CN112920807A - Heavy metal contaminated soil remediation material, preparation method thereof and remediation method of heavy metal contaminated soil - Google Patents
Heavy metal contaminated soil remediation material, preparation method thereof and remediation method of heavy metal contaminated soil Download PDFInfo
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- CN112920807A CN112920807A CN202110147853.8A CN202110147853A CN112920807A CN 112920807 A CN112920807 A CN 112920807A CN 202110147853 A CN202110147853 A CN 202110147853A CN 112920807 A CN112920807 A CN 112920807A
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- C09K17/00—Soil-conditioning materials or soil-stabilising materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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Abstract
The invention relates to the technical field of soil remediation, in particular to a heavy metal contaminated soil remediation material, a preparation method thereof and a heavy metal contaminated soil remediation method. The invention provides a heavy metal contaminated soil remediation material, which comprises the following components: a) an allosteric extension component and a passivation component in a weight ratio of (1:10) to (10:1), and b) a long-acting accelerating component accounting for 0.1-5% of the mass of the component a), wherein the allosteric extension component is at least one selected from the group consisting of a light-burned magnesite powder, hydrotalcite, sepiolite and attapulgite, and is anhydrous; the passivation component is selected from at least one of iron powder, magnetite and pyrolusite, and the surface of the passivation component is coated with phenolic substances containing plant sources; the long-acting promoting component is selected from at least one of blast furnace slag, steel slag and red mud. The material has good long-acting passivation efficiency. The invention also provides a preparation method of the repairing material and a repairing method of heavy metal contaminated soil.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a heavy metal contaminated soil remediation material, a preparation method thereof and a heavy metal contaminated soil remediation method.
Background
The soil pollution seriously threatens the functions, food safety and human living safety of an ecological system, and has the characteristics of concealment, hysteresis, accumulation and the like. Thus, soil contamination is more difficult to detect and administer than contamination with other environmental media.
Heavy metals are the most prominent pollutants in soil, and the pollution of the heavy metals in the soil is imperatively treated through science. However, the cause of heavy metal pollution of soil is complex, and the soil usually has the following characteristics: the coexistence and the large-scale distribution of a plurality of heavy metal pollutants into tablets seriously affect the environmental quality. In response to the multi-metal composite contaminated soil, the development of a novel material which is easy to prepare, economical and green and can play a long-acting repairing role is urgently needed, so that the reasonable resistance control of the migration risk of the soil pollutants is realized.
Solidification/stabilization is the most common technology for soil heavy metal pollution remediation, but after the prior stabilizing materials such as portland cement, lime and the like are added into soil, the soil is cracked due to an aging process, particularly a rainfall dry-wet cycle process, so that the heavy metal migration is increased and the remediation is ineffective. Moreover, the passivation material commonly used at present is difficult to realize long-acting passivation, and the passivation capability is easily influenced by the environment. In addition, the remediation agent for the polluted soil generally aims at single heavy metal, and the high-efficiency remediation of the soil polluted by various heavy metals is difficult to realize.
Disclosure of Invention
Based on the above, the invention provides a heavy metal contaminated soil remediation material, and a preparation method and application thereof. The repair material provided by the invention can effectively prevent the problem that various heavy metal pollutants are easy to migrate in aging processes such as rainfall dry-wet cycle and the like, and has a long-acting stabilization repair effect.
In one aspect of the present invention, there is provided a heavy metal contaminated soil remediation material, comprising:
a) an allosteric extension component and a passivation component in a weight ratio of (1:10) to (10:1), and
b) a long-acting promoting component accounting for 0.1-5% of the mass of the component a);
the allosteric extension component is selected from at least one of light-burned magnesite powder, hydrotalcite, sepiolite and attapulgite, and is anhydrous;
the passivation component is selected from at least one of iron powder, magnetite and pyrolusite, and the surface of the passivation component is coated with phenolic substances containing plant sources;
the long-acting promoting component is selected from at least one of blast furnace slag, steel slag and red mud.
In some embodiments, the material surface-coated by the inactivating component is a dry component of an aqueous extract of the plant.
In some embodiments, the subjecting of the calcined magnesite powder, the hydrotalcite, the sepiolite and the attapulgite to the anhydrous treatment is performed at 180 to 550 ℃ for 30 to 120min under a non-oxidizing atmosphere.
