CN106984641B - Chemical stabilizer for repairing heavy metal contaminated soil and repairing method of heavy metal contaminated soil - Google Patents
Chemical stabilizer for repairing heavy metal contaminated soil and repairing method of heavy metal contaminated soil Download PDFInfo
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- CN106984641B CN106984641B CN201710117728.6A CN201710117728A CN106984641B CN 106984641 B CN106984641 B CN 106984641B CN 201710117728 A CN201710117728 A CN 201710117728A CN 106984641 B CN106984641 B CN 106984641B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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Abstract
The invention discloses a chemical stabilizer for repairing heavy metal contaminated soil and a repairing method of heavy metal contaminated soil, wherein the chemical stabilizer for repairing heavy metal contaminated soil comprises a solid conditioner and a liquid stabilizer, and the solid conditioner comprises the following components in parts by weight: 40-55 parts of fly ash, 20-35 parts of phosphogypsum and 15-30 parts of red mud; the liquid stabilizer is a zero-valent nano iron mixed suspension with rhamnolipid dispersed. The method for restoring the heavy metal contaminated soil comprises the following steps: (1) applying a solid conditioner on the surface of the heavy metal contaminated soil for conditioning; (2) and spraying a liquid stabilizer to reduce the heavy metals in the polluted soil. The method for restoring the heavy metal contaminated soil has the advantages of low cost, good effect, high efficiency, environmental friendliness and the like.
Description
Technical Field
The invention relates to the technical field of soil remediation treatment, in particular to a chemical stabilizer for heavy metal contaminated soil remediation and a remediation method of heavy metal contaminated soil.
Background
With the upgrading of industrial structures and the adjustment of urban layout in China, a lot of cities emerge the phenomena of closing and moving of a large number of polluted enterprises, so that a large number of industrial polluted sites are left in the cities, wherein heavy metal polluted soil is a common type in the industrial polluted sites. Most of the polluted sites are subjected to land type change due to reutilization, and the harm of heavy metals to animals, plants and human bodies has long-term property, potential property and irreversibility, so that the corresponding repair is carried out before the polluted soil is reused to ensure the site environment and the health of residents.
At present, the heavy metal contaminated soil is mainly repaired by several methods such as physics, chemistry, biology and the like. The physical method firstly digs out the polluted soil, and then carries out leaching, air stripping or heat treatment and the like on the dug-out polluted soil, and the measures have the advantages of thorough effect, stability and the like, but have the problems of high treatment cost, complex construction and the like, and are difficult to popularize on a large scale. The biological method comprises a plant restoration technology and a microorganism restoration technology, is simple and convenient to implement, has the advantages of low investment, low environmental disturbance and the like, but also has more limiting factors: the plant species for repairing the phytoremediation technology are limited, the repairing speed is slow, the problems of reprocessing of a large amount of heavy metal accumulated plants and the like are also main factors for limiting the large-scale popularization of the phytoremediation technology; the microbial repairing technology has limited kinds of repairing microbes, and the microbial organism is small, so the amount of the repaired heavy metal is small, and the repairing speed is slow, thereby limiting the large-scale popularization of the microbial repairing technology. The chemical methods mainly comprise an extraction method, a solidification method, an electrochemical method, an application modifier method and the like. The chemical fixing method, also called chemical stabilizing method, is a mature, economic and feasible method, and the technology utilizes the physicochemical actions of hydration reaction, oxidation reduction, chelation, precipitation, adsorption and the like of a stabilizing agent or a fixing agent and the heavy metal in the soil to achieve the effect of remediation and treatment by changing the chemical form of the heavy metal in the soil or reducing the mobility of the heavy metal. Compared with other repair technologies, the method has the advantages of wide application range, large processing capacity, various fixed object types, quick response, obvious effect and the like, and has better application prospect.
