compacted; after mixing the swill-cooked dirty oil with starch and the like in the cassava starch residue, the mixture interacts with activated boron magnesium mud and Mg (OH) 2 and Ca (OH) 2 separated out from coal gangue to generate a cementing mechanism similar to the traditional glutinous rice-lime slurry in China, so that the size and the morphology of magnesium carbonate crystals can be effectively regulated and controlled, and the particles such as magnesium carbonate and the like are effectively bonded and micro-pores of the magnesium carbonate crystals are filled while the crystal particles are smaller and have a more compact structure; the inorganic mixture in turn inhibits bacterial growth, reduces the permeability of soil body, and keeps the organic components in the solidified soil stable for a long time; in addition, the added plant fiber is used as a biological reinforcement material, so that the soil strength is further effectively improved, and the soil permeability is reduced; under the combined action of the mechanisms, the soil particles are tightly bonded to form a high-strength stable structure.
(2) The fixing effect of pollutants is good, and the treatment effect on high-concentration heavy metals and organic pollutants is obvious. The curing agent realizes cementation hardening based on a biomineralization mechanism of organic/inorganic matter synergy, has the characteristics of inorganic and organic cementing materials, and effectively avoids the inhibition effect of organic pollutants on cement clinker hydration reaction; the Mg (OH) 2 crystal generated by the reaction is in a loose and porous microstructure, has good adsorption and encapsulation effects on heavy metal and organic pollutants, and the rich carbonate and phosphate can react with the heavy metal to generate highly insoluble heavy metal salt precipitate, so that the adsorption and encapsulation effects on the pollutants, especially the organic pollutants, are further enhanced by the presence of plant fibers and oil components; meanwhile, the restored soil body presents moderate alkalinity (pH is approximately equal to 10), so that the possibility of secondary dissolution of heavy metal hydroxide precipitation under the condition of ultrahigh alkalinity (pH is more than 12) of cement reinforced soil is avoided; in addition, the high-strength gel product and the adsorptive component act together to realize long-term fixation, sealing and stabilization of pollutants under carbon dioxide erosion and freeze thawing conditions.
(3) The curing agent has the advantages of wide raw material sources, simple and convenient preparation and environmental protection. The main components of the curing agent are plant ash, boron magnesium mud, phosphogypsum, coal gangue, swill-cooked dirty oil and cassava starch residues which are industrial and agricultural waste materials, and are cheap and easy to obtain; the emission of pollutants such as CO 2 and the like in the silicate cement production process is avoided, meanwhile, the damage to the soil structure is small, and the secondary development and utilization of the restored soil are utilized; the energy consumption in the production process is low, the method is environment-friendly, and the environmental and economic benefits are outstanding.
Detailed Description
The following describes the technical scheme of the present invention in detail with reference to examples. The scope of the invention is not limited by these examples, but is set forth in the claims.
The heavy metal and organic matter combined polluted soil is obtained from a Nanjing chemical plant, the water content is 16%, the main pollutant of the soil is Pb 3610 mg/kg, chlorobenzene 129 mg/kg, and the concentration of o (p) nitrochlorobenzene is 189 mg/kg.
The swill-cooked dirty oil is collected from families; the plant fiber is shredded coconut; the plant ash is crop plant ash provided by Jiangsu Huaian national information biomass power generation limited company, and mainly comprises rice hull ash with the pH value of 11.42; phosphogypsum is purchased from a slag yard of a certain chemical industry limited company in Yunnan, and the total SO 3、CaO、SiO2 and P 2O5 contents are 31.25%, 26.2%, 17.08%, 7.15% and the water content is 18.6% respectively; the boron-magnesium mud is taken from a borax-generated waste storage yard, and the MgO content of the boron-magnesium mud is 46%; the coal gangue comes from the Shaanxi Huangling mining area, the total SiO 2、Al2O3、Fe2O3 amount reaches 79.2%, the cassava starch slag is mechanically dehydrated dry slag, the water content is 13%, and the starch, crude protein and crude fiber contents are 47%, 3% and 28% respectively; the content of main elements of the compound silicate cement of conch brand PC 32.5 measured by an X-ray fluorescence spectrometer is as follows: caO 44.37 percent and SiO 227.41%、Al2O3 13.09.09 percent.
The soil leaching toxicity test method is carried out by referring to the sulfate-nitric acid method (HJT-299-2007) of the solid waste leaching toxicity leaching method.
The percentages of components and amounts of the curing agents of each of the examples and comparative examples are shown in Table 1 below.