In some embodiments, the hydrotalcite is selected from at least one of iron-magnesium hydrotalcite, iron-aluminum hydrotalcite, aluminum-magnesium hydrotalcite, calcium-aluminum hydrotalcite, calcium-magnesium hydrotalcite, and calcium-iron hydrotalcite.
In some embodiments, the particle size of the sepiolite, attapulgite, and passivating component is independently selected from 100 mesh or less.
The invention also provides a preparation method of the heavy metal contaminated soil remediation material, which comprises the following steps:
mixing the allosteric extension component, the passivation component and the long-acting acceleration component.
In some embodiments, when the allosteric extension component is a soft-burned magnesite powder, the step of calcining the magnesite powder at 800 ℃ to 1050 ℃ is further included before the step of mixing the allosteric extension component, the passivating component and the long-acting accelerating component.
In some embodiments, the method of preparing the passivating component includes:
mixing the plant protection solution and at least one of iron powder, magnetite and pyrolusite according to a solid-liquid ratio of 1: (50-500) mixing, filtering and drying;
the preparation method of the plant protection solution comprises the following steps:
pulverizing pericarp and/or leaf to obtain pulverized material; and
mixing the crushed material with water at 40-90 ℃ according to a solid-liquid ratio of 1: (10-100) mixing and filtering to prepare the plant protection solution.
Further, the drying method can adopt a vacuum oven to dry at 100-110 ℃.
In another aspect of the present invention, there is further provided a method for remedying heavy metal contaminated soil, comprising the following steps:
and adding the heavy metal contaminated soil remediation material to the contaminated soil to be remediated, and adding water for mixing.
In some embodiments, the addition amount of the heavy metal contaminated soil remediation material is 0.2 to 8 percent of the weight of the contaminated soil to be remediated, and the addition amount of water is 10 to 50 percent of the weight of the contaminated soil to be remediated.
In some embodiments, the heavy metal in the contaminated soil is at least one of Cr, Mn, Cu, Zn, As, Cd, and Pb.
Has the advantages that:
researches show that the traditional passivation component can dissolve out heavy metals contained in the traditional passivation component when directly added into soil because the surface of the traditional passivation component is often adsorbed with heavy metal impurities such as arsenic, lead, copper and the like, and is not beneficial to long-acting passivation. If water washing is used, the surface of the passivation component is oxidized, resulting in a reduction in passivation ability. The invention uses the passivation component wrapped with plant-derived phenolic substances to lead the passivation component to achieve the effect of long-acting passivation.
And light-burned magnesite powder, hydrotalcite, sepiolite or attapulgite and the like are selected as allosteric extension components which can absorb water in the rainfall process and have good ductility or have an expansion effect, so that the healing of soil cracks can be realized, and the heavy metal migration process caused by the cracks generated in the polluted soil in the rainfall process can be restrained by matching with the passivation component coated with the plant-derived phenolic substance, so that the long-acting passivation of various heavy metals is realized. The artificial accelerated aging test proves that the heavy metal contaminated soil remediation material provided by the invention can enable the remediation and stabilization effects of the contaminated soil to reach more than one hundred years.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic view of the present invention for repairing heavy metal contaminated soil using a heavy metal contaminated soil repairing material;
FIG. 2 is a graph of the MgO activity versus the calcination temperature of magnesite powder according to an embodiment of the present invention;
FIG. 3 is a scanning electron microscope image of the iron-magnesium hydrotalcite before and after anhydrous treatment in one embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. In fact, 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 scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one aspect of the present invention, there is provided a heavy metal contaminated soil remediation material, comprising:
a) an allosteric extension component and a passivation component in a weight ratio of (1:10) to (10:1), and
b) a long-acting promoting component accounting for 0.1-5% of the mass of the component a);
wherein the allosteric extension component is selected from at least one of light-burned magnesite powder, hydrotalcite, sepiolite and attapulgite, and is anhydrous;
the passivation component is selected from at least one of iron powder, magnetite and pyrolusite, and the surface of the passivation component is coated with phenolic substances containing plant sources;
the long-acting promoting component is selected from at least one of blast furnace slag, steel slag and red mud.
The invention uses the passivation component wrapped with plant-derived phenolic substances to lead the passivation component to achieve the effect of long-acting passivation.