The chemical fixing agents commonly used at present are divided into several categories, such as natural minerals, organic matters, limes, replacement metals and the like, and the chemical fixing agents respectively have the following problems: the fixing efficiency of the natural mineral type fixing agent to heavy metals is low; when the organic fixing agent is used for repairing heavy metal contaminated soil, secondary pollution exists; lime fixatives generally change the pH of soil to precipitate heavy metals as hydroxides and carbonates, and fixatives containing lime components can cause soil hardening and compatibilization after remediation after being added to soil, and the fixation effect of the compounds such as hydroxides and carbonates formed by simple hydration reaction on heavy metals in soil is easily affected by external environmental conditions, and the heavy metals in soil are potentially dissolved out again after long-term weathering and acid rain erosion. The replacement metal is mainly submicron or nanometer iron, has stronger reducing capability, and can replace the metal which is arranged behind the replacement metal in the metal activity sequence list to be deposited on the surface of the iron so as to achieve the purpose of removing pollution. However, submicron or nano iron has high cost and is easily oxidized by surrounding media (such as dissolved oxygen and water), so that the utilization efficiency of the iron is reduced; in addition, the nano zero-valent iron is slowly transferred in a non-loose medium, and the application of the nano zero-valent iron in soil remediation is further limited. Therefore, how to keep the original reactivity and the full contact with pollutants as much as possible, improve the remediation efficiency and reduce the reaction cost is the key for obtaining the remediation effect of the soil heavy metals by the nano zero-valent iron.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art, and the first purpose is to provide the chemical stabilizer for repairing the heavy metal polluted soil, which has the advantages of low cost, good effect, high efficiency and environmental friendliness; the second purpose is to provide the restoration method for restoring the heavy metal contaminated soil by applying the stabilizer.
In order to solve the technical problems, the invention adopts the following technical scheme:
a chemical stabilizer for repairing heavy metal contaminated soil comprises a solid conditioner and a liquid stabilizer, wherein the solid conditioner comprises the following components in parts by weight: 40-55 parts of fly ash, 20-35 parts of phosphogypsum and 15-30 parts of red mud; the liquid stabilizer is a rhamnolipid-coated zero-valent nano iron mixed suspension.
Preferably, the preparation method of the liquid stabilizer comprises the following steps: under the protection atmosphere and mechanical stirring, adding the rhamnolipid solution into the ferric chloride solution, and then dropwise adding NaHB4And reacting the solution to obtain the rhamnolipid-coated zero-valent nano-iron mixed suspension.
Preferably, the concentration of the rhamnolipid solution is 2 g/L-3 g/L; the concentration of the ferric chloride solution is 0.15-0.25 mol/L; the NaHB4The concentration of the solution is 0.3 mol/L-0.5 mol/L; the rhamnolipid solution, the ferric chloride solution and the NaHB4The volume ratio of the solution is 2: 1.
Preferably, the protective atmosphere is nitrogen, and the rotation speed of the mechanical stirring is 350 r/min-550 r/min.
Preferably, the solid conditioning agent comprises the following components in parts by weight: 45-50 parts of fly ash, 25-30 parts of phosphogypsum and 20-25 parts of red mud.
Preferably, the solid conditioning agent comprises the following components in parts by weight: 48 parts of fly ash, 27 parts of phosphogypsum and 22 parts of red mud.
As a general inventive concept, the present invention also provides a method for remediating heavy metal contaminated soil, comprising the steps of:
(1) applying the solid conditioner with the thickness of 1-2 cm on the surface of the heavy metal contaminated soil, and uniformly mixing the soil with the thickness of 15-25 cm on the surface of the heavy metal contaminated soil and the applied solid conditioner in a ploughing mode;
(2) and after 1-2 months, spraying the liquid stabilizer in the heavy metal contaminated soil, and after maintaining for 4-6 months, completing the restoration of the heavy metal contaminated soil.
Preferably, in the step (2), the addition amount of the liquid stabilizer is 15-30% of the mass of the soil with the thickness of 15-25 cm on the surface layer of the heavy metal polluted soil.