TABLE 1
Note 1: in each embodiment, the alkaline inorganic composite material consists of 10 parts of plant ash, 16 parts of boron-magnesium mud, 1 part of phosphogypsum and 9 parts of coal gangue according to mass.
And (2) injection: in each embodiment, the organic composite material consists of 2 parts of swill-cooked dirty oil and 1 part of cassava starch residues according to mass.
Examples
Other specific implementation steps and parameters of the embodiments are the same, and the specific details are as follows:
the curing agent is prepared according to the mass percentage of each component shown in the table 1, wherein the alkaline inorganic composite material is prepared according to the following steps:
(1) Pouring 10 kg plant ash into a plastic container according to a solid-to-liquid ratio of 1:3 adding 80 ℃ hot water, manually stirring uniformly, standing at room temperature for 3 days, and then using ZF-50L vacuum suction filtration equipment to filter out bottom sediment, thereby preparing plant ash alkali liquor for later use;
(2) The boron-magnesium mud is placed in a 105 ℃ oven to be dried for 4 h so as to be fully dried, and is poured into plant ash alkali liquor after being sieved by a 100-mesh sieve, and is stirred uniformly and kept stand for 6 h under the room temperature condition;
(3) Drying the mixture alkali liquor in a drying oven at 105 ℃ until the liquid is completely evaporated, then roasting in a muffle furnace at 600 ℃ for 2h, cooling to room temperature, grinding by a QM3SP4L planetary ball mill, and sieving by a 200-mesh sieve to obtain activated boron magnesium sludge;
(4) Placing the coal gangue in a muffle furnace, performing heat treatment at 600 ℃ for 3h, grinding by a ball mill, and sieving by a 200-mesh sieve to obtain coal gangue dry powder;
(5) The phosphogypsum is placed in a 105 ℃ oven to be dried for 4 h so as to be fully dried, and the phosphogypsum is ground by a QM3SP4L planetary ball mill and is sieved by a 200-mesh sieve to obtain phosphogypsum dry powder;
(6) Mixing the phosphogypsum dry powder, the coal gangue dry powder and the activated boron magnesium sludge, and uniformly stirring for 15min to prepare the alkaline inorganic composite material.
Further, the organic composite material is prepared according to the following steps:
(1) Heating the collected illegal cooking oil to 85-90 ℃, stirring for 10min, standing for 30: 30min, and filtering out surface scum and bottom sediment to obtain crude illegal cooking oil;
(2) Sieving the cassava starch residues with a 20-mesh sieve, and mixing the cassava starch residues with water according to a ratio of 1:6, uniformly stirring, and then placing in a microwave environment for heating treatment of 25 min, wherein the microwave frequency is 3.0 GHz, and the power density is 0.6 w/cm 2 to obtain cassava starch slurry;
(3) Taking out the cassava starch slurry, placing the cassava starch slurry in a water bath kettle at 80 ℃, and then pouring the weighed crude swill-cooked dirty oil into the slurry successively, and continuously stirring while chamfering to prepare the organic composite material.
A method of remediating contaminated soil with a curing agent comprising the steps of:
(1) Pretreating the polluted soil by using a small crushing and screening hopper to remove sundries such as broken stone with the particle size of more than or equal to 3 mm in the polluted soil, and primarily mixing uniformly;
(2) The inorganic composite material and plant fiber are paved on the surface of a polluted soil pile, and are mixed and stirred for more than 3 times by utilizing a crushing and screening hopper until the mixture is observed to be uniform by naked eyes;
(3) Placing the mixture into a cement paste stirring tank, adding an organic composite material and a proper amount of water, and uniformly stirring for 30 min;
(4) And compacting the stirred soil by using a jack to prepare a sample, wherein the compactness is 85%.
Comparative example
A method for restoring contaminated soil by portland cement comprising the steps of:
(1) Pretreating the polluted soil by using a small crushing and screening hopper to remove sundries such as broken stone with the particle size of more than or equal to 3 mm in the polluted soil, and primarily mixing uniformly;
(2) Paving the weighed silicate cement on the surface of the polluted soil pile, and mixing and stirring for more than 3 times by utilizing a crushing and screening hopper until the mixture is observed to be uniform by naked eyes;
(3) Placing the mixture into a cement paste stirring tank, adding a proper amount of water, and uniformly stirring for 30 min;
(4) And compacting the stirred soil by using a jack to prepare a sample, wherein the compactness is 85%.
