CN114989828A - Novel curing agent for curing heavy metal copper polluted soil and use method thereof - Google Patents

Novel curing agent for curing heavy metal copper polluted soil and use method thereof Download PDF

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CN114989828A
CN114989828A CN202210735672.1A CN202210735672A CN114989828A CN 114989828 A CN114989828 A CN 114989828A CN 202210735672 A CN202210735672 A CN 202210735672A CN 114989828 A CN114989828 A CN 114989828A
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curing agent
heavy metal
red mud
slag
curing
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李丽华
李欣
肖衡林
李文涛
庄心善
陈娜
钟楚珩
白玉霞
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Hubei University of Technology
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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
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    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
    • 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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    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/06—Calcium compounds, e.g. lime
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to the technical field of heavy metal polluted soil remediation, in particular to a novel curing agent for curing heavy metal copper polluted soil and a using method thereof, wherein the curing agent comprises, by mass, 20% -30% of red mud, 20% -30% of alkaline residue and 50% -60% of slag. The curing agent comprises slag micro powder, red mud and alkaline residue, the activity of the slag micro powder can be effectively excited by adding the red mud and the alkaline residue with strong basicity, the generation of land salinization is avoided while the red mud and the alkaline residue are consumed, and the aim of curing heavy metal polluted soil can be better achieved. The novel curing agent can replace the traditional curing agents such as cement and lime, reduces the problems of extra production cost and carbon emission, simultaneously consumes slag micro powder, red mud and caustic sludge to stack and cause salinization of land, can also achieve the aim of repairing soil mass polluted by heavy metal ions, and has the characteristics of simple operation, high efficiency, economy, environmental protection and the like.

Description

Novel curing agent for curing heavy metal copper polluted soil and use method thereof
Technical Field
The invention relates to the technical field of heavy metal polluted soil remediation, in particular to a novel curing agent for curing heavy metal copper polluted soil and a using method thereof.
Background
With the modernization of industrial and agricultural production, the heavy metal pollution of soil becomes a serious environmental problem facing the world, and the heavy metal pollution poses a great threat to the survival and development of human beings. In addition, heavy metal ions can damage the soil structure, and only the soil expansion causes the soil quality problems such as uneven settlement of the foundation and the like. The accumulation of heavy metal ions in soil can affect or even threaten the physical and psychological health of soil, ecosystems, animals and plants, and even human beings. Therefore, in order to effectively prevent the soil contaminated by heavy metal ions and to better master the technology for remediating the contaminated soil containing heavy metal ions, it is necessary to intensively study the solidification characteristics of the heavy metal ion contaminated soil.
At present, one of the commonly used restoration methods for heavy metal ion polluted soil in China is a solidification stabilization technology, which mixes a solidification stabilization agent with a polluted medium and realizes the fixation of poisons in the soil by two different means of physical action and chemical action, thereby reducing the environmental safety of the polluted medium and enabling the polluted medium to meet the standard requirement of the use environment. The solidification action is to convert a physically unstable harmful poison into a solid whole with a stable structure through the action of physical closure and the like, so that the harmful poison is converted into a granular or blocky solid from a granular body and the like, and the capability of releasing the solid whole to the environment is further reduced, and the action does not involve the chemical reaction between the pollutant and a solidification and stabilization medicament; the stabilization is to change the occurrence of pollutants in soil by utilizing the effective chemical reaction between the solidified stabilizing agent or the product thereof and the poison, convert the pollutants from an active state to a state with poor chemical activity, and further reduce the environmental hazard. Compared with other technologies, the solidification and stabilization technology has obvious advantages in the aspects of economic cost, convenience in use, long-acting effect, possibility of recycling in soil treatment projects and the like, and is the most effective means for treating the foundation soil polluted by the heavy metal pollutants.
