KR101777950B1 - Solidification/stabilization method of heavy metal in soil - Google Patents
Solidification/stabilization method of heavy metal in soil Download PDFInfo
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- KR101777950B1 KR101777950B1 KR1020160022114A KR20160022114A KR101777950B1 KR 101777950 B1 KR101777950 B1 KR 101777950B1 KR 1020160022114 A KR1020160022114 A KR 1020160022114A KR 20160022114 A KR20160022114 A KR 20160022114A KR 101777950 B1 KR101777950 B1 KR 101777950B1
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- slag
- soil
- carbon dioxide
- water
- mixed
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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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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
Abstract
The method of solidifying heavy metals in soil according to the present invention comprises mixing water and carbon dioxide into a slag containing at least one of blast furnace slag and ladle slag and mixing the slag with water and carbon dioxide- And soil.
Description
The present invention relates to a method for solidifying / stabilizing heavy metals, and more particularly to a method for solidifying / stabilizing heavy metals in soil.
Due to the rapid growth of economic growth and industrial activities in the past decades, Korea has been exposed to a large number of pollutants in the natural environment and accumulates them as a threat to public health. In particular, heavy metals in pollutants can move to people along the food chain while circulating the biosphere, and the environment contaminated by heavy metals is becoming a bigger problem. In particular, soil contaminated with heavy metals can be accompanied by contamination of groundwater, and treatment of heavy metals in soil is a very important problem.
As a method for treating contaminants in the soil, there is a soil washing method in which the soil is purified by dissolving the contaminants to the outside. The soil washing method has an advantage that it can be applied to various pollutants, but it has a disadvantage that it is difficult to apply to a large scale soil and it is expensive. Another method for treating contaminated soils is to solidify / stabilize so that contaminants in the soil do not leak into the surrounding environment.
The solidification / stabilization method stabilizes the pollutants chemically by using stabilization to reduce the fluidity, toxicity and solubility, stabilizes the pollutants through the solidifying agent, solidifies them in the non-solidified state, and physically blocks the dissolution of the pollutants. . The solidification / stabilization method can limit the behavior of pollutants in the soil, and it is recognized as a very useful method because it can treat a wide range of contaminated soil with a short treatment period and low cost. However, until now, There is a lack of methods for solids / stabilization.
Therefore, further studies on solidification / stabilization method of heavy metals in soils that can solidify / stabilize heavy metal ions in soil more efficiently are needed.
It is an object of the present invention to provide a solidification / stabilization method of heavy metals in soil which can solidify / stabilize heavy metals with excellent efficiency.
A method for solidification / stabilization of heavy metals in the soil for one purpose of the present invention comprises mixing water and carbon dioxide into a slag comprising at least one of a blast furnace slag and a laddle slag And mixing the slag and the soil mixed with the water and the carbon dioxide.
In one embodiment, the heavy metal may include at least one of As, Pb, Cd, Cr, Cu, and Ni.
In one embodiment, the mixing of the slag with water and carbon dioxide may be carried out at a temperature of from 1 占 폚 to 40 占 폚 and a pressure of from 1 bar to 10 bar.
In one embodiment, in mixing water and carbon dioxide into the slag, the water and the slag may be mixed in a volume ratio of 1: 0.3 to 1: 1.
In one embodiment, 30 to 100 parts by weight of slag mixed with water and carbon dioxide may be mixed with 100 parts by weight of the soil in the mixing of the slag and the soil mixed with the water and the carbon dioxide.
According to the solidification / stabilization method for heavy metals in the soil of the present invention, it is possible to solidify and stabilize heavy metal ions in soil contaminated with heavy metals by using blast furnace slag, ladle slag, or a mixture thereof. In addition, by solidifying and stabilizing the heavy metal ions in the soil, the release of heavy metal ions from the soil can be suppressed. In addition, since industrial by-products such as blast furnace slag and ladle slag are used for solidifying / stabilizing the heavy metals in the soil, it is possible to solidify and stabilize heavy metals in the soil environmentally and economically.
1 is a view for explaining a solidification / stabilization method of heavy metals in soil according to the present invention.
FIG. 2 is a view for explaining solidification / stabilization efficiency of heavy metals in soil according to embodiments of the present invention. FIG.
3 is a view for explaining solidification / stabilization efficiency of heavy metals in soil according to comparative examples of the present invention.
4 is a view for explaining solidification / stabilization efficiency of heavy metals in soil according to embodiments of the present invention.