Specific experimental comparative data are shown in table 2 below.
TABLE 2
From the table, the curing agent prepared finally can effectively fix heavy metals and organic pollutants in soil, reduce leaching toxicity of the heavy metals and the organic pollutants, improve mechanical strength of polluted soil and enable the cured soil to be alkaline to a moderate degree. The curing agent has the advantages of outstanding repairing effect, low cost and environmental friendliness, and is worthy of large-scale popularization and application.
Claims (4)
1. An environment-friendly curing agent is characterized in that: the composite material consists of 75-90% of alkaline inorganic composite material, 5-20% of organic composite material and 5% of plant fiber according to mass percentage; wherein the alkaline inorganic composite material consists of 10 parts of plant ash, 16 parts of boron-magnesium mud, 1 part of phosphogypsum and 9 parts of coal gangue by mass, and the organic composite material consists of 2 parts of swill-cooked dirty oil and 1 part of cassava starch residue by mass;
the alkaline inorganic composite material is prepared by the following steps:
(1) Pouring plant ash into a plastic container according to a solid-to-liquid ratio of 1:3 adding hot water, stirring uniformly, standing at room temperature for 3 days, and filtering out bottom sediment to prepare plant ash alkali liquor for later use;
(2) The boron-magnesium mud is placed in a 105 ℃ oven to be dried for 4 h so as to be fully dried, and is poured into plant ash alkali liquor after being screened, stirred evenly and kept stand for 6 h under the condition of room temperature;
(3) Placing the mixture subjected to standing in the step (2) in a baking oven at 105 ℃ for drying until the liquid is completely evaporated, then placing the mixture in a muffle furnace at 600 ℃ for roasting 2h, cooling to room temperature, grinding and sieving to obtain activated boron magnesium sludge;
(4) Placing the coal gangue in a muffle furnace, performing heat treatment at 600 ℃ for 3 h, cooling, grinding and sieving to obtain coal gangue dry powder;
(5) Drying phosphogypsum in a 105 ℃ oven to obtain 4 h, fully drying, grinding and sieving to obtain phosphogypsum dry powder;
(6) Mixing the phosphogypsum dry powder, the coal gangue dry powder and the activated boron magnesium sludge, and uniformly stirring for 15min to prepare an alkaline inorganic composite material;
The organic composite material is prepared by the following steps:
(1) Heating and stirring the collected waste swill-cooked dirty oil, and filtering out surface scum and bottom sediment to obtain crude swill-cooked dirty oil;
(2) Sieving the cassava starch residues with a 20-mesh sieve, and mixing the cassava starch residues with water according to a ratio of 1:6, uniformly stirring, and then placing in a microwave environment for heating treatment of 25 min, wherein the microwave frequency is 3.0 GHz, and the power density is 0.6 w/cm 2 to obtain cassava starch slurry;
(3) Taking out the cassava starch slurry, placing the cassava starch slurry in a water bath kettle at 80 ℃, and then pouring the weighed crude swill-cooked dirty oil into the slurry, and continuously stirring while chamfering to prepare the organic composite material.
2. The environment-friendly curing agent according to claim 1, wherein the plant fiber is one or more of sisal fiber, bamboo fiber, wood fiber and coconut fiber.
3. A method of remediating contaminated soil with an environmentally friendly curative according to claim 1, said method comprising the steps of:
(1) Pretreating the polluted soil by using a crushing screening hopper to remove broken stone in the polluted soil, and primarily and uniformly mixing;
(2) The inorganic composite material and plant fiber are paved on the surface of a polluted soil pile, and are mixed and stirred for more than 3 times by utilizing a crushing and screening hopper until the mixture is observed to be uniform by naked eyes;
(3) Placing the mixture into a stirring tank, adding an organic composite material and a proper amount of water, and uniformly stirring for 30 min;
(4) The stirred soil is compacted and buried in an ectopic way, and the compaction degree is more than or equal to 80%;
(5) And (5) finishing the repair.
4. The method for restoring polluted soil by using the environment-friendly curing agent as claimed in claim 3, wherein the mass ratio of the curing agent to the polluted soil is 10: 100-25: between 100; and the concentration of heavy metal pollutants in the soil is less than or equal to 10000 mg/kg, and the concentration of organic pollutants is less than or equal to 3000 mg/kg.
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| CN107021714B (en) * | 2017-04-14 | 2020-03-31 | 东南大学 | Curing agent for heavy metal contaminated soil and preparation and application methods thereof |
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