Disclosure of Invention
One of the purposes of the invention is to provide a novel curing agent for curing heavy metal copper polluted soil, which solves the problem of solid waste stockpiling of red mud, slag and alkaline residue while repairing the heavy metal polluted soil.
The invention also aims to provide a use method of the novel curing agent for curing the heavy metal copper polluted soil, which is simple to operate and convenient to adjust.
The scheme adopted by the invention for realizing one of the purposes is as follows: a novel curing agent for curing heavy metal copper polluted soil comprises, by mass, 20-30% of red mud, 20-30% of alkaline residue and 50-60% of slag.
Preferably, the caustic sludge is industrial waste residue generated in the soda ash industry, the main component of the caustic sludge exists in the form of calcium salts such as calcium carbonate and calcium sulfate, the CaO content exceeds 60% by mass percentage, and the SO content is more than 60% by mass percentage 3 And SiO 2 The total content is up to 20 percent, and the Cl content is up to 10 percent.
Preferably, the slag mainly comprises a molten silicate and aluminosilicate, and CaO and SiO are calculated according to mass percentage 2 And Al 2 O 3 The total mass is over 85 percent.
Preferably, the red mud is industrial waste residue generated in the aluminum production industry, and the main chemical components comprise the following components in percentage by mass: more than 50% of iron and aluminum oxides and more than 20% of SiO in total 2 And CaO, wherein the iron and aluminum oxides are mainly Fe 2 O 3 And Al 2 O 3 。
The second scheme adopted by the invention for achieving the purpose is as follows: the use method of the novel curing agent for curing the heavy metal copper polluted soil comprises the following steps:
(1) drying and screening the red mud, the slag and the alkaline residue, and mixing the materials according to a certain mass ratio to obtain the curing agent;
(2) adding the obtained curing agent into a soil sample to be treated according to a certain amount, uniformly mixing, performing compaction treatment to prepare a soil sample, and placing and maintaining the soil sample for a certain age.
Preferably, in the step (1), the particle sizes of the screened alkaline residue, slag and red mud are all less than 2 mm.
Preferably, in the step (2), the addition amount of the curing agent accounts for 10% -30% of the soil sample to be treated.
Preferably, in the step (2), the soil sample to be treated is compacted after the water content is adjusted to 18% -23%.
Preferably, in the step (2), the soil sample after being cured for 7-28 days can be used as roadbed filling or natural soil.
The mechanism of the invention is summarized as follows:
a large amount of chemical components CaO contained in the curing agent red mud, the alkaline residue and the slag are used as a soil body supporting framework and can promote the hydration reaction between the curing agents to generate more gelled substances, and a large amount of Ca in the curing agents 2+ Reacting with OH-plasma to form Ca (OH) 2 The oxides are precipitated to play a role in filling and cementing pores in soil, so that the internal structure of the soil is more compact and stable, and the compressive strength is improved; secondly, the specific surface areas of the alkaline residue and the red mud are large, the alkaline residue and the red mud have strong adsorbability, and the alkaline residue and the red mud have good adsorbability on heavy metal ions; in addition, the surface active adsorption sites of iron and aluminum oxides contained in the curing agent combine copper ions in a water soluble state and an exchange state, so that the effectiveness of the copper ions is greatly weakened.
The industrial solid waste alkali residue adopted in the invention is industrial waste residue generated in the industrial process of producing soda ash, the red mud is industrial waste residue generated in the industrial process of producing aluminum, the alkali residue and the red mud both have certain alkalinity, the potential activity of slag micro powder can be effectively excited, and the hydration reaction is more thorough, so that a good solidification effect is achieved, the industrial solid waste is selected as the curing agent of the heavy metal polluted soil body, the ecological civilization concept of green development is met, and the purpose of treating waste with waste is achieved and the resources are comprehensively utilized.