5 is a view for explaining solidification / stabilization efficiency of heavy metals in soil according to comparative examples of the present invention.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention is capable of various modifications and various forms, and specific embodiments are illustrated in the drawings and described in detail in the text. It is to be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but on the contrary, is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. Like reference numerals are used for like elements in describing each drawing.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the term "comprises" or "having ", etc. is intended to specify that there is a feature, step, operation, element, part or combination thereof described in the specification, , &Quot; an ", " an ", " an "
Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.
1 is a view for explaining a solidification / stabilization method of heavy metals in soil according to the present invention.
1, a solidification / stabilization method for solidification of soil according to the present invention is a solidification / stabilization method in which a slag containing at least one of a blast furnace slag and a ladle slag is filled with water and / Carbon dioxide is mixed (step S110).
At this time, the slag can be mixed with water and carbon dioxide at a temperature of 1 to 40 DEG C and a pressure of 1 to 10 bar, and the water and the slag can be mixed in a volume ratio of 1: 0.3 to 1: 1 .
Generally, a slag is a mixture of an acidic oxide and a basic oxide, and refers to a non-ferrous metal material produced by the action of a solvent when iron is dissolved. Slag is also referred to as a by-product of the steel industry and contains a large amount of calcium oxide (CaO), silica (SiO 2 ), aluminum oxide (Al 2 O 3 ) and the like. Blast furnace slag is a slag generated when forming pig iron from an iron ore in a blast furnace, and ladle slag is a slag generated when a steel is manufactured by refining pig iron, scrap iron, etc., and is also referred to as steel making slag.
For example, water may be mixed with slag containing blast furnace slag, ladle slag, or a mixture thereof, and carbon dioxide may be injected to form slag mixed with water and carbon dioxide. At this time, the slag mixed with water and carbon dioxide may be a slag containing carbonate (CaCO 3 ) with fixed carbon dioxide.
Then, the slag mixed with the water and the carbon dioxide is mixed with the soil to solidify / stabilize the heavy metal in the soil (step S120).
The heavy metal in the soil may include at least one of arsenic (As), lead (Pb), cadmium (Cd), chromium (Cr), copper (Cu), and nickel (Ni).
At this time, 30 to 100 parts by weight of slag mixed with water and carbon dioxide may be mixed with 100 parts by weight of the soil.
Solidification / stabilization of heavy metals is a method of physically and chemically stabilizing heavy metals mixed with non-solid heavy metals by mixing solid materials and inhibiting heavy metal leaching. According to the solidification / stabilization method for heavy metals in the soil of the present invention, heavy metals in contaminated soil can be efficiently stabilized and solidified using slag mixed with water and carbon dioxide as the solidifying / stabilizing agent. Concretely, when the slag mixed with water and carbon dioxide is mixed with the contaminated soil, the pH of the contaminated soil is increased, thereby increasing the soil adsorption of heavy metal ions in the contaminated soil, or forming a heavy metal ion hydroxide or insoluble salt So that the heavy metal ions in the contaminated soil can be efficiently solidified / stabilized.
According to the solidification / stabilization method for heavy metals in the soil of the present invention, since the blast furnace slag and ladle slag, which are industrial by-products, are used to solidify / stabilize heavy metals in contaminated soil, it is possible to treat heavy metal ions in the soil economically and environmentally .
In addition, the heavy metal may be solidified / stabilized and used as an aggregate.
Hereinafter, the method for solidifying / stabilizing heavy metals in the soil of the present invention will be described in more detail with reference to the following examples.
In order to confirm the solidification / stabilization of heavy metals in the soil according to Examples 1 to 3 of the present invention, 25 g of BOF slag was mixed with 20 mL of distilled water and placed in the reactor. Then, carbon dioxide was injected into the reactor to form blast furnace slag (hereinafter referred to as slag 1) treated with distilled water and carbon dioxide. Next, 0.3 g, 0.6 g and 1.0 g of the slag 1 were added to 1 g of contaminated soil containing lead, cadmium, chromium, copper and nickel, respectively, and mixed uniformly. Thereafter, the water content was adjusted to 50% and the reaction was conducted for 1 day to perform heavy metal solidification / stabilization in the soil according to Examples 1 to 3 of the present invention.