And light-burned magnesite powder, hydrotalcite, sepiolite or attapulgite and the like are selected as allosteric extension components which can absorb water in the rainfall process and have good ductility or have an expansion effect, so that the healing of soil cracks can be realized, and the heavy metal migration process caused by the cracks generated in the polluted soil in the rainfall process can be restrained by matching with the passivation component coated with the plant-derived phenolic substance, so that the long-acting passivation of various heavy metals is realized. The artificial accelerated aging test proves that the heavy metal contaminated soil remediation material provided by the invention can enable the remediation and stabilization effects of the contaminated soil to reach more than one hundred years.
The magnesite mainly comprises magnesium carbonate minerals, the calcined magnesite powder mainly comprises magnesium oxide, and the magnesium oxide can generate hydration reaction when meeting water to produce a magnesium hydroxide sheet structure, so that the magnesium carbonate powder has good ductility and can enhance the healing capacity of soil cracks.
The hydrotalcite has good memory effect, can be recovered into a sheet structure when meeting water, and has good ductility, so that the healing capacity of soil cracks is enhanced.
After the sepiolite and the attapulgite absorb water, slippage can occur between layers, so that the expansion effect is achieved, soil cracks are adhered, and healing of the soil cracks is promoted.
The blast furnace slag is mainly derived from industrial slag, such as slag generated in iron smelting or steel making processes. The main component of blast furnace slag is alumina (Al)2O3) Silicon dioxide (SiO)2) Magnesium oxide (MgO), calcium oxide (CaO), sodium oxide (Na)2O), potassium oxide (K)2O), iron oxide (FeO) and sulfur trioxide (SO)3)。
The steel slag belongs to a byproduct generated in an industrial process. The steel slag can be electric furnace steel slag, open-hearth steel slag or converter steel slag. The steel slag mainly contains iron, calcium oxide (CaO), magnesium oxide (MgO), manganese oxide (MnO) and the like.
The red mud also belongs to a byproduct generated in an industrial process, and is mainly derived from wastes after bauxite smelting. The red mud mainly contains iron oxide (Fe)2O3) Alumina (Al)2O3) Silicon dioxide (SiO)2) And calcium oxide (CaO).
Inorganic long-chain polymer structures such as-Si-O-Si-O-, -Si-O-Al-O-, -Fe-O-Si-O-Al-O-and the like can be formed between the long-acting promoting components such as the blast furnace waste residue, the steel slag, the red mud and the like and between the long-acting promoting components and the passivating components, so that heavy metals can be wrapped, and the long-acting passivation of the heavy metals is further promoted.
In some embodiments, the material surface-coated with the inactivating component is a dried component of an aqueous extract of the plant.
In some embodiments, the non-aqueous treatment of the calcined magnesite powder, the hydrotalcite, the sepiolite and the attapulgite is carried out under a non-oxidizing atmosphere at 180 ℃ to 550 ℃ for 30min to 120 min.
Further, a specific method of the anhydrous treatment is a heat activation treatment. The original water in the materials is removed through thermal activation treatment, so that excessive water absorption before the materials are added into soil is prevented, and the healing effect of soil cracks is reduced.
In some embodiments, the hydrotalcite is selected from at least one of iron-magnesium hydrotalcite, iron-aluminum hydrotalcite, aluminum-magnesium hydrotalcite, calcium-aluminum hydrotalcite, calcium-magnesium hydrotalcite, and calcium-iron hydrotalcite. In a preferred embodiment, the hydrotalcite is selected from iron magnesium hydrotalcites.
In some embodiments, the particle size of the sepiolite, attapulgite, and passivating component is independently selected from 100 mesh or less.
The invention also provides a preparation method of the heavy metal contaminated soil remediation material, which comprises the following steps:
mixing the allosteric extension component, the passivation component and the long-acting acceleration component.
In some embodiments, the allosteric extension component, passivating component, and long-term acceleration component are mixed using methods including, but not limited to, dry ball milling, ultrasonic dispersion, and the like, for a mixing time of 30min to 120 min.
In some embodiments, when the allosteric extension component is a soft-burned magnesite powder, the step of calcining the magnesite powder at 800 ℃ to 1050 ℃ is further included before the step of mixing the allosteric extension component, the passivating component and the long-acting accelerating component.