The invention has the following advantages and beneficial effects:
the novel composite curing agent for repairing heavy metal polluted soil comprises slag micro-powder, red mud and alkaline residue, the activity of the slag micro-powder can be effectively excited by adding the red mud and the alkaline residue with strong basicity, the generation of land salinization is avoided while the red mud and the alkaline residue are consumed, and the aim of curing the heavy metal polluted soil can be better achieved.
The red mud in the novel curing agent is waste residue generated after aluminum is extracted in the aluminum production industry, and the piling of the red mud not only occupies a large amount of valuable land resources, but also needs higher piling cost, has great influence on the environment, and can be used for restoring heavy metal ion polluted soil by utilizing waste resources.
The alkaline residue in the novel curing agent is industrial waste residue discharged in the production process of soda ash, has the characteristics of strong alkalinity, high salinity, high water content and the like, is mainly treated in a local stockpiling mode at present, consumes a large amount of financial resources, occupies a large amount of land resources, blocks economic sustainable development, and can be used for repairing heavy metal ion polluted soil by utilizing waste resources.
The novel curing agent can replace the traditional curing agents such as cement and lime, reduces the problems of extra production cost and carbon emission to a certain extent, consumes slag micro powder, red mud and alkali slag to stack and cause land salinization, can also achieve the aim of repairing heavy metal ion polluted soil body, realizes the green resource utilization idea of 'treating waste with waste and changing waste into valuable', and has the characteristics of simple operation, high efficiency, economy, green environmental protection and the like.
Drawings
FIG. 1 is a graph showing an alignment of unconfined data of a soil sample prepared in example 1;
FIG. 2 is a graph showing the copper concentration in the leachate after curing the contaminated soil with different initial copper concentrations in examples 1-5 with the curing agent.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
The slag micropowder of the embodiment of the invention is obtained from concrete companies, and mainly comprises the following components of fused mass of silicate and aluminosilicate, CaO and SiO 2 And Al 2 O 3 The total content is over 85 percent. The red mud is obtained from aluminum plant, dried, ground to 2mm sieve, and contains iron and aluminum oxide over 50% and SiO with total content of more than 20% 2 And CaO. The caustic sludge is provided by cleaning company in Henan, oven-dried, and ground to 2mm sieve, and contains calcium salts such as calcium carbonate and calcium sulfate as main ingredients, CaO content more than 60%, and SO 3 And SiO 2 The total content is up to 20 percent. The XRF is utilized to detect the chemical component content of the red mud, the alkaline residue and the slag adopted by the invention, and the specific detection results are shown in the following table:
TABLE 1 Red mud chemical composition
Figure BDA0003715283330000031
TABLE 2 alkaline residue chemistry
Figure BDA0003715283330000032
TABLE 3 slag chemistry
Figure BDA0003715283330000041
Example 1:
a method for solidifying heavy metal copper polluted soil sequentially comprises the following steps:
(1) weighing a certain amount of red mud, slag micro powder and alkaline residue according to the mixing proportion, grinding until the red mud, slag micro powder and alkaline residue can pass through a 2mm sieve, drying the red mud and slag micro powder at 105 ℃, drying the alkaline residue at 60 ℃, and then uniformly mixing the curing agent according to 60% of the slag micro powder, 20% of the red mud and 20% of the alkaline residue.
(2) And (2) weighing a certain amount of polluted soil, grinding the polluted soil into fine particles which can pass through a 2mm sieve, mixing the fine particles with the curing agent uniformly mixed in the step (1), and uniformly stirring, wherein the proportion of the curing agent is 15% of the mass of the whole soil sample.