Compared with the prior art, the invention has the advantages that:
1. the chemical stabilizer for repairing the heavy metal contaminated soil disclosed by the invention promotes the capability of repairing the heavy metal contaminated soil by the combined action of the solid conditioner and the liquid stabilizer through the organic combination of the solid conditioner and the liquid stabilizer. The solid conditioner is a mixture consisting of fly ash, phosphogypsum and red mud, and on one hand, a high-permeability rigid grid structure can be formed in heavy metal polluted soil, so that the uniform and rapid penetration of the liquid stabilizer containing nano zero-valent iron is facilitated; on the other hand, the heavy metal in the polluted soil can be adsorbed, collected and chelated, and the nano zero-valent iron is favorable for quickly and accurately reducing the heavy metal in the polluted soil; thereby greatly improving the utilization efficiency of the nano zero-valent iron and greatly reducing the cost of repairing the heavy metal contaminated soil.
2. According to the invention, the rhamnolipid is used for dispersing the zero-valent nano-iron, on one hand, the rhamnolipid is used for dispersing the periphery of the nano-zero-valent iron particles, and the nano-zero-valent iron particles are surrounded by the organic network in a similar way, so that the contact area between the nano-zero-valent iron particles and the surrounding media (such as dissolved oxygen and water) is effectively reduced, the nano-zero-valent iron is prevented from reacting with the surrounding media, and the higher reaction activity of the nano-zero-valent iron is maintained. On the other hand, the rhamnolipid can change the surface charge distribution of the nano zero-valent iron and generate an electrostatic stabilization effect, a steric hindrance effect and an electrostatic steric hindrance stabilization effect, so that the agglomeration effect among the nano zero-valent iron can be effectively prevented, and the dispersibility and the stability of the nano zero-valent iron are improved. In addition, carboxyl and hydroxyl of rhamnolipid can form chelate with heavy metal, especially have good chelating effect on heavy metal lead, and further facilitate rapid and accurate reduction of heavy metal in polluted soil by nano zero-valent iron. Therefore, the liquid-state stabilizer can further improve the efficiency of reducing the heavy metal in the polluted soil by the nano zero-valent iron and reduce the cost of restoring the heavy metal polluted soil.
Drawings
FIG. 1 is an SEM photograph of a liquid stabilizer of example 1 of the present invention, wherein the (b) drawing is a high-resolution drawing of the (a) drawing.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
Example 1:
preparation of chemical stabilizer for heavy metal contaminated soil remediation
(1) Preparation of solid conditioner: uniformly mixing the fly ash, the phosphogypsum and the red mud according to the weight ratio of 48: 27: 22 to obtain a solid conditioner;
(2) preparation of liquid stabilizer: under the nitrogen atmosphere and the mechanical stirring (the rotating speed is 400r/min), the rhamnolipid solution (2g/L) and FeCl with the volume ratio of 2: 1 are added3After the solution (0.2mol/L) is fully mixed, the solution is dripped and FeCl is added3Solution of equal volume of NaHB4Reacting the solution (0.4mol/L), and obtaining the rhamnolipid-coated zero-valent nano-iron mixed suspension after the reaction is finished when bubbles are not generated, and sealing and storing at normal temperature.
Fig. 1 is a scanning electron microscope image of the rhamnolipid-coated zero-valent nano-iron mixed suspension prepared in this example, and it can be seen from the image that the zero-valent nano-iron particles are uniformly dispersed, and the rhamnolipid successfully coats the zero-valent nano-iron.
Dispersing zero-valent nano-iron purchased in the market into water, wherein the content of the zero-valent nano-iron in a dispersion liquid is the same as that of the zero-valent nano-iron mixed suspension coated with the rhamnolipid prepared in the step (2), respectively spraying the dispersion liquid of the zero-valent nano-iron and the zero-valent nano-iron mixed suspension coated with the rhamnolipid prepared in the step (2) with the same volume into soil with seriously overproof lead content, and respectively measuring the percentage content of weak acid extraction state and reducible state of heavy metal lead in the soil after 2 months, wherein the result is shown in table 1, and the stabilizing efficiency of the zero-valent nano-iron coated with the rhamnolipid to the lead in the soil is obviously higher than that of the zero-valent nano-iron from the table 1.