The main component of magnesite is MgCO3After calcination, MgO is mainly produced. Different calcination temperatures will affect the activity of the resulting MgO, which is primarily referred to as its ability to undergo hydration reactions. The invention selects light-burned magnesite powder as an allosteric extension component, and needs good ductility, so that the calcination temperature needs to be controlled, and the high activity of MgO in the calcined product is ensured.
In some embodiments, a method of preparing a passivating component includes:
mixing the plant protection solution and at least one of iron powder, magnetite and pyrolusite according to a solid-liquid ratio of 1: (50-500) mixing, filtering and drying;
the preparation method of the plant protection solution comprises the following steps:
pulverizing pericarp and/or leaf to obtain pulverized material; and
mixing the crushed material with water at 40-90 ℃ according to a solid-liquid ratio of 1: (10-100) mixing and filtering to prepare the plant protection solution.
In the present invention, as further illustration, the pericarp and/or leaves are mainly selected from plants with high content of phenolic substances such as tannin, flavone, etc., including but not limited to tea leaves, pine leaves, birch leaves, mulberry leaves, peach leaves, poplar leaves, banana peel, watermelon peel, apple peel, pear peel, grape peel, etc. Preferably, the pericarp is selected from at least one of banana peel and watermelon peel, and the leaf is selected from at least one of tea leaf, pine leaf and birch leaf, more preferably, the leaf is tea leaf.
In some embodiments, the peel and leaves are dry. Preferably, the particle size of the pulverized product is 5cm or less.
In another aspect of the present invention, there is further provided a method for remedying heavy metal contaminated soil, comprising the following steps:
and adding the heavy metal contaminated soil remediation material to the contaminated soil to be remediated, and adding water for mixing.
As shown in figure 1, after the repairing material provided by the invention is added into soil, a homogeneous inorganic net structure can be formed, and the heavy metal is stabilized through adsorption, wrapping and the like. Once the soil has cracks due to the action of rainfall, the moisture in the cracks can induce the destructural extension components such as light-burned magnesite powder, hydrotalcite, sepiolite, attapulgite and the like to extend, so that the cracks are filled, and the heavy metal is prevented from migrating to the external environment.
In some embodiments, the addition amount of the heavy metal contaminated soil remediation material is 0.2% -8% of the weight of the contaminated soil to be remediated, and the addition amount of water is 10% -50% of the weight of the contaminated soil to be remediated.
In some embodiments, the heavy metal in the contaminated soil is at least one of Cr, Mn, Cu, Zn, As, Cd, and Pb.
The heavy metal contaminated soil remediation material, the preparation method thereof, and the remediation method of heavy metal contaminated soil according to the present invention will be described in further detail below with reference to specific examples and comparative examples.
Example 1 preparation of heavy Metal contaminated soil remediation Material
(1) Determination of calcination temperature of magnesite powder
The activity of MgO, which is a calcined product of magnesite powder, is confirmed according to a titration method. The specific method comprises the following steps: 1g of magnesite powder at different calcination temperatures is added into 80ml of 0.25mol/L acetic acid solution, phenolphthalein is used as an indicator, and the time for the solution to change from colorless to red is used as a standard for judging the activity of MgO. As can be seen from FIG. 2, the MgO activity and the calcination temperature are in an exponential relationship, and the specific calcination temperature and MgO activity are shown in Table 1. From this result, it was found that the MgO activity was high when the time for the solution to change from colorless to red was 500 seconds or less.
TABLE 1 calcination temperature of magnesite powder and MgO reaction Activity
| Calcination temperature (. degree.C.) of magnesite powder | MgO reactivity (time to change color, s) |
| 850 | 150 |
| 950 | 247 |
| 1050 | 439 |
| 1150 | 818 |
(2) Preparation of plant protection liquid
The banana peel is rinsed with deionized water, naturally dried in the air and cut into 5 cm-sized fragments. Mixing the crushed banana peel and deionized water according to a solid-liquid ratio of 1:60, soaking at 80 ℃ for 90min, and filtering to obtain a first plant protection solution.
(3) Preparation of the passivating component
Soaking 100-mesh magnetite and a first plant protection solution at normal temperature for 30min according to a solid-to-liquid ratio of 1:50, filtering, and drying in a vacuum oven at 105 ℃ to obtain a passivation component;
(4) preparation of the allosteric extension component
Placing MgO prepared by calcining at 850 ℃ in the step (1) at 350 ℃, and introducing N2The muffle furnace is subjected to heat activation treatment for 2 hours.