(3) And adjusting the water content of the soil sample to reach 18-23%, fully and uniformly mixing, and then curing for 7-28 days to achieve the aim of curing the heavy metal polluted soil. FIG. 1 is a comparative diagram of analysis of unconfined compressive strength data of soil samples maintained for 7d, 14d and 28d, wherein the unconfined compressive strength data of the soil samples maintained for 7d after curing are 591, 610, 727, 463 and 411kPa respectively after different copper concentrations (0, 0.2%, 0.5%, 1% and 2%) are cured, the compressive strength is continuously enhanced with age, the unconfined compressive strength of the soil samples after curing, which is required by the US EPA, is required to reach 350kPa, as shown in FIG. 2, the copper ion concentration in the cured copper polluted soil leachate is shown, and it can be seen from the diagram that after the leachate is cured by the curing agent under different initial copper concentrations (0.2%, 0.5%, 1% and 2%), the copper concentration in the leachate is 7.08, 22.51, 31.65 and 60.35mg/kg respectively, and the leaching rate is 99% and is far below the standard limit value of 100 mg/kg.
Example 2:
a method for solidifying heavy metal copper polluted soil sequentially comprises the following steps:
(1) drying and screening industrial solid waste red mud and slag at 105 ℃, and drying and screening alkaline residue at 60 ℃;
(2) the industrial solid waste is sieved by a 2mm sieve, the mixture ratio of the red mud to the alkaline residue is 20 percent, the alkaline residue to the slag is 50 percent, and the total amount of the curing agent is 15 percent of the total soil sample content and is added and mixed evenly to obtain a compound A;
(3) drying the heavy metal polluted soil body to be repaired at 105 ℃, and sieving the soil body with a 2mm sieve;
(4) adding the mixed curing agent A uniformly mixed according to the proportion into the soil sample obtained in the step (3), and uniformly mixing to obtain a compound B;
(5) adjusting the water content of the compound B to enable the water content of the compound B to reach 18% -23% to obtain a compound C;
(6) preparing the compound C into a soil sample according to a static pressure method, placing and maintaining the soil sample for a certain age, taking out the soil sample to obtain a soil body which can be reused, and effectively sealing and storing the copper element. The concentration of copper ions in the solidified copper polluted soil leachate is shown in figure 2, after solidification is carried out by a solidifying agent under different initial copper concentrations (0.2%, 0.5%, 1% and 2%), the concentration of copper in the leachate is respectively 6.62, 13.59, 20.05 and 44.56mg/kg, the leaching rate reaches 99% and is far lower than the standard limit value of 100mg/kg, and the solidification effect of solidifying the heavy metal polluted soil by compounding the solidifying agent red mud, alkali slag and slag is very good.
Example 3
A method for solidifying heavy metal copper polluted soil sequentially comprises the following steps:
(1) drying and screening industrial solid waste red mud and slag at 105 ℃, and drying and screening alkaline residue at 60 ℃;
(2) the industrial solid waste is sieved by a 2mm sieve, the mixture ratio of the slag micro powder to the red mud is 50 percent, the alkali slag is 20 percent, the mixture ratio of the slag micro powder to the red mud is evenly mixed, and the total amount of the curing agent is added according to 15 percent of the total soil sample content and evenly mixed to obtain a compound A;
(3) drying the heavy metal polluted soil body to be repaired at 105 ℃, and sieving the soil body with a 2mm sieve;
(4) adding the mixed curing agent A uniformly mixed according to the proportion into the soil sample obtained in the step (3), and uniformly mixing to obtain a compound B;
(5) adjusting the water content of the compound B to enable the water content of the compound B to reach 18% -23% to obtain a compound C;
(6) preparing the compound C into a soil sample according to a static pressure method, placing and maintaining the soil sample for a certain age, taking out the soil sample to obtain a soil body which can be reused, and effectively sealing and storing the copper element. The concentration of copper ions in the solidified copper polluted soil leachate is shown in figure 2, after curing and maintenance are carried out for 28 days by using a curing agent under different initial copper concentrations (0.2%, 0.5%, 1% and 2%), the copper concentrations in the leachate are respectively 7.59, 16.41, 27.58 and 53.49mg/kg, and the leaching rate reaches 99% and is far lower than the standard limit value of 100 mg/kg.