The level of solidification / stabilization of heavy metals in the soil was evaluated by TCLP (US EPA, Method SW846, # 1311) method, which is the dissolution test method of US EPA. The dissolution test method (hereinafter referred to as TCLP) of US and EPA was carried out according to the pH of the sample. When the pH was 5 or more, 5.7 mL of 0.1 M (6 g / L) glacial acetic acid (CH 3 COOH) The solution dissolved in distilled water was injected at a ratio of 1:20 with the sample, and eluted with a tumbler at 200 rpm for 18 hours at room temperature. If the pH is less than 5, add 5.7 mL of glacial acetic acid to 500 mL of distilled water, add 64 mL of 1 M NaOH, dilute 1 L of the solution with the sample at a weight ratio of 1:20, And eluted with stirring. The results are shown in Fig.
FIG. 2 is a view for explaining solidification / stabilization efficiency of heavy metals in soil according to embodiments of the present invention. FIG.
In FIG. 2, "TCLP" represents the TCLP standard, "Control" represents mine tailing as a control group, and "Slag 1" represents blast furnace slag mixed with water and carbon dioxide.
Also, solidification / stabilization of heavy metals in the soil according to Comparative Examples 1 to 3 was carried out in substantially the same manner as in Examples 1 to 3, except that the blast furnace slag was not treated with carbon dioxide. The results are shown in Fig.
3 is a view for explaining solidification / stabilization efficiency of heavy metals in soil according to comparative examples of the present invention.
In FIG. 3, "TCLP" represents a TCLP standard, "Control" represents a light mass as a control group, and "Comparative Slag 1" represents a blast furnace slag in which carbon dioxide is not mixed.
2 and 3 together show that the degree of heavy metal elution when 0.3 g, 0.6 g and 1.0 g of slag 1 were added, respectively, showed that when 0.3 g, 0.6 g and 1.0 g of the comparative slag 1 were added, Which is lower than the elution degree. The solidification / stabilization degree of heavy metal in the case of mixing the slag 1 with the soil is better than the case of mixing the slag 1 with the soil.
Specifically, arsenic and nickel were not eluted in the soil mixed with the slag 1 according to Examples 1 to 3 of the present invention, whereas in the soil in which the comparative slag 1 was mixed according to Comparative Examples 1 to 3, the arsenic content was very high As shown in Fig. In addition, according to Examples 1 to 3 of the present invention, it is confirmed that the degree of lead, chromium, and cadmium elution from the soil mixed with slag 1 is low. Copper was partially eluted, but it was lower than that of the control group, Tumi, and the overall degree of leaching of heavy metals was remarkably decreased.
That is, according to Examples 1 to 3 of the present invention, the leaching of heavy metals in the case of mixing the slag 1 with the soil is excellent, which is excellent in the solidification / stabilization efficiency of heavy metals in the soil according to Examples 1 to 3 of the present invention it means.
In addition, according to Example 1 of the present invention, it can be confirmed that even when 0.3 g of slag 1 and 1.0 g of heavy metal contaminated soil are mixed, the heavy metal elution from the soil is suppressed well.
Therefore, it can be confirmed that the heavy metal can be solidified / stabilized with excellent efficiency even if a slag mixed with a small amount of water and carbon dioxide is used according to the present invention.
Next, in order to confirm the solidification / stabilization of heavy metals in the soil according to Examples 4 to 6 of the present invention, in substantially the same manner as in Examples 1 to 3 except for using ladle slag, Solidification / stabilization of heavy metals in the soil according to Examples 1 to 3 was carried out and its efficiency was confirmed using TCLP. The results are shown in Fig.
4 is a view for explaining solidification / stabilization efficiency of heavy metals in soil according to embodiments of the present invention.
In Fig. 4, "TCLP" represents the TCLP standard, "Control" represents the mine tailing which is the control group, and "Slag 2" represents the ladle slag mixed with water and carbon dioxide.
In addition, solidification / stabilization of heavy metals was carried out substantially the same as solidification / stabilization of heavy metals in the soil according to Comparative Examples 1 to 3 except for using ladle slag, and efficiency was confirmed by using TCLP. The results are shown in Fig.
5 is a view for explaining solidification / stabilization efficiency of heavy metals in soil according to comparative examples of the present invention.
In FIG. 5, "TCLP" represents a TCLP standard, "Control" represents a light mass as a control group, and "Comparative Slag 2" represents a ladle slag in which carbon dioxide is not mixed.