(5) Preparation of heavy metal contaminated soil remediation material
The prepared allosteric extension component and passivation component are taken according to the weight ratio of 1:1 and placed in a ball mill, and blast furnace slag is added according to 1 percent of the total weight of the allosteric extension component and the passivation component for dry ball milling for 60 min.
Example 2
The preparation method of example 2 is substantially the same as that of example 1 except that: the preparation method of the allosteric extension component comprises the following steps:
placing MgO prepared by calcining at 950 ℃ at 350 ℃, and introducing N2The muffle furnace is subjected to heat activation treatment for 2 hours.
Example 3
The preparation of example 3 is essentially the same as example 1, except that: the preparation method of the allosteric extension component comprises the following steps:
placing MgO prepared by calcining at 1050 ℃ at 350 ℃, and introducing N2The muffle furnace is subjected to heat activation treatment for 2 hours.
Example 4
Example 4 was prepared essentially as in example 1, except that: the preparation method of the allosteric extension component comprises the following steps:
placing iron-magnesium hydrotalcite at 550 deg.C, and introducing N2The muffle furnace is subjected to heat activation treatment for 2 hours. FIG. 3 is an SEM image of iron-magnesium hydrotalcite before and after anhydrous treatment, and it can be seen that iron is present after anhydrous treatmentThe magnesium hydrotalcite is not in a sheet structure any more, which indicates that the moisture in the iron-magnesium hydrotalcite is successfully removed.
Example 5
The preparation of example 5 is essentially the same as example 1, except that: the preparation method of the allosteric extension component comprises the following steps:
placing sepiolite at 200 deg.C, and introducing N2The muffle furnace is subjected to heat activation treatment for 2 hours.
Example 6
Example 6 was prepared essentially as in example 1, except that: the preparation method of the allosteric extension component comprises the following steps:
respectively placing attapulgite at 200 deg.C, and introducing N2The muffle furnace is subjected to heat activation treatment for 2 hours.
Examples 7 to 12 were prepared substantially in the same manner as in example 1, except that: the allosteric extension components are different, and the preparation method of the plant protection solution and the preparation method of the passivation component are as follows:
(1) preparation of plant protection liquid
The green tea leaves are rinsed with deionized water, naturally air-dried and ground to obtain pieces of 1cm in size. Mixing the green tea fragments with deionized water at a solid-to-liquid ratio of 1:30, soaking at 60 deg.C for 60min, and filtering to obtain a second plant protection solution.
(2) Preparation of the passivating component
And (3) taking 100-mesh iron powder and a second plant protection solution, soaking for 90min at normal temperature according to the solid-to-liquid ratio of 1:40, filtering, and drying in a vacuum oven at 105 ℃ to obtain a second passivation component.
Comparative example 1
The preparation method of comparative example 1 is substantially the same as that of example 7 except that: no allosteric extension component was added.
Comparative example 2
The preparation method of comparative example 2 is substantially the same as that of example 7 except that: no passivation component was added.
Comparative example 3
The preparation method of comparative example 3 is substantially the same as that of example 7 except that: and adding iron powder which is not soaked in the second plant protection solution as a passivation component.
The compositions of examples 1 to 12 and comparative examples 1 to 3 are shown in Table 2.
TABLE 2 formulation composition of allosteric extension component and passivation component
| Allosteric extension component | Passivating component | |
| Example 1 | Anhydrous MgO obtained by calcination at 850 DEG C | Magnetite soaked in first plant protection solution |
| Example 2 | Anhydrous MgO obtained by calcination at 950 ℃ | Magnetite soaked in first plant protection solution |
| Example 3 | Anhydrous MgO obtained by calcination at 1050 deg.C | Magnetite soaked in first plant protection solution |
| Example 4 | Anhydrous iron-magnesium hydrotalcite | Magnetite soaked in first plant protection solution |
| Example 5 | Anhydrous sepiolite | Magnetite soaked in first plant protection solution |
| Example 6 | Anhydrous attapulgite | Magnetite soaked in first plant protection solution |
| Example 7 | Anhydrous MgO obtained by calcination at 850 DEG C | Iron powder soaked in the second plant protection solution |
| Example 8 | Anhydrous MgO obtained by calcination at 950 ℃ | Iron powder soaked in the second plant protection solution |
| Example 9 | Anhydrous MgO obtained by calcination at 1050 deg.C | Iron powder soaked in the second plant protection solution |
| Example 10 | Anhydrous iron-magnesium hydrotalcite | Iron powder soaked in the second plant protection solution |
| Example 11 | Anhydrous sepiolite | Iron powder soaked in the second plant protection solution |
| Example 12 | Anhydrous attapulgite | Iron powder soaked in the second plant protection solution |
| Comparative example 1 | / | Iron powder soaked in the second plant protection solution |
| Comparative example 2 | Anhydrous MgO obtained by calcination at 850 DEG C | / |
| Comparative example 3 | Anhydrous MgO obtained by calcination at 850 DEG C | Iron powder |
Examples 13 to 17 were prepared substantially the same as in example 7, except that: the long-acting promoting component is red mud, and the addition amount of the long-acting promoting component is 0.1 percent of the total weight of the allosteric extension component and the passivation component; the weight ratio of the allosteric extension component to the passivation component is 1:10, 1:5, 1:1, 5:1, 10:1, respectively.