Example 4
A method for solidifying heavy metal copper polluted soil sequentially comprises the following steps:
(1) drying and screening industrial solid waste red mud and slag at 105 ℃, and drying and screening alkaline slag at 60 ℃;
(2) the industrial solid waste is sieved by a 2mm sieve, the mixture ratio of the slag micro powder to the red mud is 50 percent, the alkali slag is 25 percent, the mixture ratio of the slag micro powder to the red mud is uniformly mixed, and the total amount of the curing agent is added according to 15 percent of the total soil sample content and is uniformly mixed to obtain a compound A;
(3) drying the heavy metal polluted soil body to be repaired at 105 ℃, and sieving the soil body with a 2mm sieve;
(4) adding the mixed curing agent A uniformly mixed according to the proportion into the soil sample obtained in the step (3), and uniformly mixing to obtain a compound B;
(5) adjusting the water content of the compound B to enable the water content of the compound B to reach 18% -23% to obtain a compound C;
(6) preparing the compound C into a soil sample according to a static pressure method, placing and maintaining the soil sample for a certain age, taking out the soil sample to obtain a soil body which can be reused, and effectively sealing and storing the copper element. The concentration of copper ions in the solidified copper polluted soil leachate is shown in figure 2, after curing maintenance is carried out for 28 days by using a curing agent under different initial copper concentrations (0.2%, 0.5%, 1% and 2%), the copper concentrations in the leachate are respectively 6.67, 11.02, 28.28 and 55.47mg/kg, and the leaching rate reaches 99% and is far lower than the standard limit value of 100 mg/kg.
Example 5
A method for solidifying heavy metal copper polluted soil sequentially comprises the following steps:
(1) drying and screening industrial solid waste red mud and slag at 105 ℃, and drying and screening alkaline slag at 60 ℃;
(2) uniformly sieving industrial solid waste by a 2mm sieve, uniformly mixing the three materials according to the mixing proportion of 55 percent of slag micro powder, 20 percent of red mud and 25 percent of alkaline residue, and uniformly adding the total amount of a curing agent according to 15 percent of the content of the whole soil sample and mixing to obtain a compound A;
(3) drying the heavy metal polluted soil body to be repaired at 105 ℃, and sieving the soil body with a 2mm sieve;
(4) adding the mixed curing agent A uniformly mixed according to the proportion into the soil sample obtained in the step (3), and uniformly mixing to obtain a compound B;
(5) adjusting the water content of the compound B to enable the water content of the compound B to reach 18% -23% to obtain a compound C;
(6) preparing the compound C into a soil sample according to a static pressure method, placing and maintaining the soil sample for a certain age, taking out the soil sample to obtain a soil body which can be reused, and effectively sealing and storing the copper element. The concentration of copper ions in the solidified leaching solution of the copper-polluted soil is shown in figure 2, after curing and maintenance are carried out for 28 days by using a curing agent under different initial copper concentrations (0.2%, 0.5%, 1% and 2%), the copper concentrations in the leaching solution are respectively 8.15, 13.55, 30.27 and 57.39mg/kg, and the leaching rate reaches 99% and is far lower than the standard limit value of 100 mg/kg.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims (9)

1. A novel curing agent for curing heavy metal copper polluted soil is characterized in that: the red mud-alkali slag-resistant red mud-alkali slag-resistant slag-alkali slag-resistant red mud-alkali slag-resistant red mud-alkali slag composite material comprises, by mass, 20% -30% of red mud, 20% -30% of alkali slag and 50% -60% of slag.
2. The novel curing agent for curing heavy metal copper contaminated soil according to claim 1, wherein: the caustic sludge is industrial waste residue generated in the soda industry, the main components of the caustic sludge exist in the form of calcium salts such as calcium carbonate and calcium sulfate, the CaO content exceeds 60% according to the mass percentage, and the SO content is higher than that of the caustic sludge 3 And SiO 2 The total content is up to 20 percent, and the Cl content is up to 10 percent.