4 and 5, the comparative slag 2 according to Examples 4 to 6 of the present invention, to which 0.3 g, 0.6 g and 1.0 g of slag 2 were added, respectively, was 0.3 g, 0.6 g, And Comparative Examples 4 to 6 in which 1.0 g was added. That is, it can be confirmed that the solidification / stabilization efficiency of heavy metals in soil according to Examples 4 to 6 of the present invention is excellent.
Specifically, arsenic, copper, and nickel were not eluted in the soil mixed with slag 2 according to Examples 4 to 6 of the present invention, whereas arsenic, copper, and nickel were not eluted in the soil mixed with Comparative Slag 2 according to Comparative Examples 4 to 6 Copper was eluted and arsenic was eluted to a very high level. In addition, according to Examples 4 to 6 of the present invention, it can be confirmed that the soil obtained by mixing the slag 2 has a low degree of lead, chrome and cadmium dissolution.
According to Example 4 of the present invention, when 0.3 g of slag 2 and 1.0 g of soil are mixed, it is confirmed that the release of heavy metals from the soil is suppressed well, which means that a small amount of water and carbon dioxide It can be confirmed that it is possible to solidify / stabilize heavy metals with excellent efficiency even when mixed slag is used.
Thus, according to Examples 4 to 6 of the present invention, the leaching of heavy metals in the case of mixing the slag 2 with the soil was suppressed with excellent efficiency. Thus, the solidification / stabilization efficiency of heavy metals in the soil according to Examples 4 to 6 of the present invention Can be confirmed.
2 to 5, it can be confirmed that the leaching of heavy metals in the soil can be effectively suppressed according to Examples 1 to 6 of the present invention, that is, the heavy metal solidification / According to the stabilization method, it can be confirmed that excellent efficiency can solidify / stabilize the heavy metals in the soil.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims. It can be understood that it is possible.
Claims (5)
Mixing the slag and the soil mixed with the water and the carbon dioxide,
When the slag is blast furnace slag,
The slag mixed with water and carbon dioxide solidifies / stabilizes nickel (Ni) in the soil to exhibit improved nickel dissolution inhibition compared to soil treated with slag without carbon dioxide,
When the slag is ladle slag,
Characterized in that said water and carbon dioxide mixed slag solidify / stabilize copper (Cu) in said soil to exhibit improved copper dissolution inhibition over treatment of the soil with no carbon dioxide-treated ladle slag.
Methods of solidification / stabilization of heavy metals in soil.
Wherein the step of mixing water and carbon dioxide in the slag is carried out at a temperature of 1 to 40 DEG C and a pressure of 1 to 10 bar.
Solidification / stabilization of heavy metals in soil.
Mixing the slag with water and carbon dioxide, and pre-treating the slag,
Wherein the water and the slag are mixed in a volume ratio of 1: 0.3 to 1: 1.
Solidification / stabilization of heavy metals in soil.
In the step of mixing the slag and the soil mixed with the water and the carbon dioxide,
Wherein 30 to 100 parts by weight of the slag mixed with water and carbon dioxide is mixed with 100 parts by weight of the soil.
Solidification / stabilization of heavy metals in soil.
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| CN111040767A (en) * | 2018-10-15 | 2020-04-21 | 香港科技大学 | Soil conditioner, method for improving quality of medicinal plants, application of soil conditioner and method for planting medicinal plants |
| CN112779017B (en) * | 2020-12-31 | 2022-04-29 | 南京工业大学 | Heavy metal contaminated soil remediation agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000282034A (en) | 1999-03-31 | 2000-10-10 | Sumitomo Metal Ind Ltd | Method for preventing soil acidification and for stabilizing soil ph |
| KR101373800B1 (en) * | 2013-07-23 | 2014-03-18 | (주)신명건설기술공사 | Apparatus for producing calcium carbonate from slag and corbon dioxide |
| JP2014147912A (en) * | 2013-02-04 | 2014-08-21 | Nippon Steel & Sumitomo Metal | Method for insolubilizing poisonous metal in contaminated soil |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000282034A (en) | 1999-03-31 | 2000-10-10 | Sumitomo Metal Ind Ltd | Method for preventing soil acidification and for stabilizing soil ph |
| JP2014147912A (en) * | 2013-02-04 | 2014-08-21 | Nippon Steel & Sumitomo Metal | Method for insolubilizing poisonous metal in contaminated soil |
| KR101373800B1 (en) * | 2013-07-23 | 2014-03-18 | (주)신명건설기술공사 | Apparatus for producing calcium carbonate from slag and corbon dioxide |
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