Comparative example 4
The preparation method of comparative example 4 is substantially the same as that of example 14 except that: no allosteric extension component was added.
Comparative example 5
The preparation method of comparative example 5 is substantially the same as that of example 14 except that: no passivation component was added.
Comparative example 6
The preparation method of comparative example 6 is substantially the same as that of example 14 except that: and adding iron powder which is not soaked in the second plant protection solution as a passivation component.
The specific formulations of examples 13 to 17 and comparative examples 4 to 6 are shown in Table 3.
TABLE 3 formulation composition
| Weight ratio of | Allosteric extension component | Passivating component | |
| Example 13 | 1:10 | Anhydrous MgO obtained by calcination at 850 DEG C | Iron powder soaked in the second plant protection solution |
| Example 14 | 1:5 | Anhydrous MgO obtained by calcination at 850 DEG C | Iron powder soaked in the second plant protection solution |
| Example 15 | 1:1 | Anhydrous MgO obtained by calcination at 850 DEG C | Iron powder soaked in the second plant protection solution |
| Example 16 | 5:1 | Anhydrous MgO obtained by calcination at 850 DEG C | Iron powder soaked in the second plant protection solution |
| Example 17 | 10:1 | Anhydrous MgO obtained by calcination at 850 DEG C | Iron powder soaked in the second plant protection solution |
| Comparative example 4 | 1:5 | / | Iron powder soaked in the second plant protection solution |
| Comparative example 5 | 1:5 | Anhydrous MgO obtained by calcination at 850 DEG C | / |
| Comparative example 6 | 1:5 | Anhydrous MgO obtained by calcination at 850 DEG C | Iron powder |
EXAMPLE 18 remediation of heavy Metal contaminated soil
The heavy metal contaminated soil remediation materials prepared in the embodiments 1 to 12 and the comparative examples 1 to 3 are respectively added into the heavy metal combined contaminated soil according to 5% of the weight of the contaminated soil to be remediated (the types and the contents of the heavy metals are shown in table 4), and water in an amount of 30% of the weight of the contaminated soil to be remediated is added, and the mixture is cultured for 7 days. Then, the leaching toxicity of the passivated soil was tested according to the HJ557-2010 standard, the leaching concentration of heavy metals was measured by ICP-MS, and the passivation rate compared with the original soil was calculated, and the results are shown in Table 5.
TABLE 4 heavy metal species and content in soil
| Species of | Content (mg/kg) |
| Cr | 47.3±4.9 |
| Mn | 2163.3±78.5 |
| Cu | 270.0±40.7 |
| Zn | 7533.3±1364.7 |
| As | 12666.7±996.4 |
| Cd | 35.7±9.2 |
| Pb | 2758.7±353.7 |
TABLE 5 short-term passivation Effect
Note: the heavy metal concentration of the soil without passivation treatment in the leaching solution is as follows: cr 5.7. mu.g/L, Mn 3922.3. mu.g/L, Cu 24.6. mu.g/L, Zn
885.9μg/L，As 42.3μg/L，Cd 12.1μg/L，Pb 4.5μg/L。
According to the test results, the heavy metal contaminated soil remediation material provided by the invention has an excellent short-term passivation effect and high passivation efficiency.