Example 2:
a method for restoring heavy metal contaminated soil comprises the following steps:
(1) applying the solid conditioner with the thickness of 2cm prepared in the step (1) of the example 1 on the surface of heavy metal polluted soil in a certain lead-zinc mining area in a water gap mountain of Chaning city, and then uniformly mixing the soil with the thickness of 25cm on the surface layer of the heavy metal polluted soil and the applied solid conditioner in a ploughing mode;
(2) after 2 months, the liquid stabilizer prepared in step (2) of example 1 was sprayed in heavy metal contaminated soil in an amount of 25% by weight per kg of contaminated soil. After 6 months of maintenance, most of heavy metals Pb, Zn, Cu, Cd and Hg in the original heavy metal contaminated soil are reduced into low-price immobilized heavy metals, which shows that the method realizes in-situ remediation of the heavy metal contaminated soil, and the environmental quality of the remediated soil meets the requirement of the first-level standard value of soil environmental quality Standard (GB 15618-plus 1995) in China.
Comparative example 1:
a method for restoring heavy metal contaminated soil comprises the following steps:
the liquid stabilizer prepared in the step (2) of example 1 is sprayed in heavy metal contaminated soil of a lead and zinc mining area in Ningshan city of Henning, and the addition amount of each kilogram of contaminated soil is 25 wt%. After 8 months of maintenance, most of heavy metals Pb, Zn, Cu, Cd and Hg in the original heavy metal contaminated soil are reduced into low-valent immobilized heavy metals, the percentage content of the heavy metal lead residue state in the repaired soil is determined to be 81.3%, and the percentage content of the heavy metal lead residue state in the repaired soil in the embodiment 1 is up to 92.5%, which shows that the heavy metal contaminated soil is conditioned by the solid conditioner in the early stage, on one hand, a high-permeability rigid grid structure can be formed in the heavy metal contaminated soil, and the uniform and rapid permeation of a liquid stabilizer containing nano zero-valent iron is facilitated; on the other hand, the heavy metal in the polluted soil can be adsorbed, collected and chelated, and the nano zero-valent iron is favorable for quickly and accurately reducing the heavy metal in the polluted soil; thereby greatly improving the utilization efficiency of the nano zero-valent iron.
Example 3:
a method for restoring heavy metal contaminated soil comprises the following steps:
(1) applying the solid conditioner with the thickness of 2cm, prepared in the step (1) in the example 1, on the surface of the heavy metal polluted soil left in history of a certain colored mining area in the Xianghua mountain area in Linwu county, and then uniformly mixing the soil with the thickness of 20cm on the surface of the heavy metal polluted soil and the applied solid conditioner in a turning mode;
(2) after 2 months, the liquid stabilizer prepared in step (2) of example 1 was sprayed in heavy metal contaminated soil in an amount of 20% by weight per kg of contaminated soil. After 6 months of maintenance, the heavy metals Pb, Zn, Cu, Cd and Hg in the original heavy metal contaminated soil are reduced into low-price immobilized heavy metals, which shows that the method realizes the in-situ remediation of the heavy metal contaminated soil, and the environment quality of the remediated soil meets the requirement of the first-grade standard value of the soil environment quality standard (GB 15618-.
Finally, it must be said here that: the above embodiments are only used for further detailed description of the technical solutions of the present invention, and should not be understood as limiting the scope of the present invention, and the insubstantial modifications and adaptations made by those skilled in the art according to the above descriptions of the present invention are within the scope of the present invention. Finally, it must be said here that: the above embodiments are only used for further detailed description of the technical solutions of the present invention, and should not be understood as limiting the scope of the present invention, and the insubstantial modifications and adaptations made by those skilled in the art according to the above descriptions of the present invention are within the scope of the present invention.