3. The novel curing agent for curing heavy metal copper contaminated soil according to claim 1, wherein: the slag mainly comprises silicate and aluminosilicate melt, and CaO and SiO are calculated according to mass percentage 2 And Al 2 O 3 Total mass of the product is overAnd (4) passing through 85%.
4. The novel curing agent for curing heavy metal copper contaminated soil according to claim 1, wherein: the red mud is industrial waste residue generated in the aluminum production industry, and mainly comprises the following chemical components in percentage by mass: more than 50% of iron and aluminum oxides and more than 20% of SiO in total 2 And CaO, wherein the iron and aluminum oxides are mainly Fe 2 O 3 And Al 2 O 3 。
5. The use method of the novel curing agent for curing heavy metal copper contaminated soil according to any one of claims 1 to 4, wherein: the method comprises the following steps:
(1) drying and screening the red mud, the slag and the alkaline residue, and mixing the materials according to a certain mass ratio to obtain the curing agent;
(2) adding the obtained curing agent into a soil sample to be treated according to a certain amount, uniformly mixing, performing compaction treatment to prepare a soil sample, and placing and maintaining the soil sample for a certain age.
6. The use method of the novel curing agent for curing heavy metal copper contaminated soil according to claim 5, wherein: in the step (1), the particle sizes of the screened caustic sludge, slag and red mud are all less than 2 mm.
7. The use method of the novel curing agent for curing heavy metal copper contaminated soil according to claim 5, wherein: in the step (2), the addition amount of the curing agent accounts for 10-30% of the soil sample to be treated.
8. The use method of the novel curing agent for curing heavy metal copper contaminated soil according to claim 5, wherein: in the step (2), the water content of the soil sample to be treated is adjusted to 18-23% and then compacted.
9. The use method of the novel curing agent for curing heavy metal copper contaminated soil according to claim 5, wherein: in the step (2), the soil sample after being maintained for 7-28 days can be used as roadbed filling or natural soil.
CN202210735672.1A 2022-06-27 2022-06-27 Novel curing agent for curing heavy metal copper polluted soil and use method thereof Pending CN114989828A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102899048A (en) * 2012-09-29 2013-01-30 浙江大学宁波理工学院 Flue gas desulphuration gypsum-alkaline residue soil stabilizer
CN103242849A (en) * 2013-05-17 2013-08-14 中国科学院南京土壤研究所 Comprehensive conditioner for restoring acid soil polluted by copper and cadmium and preparation method of comprehensive conditioner
CN108192633A (en) * 2017-12-28 2018-06-22 武汉都市环保工程技术股份有限公司 A kind of heavy-metal composite pollution soil remediation material and restorative procedure based on alkaline residue
CN113549463A (en) * 2021-07-20 2021-10-26 安徽省城建基础工程有限公司 Curing agent for repairing heavy metal polluted soil and application thereof
CN114644929A (en) * 2020-12-17 2022-06-21 湖北工业大学 Novel composite curing agent for heavy metal Cd-polluted soil and use method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102899048A (en) * 2012-09-29 2013-01-30 浙江大学宁波理工学院 Flue gas desulphuration gypsum-alkaline residue soil stabilizer
CN103242849A (en) * 2013-05-17 2013-08-14 中国科学院南京土壤研究所 Comprehensive conditioner for restoring acid soil polluted by copper and cadmium and preparation method of comprehensive conditioner
CN108192633A (en) * 2017-12-28 2018-06-22 武汉都市环保工程技术股份有限公司 A kind of heavy-metal composite pollution soil remediation material and restorative procedure based on alkaline residue
CN114644929A (en) * 2020-12-17 2022-06-21 湖北工业大学 Novel composite curing agent for heavy metal Cd-polluted soil and use method thereof
CN113549463A (en) * 2021-07-20 2021-10-26 安徽省城建基础工程有限公司 Curing agent for repairing heavy metal polluted soil and application thereof

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