Claims (6)
1. The chemical stabilizer for repairing the heavy metal contaminated soil is characterized by comprising a solid conditioner and a liquid stabilizer, wherein the solid conditioner comprises the following components in parts by weight: 40-55 parts of fly ash, 20-35 parts of phosphogypsum and 15-30 parts of red mud; the liquid stabilizer is a zero-valent nano iron mixed suspension with rhamnolipid dispersed;
the preparation method of the liquid stabilizer comprises the following steps: under the protection atmosphere and mechanical stirring, adding the rhamnolipid solution into the ferric chloride solution, and then dropwise adding NaHB4Reacting the solution to obtain a rhamnolipid dispersed zero-valent nano-iron mixed suspension;
the concentration of the rhamnolipid solution is 2 g/L-3 g/L; the concentration of the ferric chloride solution is 0.15-0.25 mol/L; the NaHB4The concentration of the solution is 0.3 mol/L-0.5 mol/L; the rhamnolipid solution, the ferric chloride solution and the NaHB4The volume ratio of the solution is 2: 1.
2. The chemical stabilizer for repairing heavy metal contaminated soil according to claim 1, wherein the protective atmosphere is nitrogen, and the rotation speed of the mechanical stirring is 350 r/min-550 r/min.
3. The chemical stabilizer for repairing the heavy metal contaminated soil according to claim 1, wherein the solid conditioner comprises the following components in parts by weight: 45-50 parts of fly ash, 25-30 parts of phosphogypsum and 20-25 parts of red mud.
4. The chemical stabilizer for repairing the heavy metal contaminated soil according to claim 3, wherein the solid conditioner comprises the following components in parts by weight: 48 parts of fly ash, 27 parts of phosphogypsum and 22 parts of red mud.
5. The method for restoring the heavy metal contaminated soil is characterized by comprising the following steps:
(1) applying the solid conditioner as claimed in any one of claims 1 to 4 with the thickness of 1cm to 2cm on the surface of the heavy metal contaminated soil, and uniformly mixing the soil with the thickness of 15cm to 25cm on the surface layer of the heavy metal contaminated soil and the applied solid conditioner in a turning mode;
(2) spraying the liquid stabilizer of any one of claims 1 to 4 to the heavy metal contaminated soil after 1 to 2 months, and completing remediation of the heavy metal contaminated soil after 4 to 6 months of maintenance.
6. The method for remediating heavy metal contaminated soil as recited in claim 5, wherein in the step (2), the amount of the liquid stabilizer added is 15% to 30% of the mass of the heavy metal contaminated soil with a surface layer having a thickness of 15cm to 25 cm.
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| CN111073656A (en) * | 2018-10-18 | 2020-04-28 | 南京化学工业园环保产业协同创新有限公司 | Novel heavy metal stabilizer and method for treating heavy metal contaminated soil by using same |
| CN113578916B (en) * | 2021-06-23 | 2022-05-10 | 常熟理工学院 | Method for realizing resource utilization of phosphogypsum by utilizing waste incineration fly ash |
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| CN102234168A (en) * | 2010-05-06 | 2011-11-09 | 中国科学院生态环境研究中心 | Preparation and application method of mineral substance stabilizing agent for controlling releasing of phosphorus and heavy metals in dredged bottom sediment |
| CN103436265B (en) * | 2013-08-23 | 2016-04-13 | 付融冰 | A kind of contaminated soil, bed mud and mud deoxidization, degradation stablizer and preparation method thereof and using method |
| CN104194795A (en) * | 2014-06-10 | 2014-12-10 | 青岛华仁技术孵化器有限公司 | Novel in-situ passivation modifier and preparing method thereof |
| CN104226987B (en) * | 2014-09-30 | 2016-08-24 | 湖南大学 | A kind of modified Nano Zero-valent Iron and preparation method thereof |
| CN105399199A (en) * | 2015-12-23 | 2016-03-16 | 成都理工大学 | Preparation method of biosurfactants-modified nano-iron/carbon composite material and application in removing nitrate nitrogen in underground water |
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