EXAMPLE 19 remediation of heavy Metal contaminated soil
The heavy metal contaminated soil remediation materials prepared in the embodiments 13 to 17 and the comparative examples 4 to 6 are respectively added into the heavy metal combined contaminated soil according to 5% of the weight of the contaminated soil to be remediated (the types and the contents of the heavy metals are shown in table 6), and water in an amount of 40% of the weight of the contaminated soil to be remediated is added. Then judging the long-acting property of the stabilization of the composition through an artificial accelerated aging test, which comprises the following specific steps:
adding carbon dioxide saturated water into the soil according to the solid-liquid ratio of 1:9.625, oscillating the soil in a constant-temperature shaking table for 8 hours to simulate the influence of total rainfall of 6.25 years (annual rainfall is 2000mm), pouring out the supernatant, drying the supernatant at 40 ℃, and performing 16 circulation processes in total, wherein the process is called quantitative dry-wet circulation. The samples after the 4 th, 8 th, 12 th and 16 th cycles of dry and wet were taken for the calculation of the stabilization rate. The aging processes for 0, 25, 50, 75 and 100 years were simulated using the above artificial aging test method, respectively, and the stabilization rates were calculated as shown in table 7.
TABLE 6 heavy metals species and content in soil
| Species of | Content (mg/kg) |
| Cu | 278.1 |
| As | 79.5 |
| Cd | 136.8 |
| Pb | 3952.5 |
TABLE 7 Long-term passivation Effect
According to the test results, the heavy metal contaminated soil remediation material provided by the invention has a good long-acting passivation effect, and the long-term passivation rate is maintained to be more than 65%.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. A heavy metal contaminated soil remediation material, comprising:
a) an allosteric extension component and a passivation component in a weight ratio of (1:10) to (10:1), and
b) a long-acting promoting component accounting for 0.1-5% of the mass of the component a);
the allosteric extension component is selected from at least one of light-burned magnesite powder, hydrotalcite, sepiolite and attapulgite, and is anhydrous;
the passivation component is selected from at least one of iron powder, magnetite and pyrolusite, and the surface of the passivation component is coated with phenolic substances containing plant sources;
the long-acting promoting component is selected from at least one of blast furnace slag, steel slag and red mud.
2. The heavy metal contaminated soil remediation material of claim 1, wherein the substance surface-coated with the passivating component is a dry component of an aqueous extract of a plant.
3. The heavy metal contaminated soil remediation material of claim 1 or 2, wherein the conditions for subjecting the lightly calcined magnesite powder, the hydrotalcite, the sepiolite and the attapulgite to the anhydrous treatment are 180 ℃ to 550 ℃ in a non-oxidizing atmosphere for 30min to 120 min.
4. The heavy metal-contaminated soil remediation material of claim 1 or 2, wherein said hydrotalcite is selected from at least one of iron-magnesium hydrotalcite, iron-aluminum hydrotalcite, aluminum-magnesium hydrotalcite, calcium-aluminum hydrotalcite, calcium-magnesium hydrotalcite, and calcium-iron hydrotalcite.
5. The heavy metal contaminated soil remediation material of claim 1, wherein the particle size of said sepiolite, attapulgite and passivating component is independently selected from the group consisting of 100 mesh or less.
6. The preparation method of the heavy metal contaminated soil remediation material of any one of claims 1 to 5, comprising the steps of:
mixing the allosteric extension component, the passivation component and the long-acting acceleration component.
7. A method of preparation according to claim 6, wherein when the allosteric extension component is a soft-burned magnesite powder, the method further comprises the step of calcining the magnesite powder at 800 ℃ to 1050 ℃ before the step of mixing the allosteric extension component, the passivating component and the long-lasting accelerating component.
8. The method of manufacturing according to claim 6 or 7, wherein the passivation component is manufactured by a method comprising:
mixing the plant protection solution and at least one of iron powder, magnetite and pyrolusite according to a solid-liquid ratio of 1: (50-500) mixing, filtering and drying;
the preparation method of the plant protection solution comprises the following steps:
pulverizing pericarp and/or leaf to obtain pulverized material; and
mixing the crushed material with water at 40-90 ℃ according to a solid-liquid ratio of 1: (10-100) mixing and filtering to prepare the plant protection solution.
9. The method for restoring the heavy metal contaminated soil is characterized by comprising the following steps:
the heavy metal contaminated soil remediation material of any one of claims 1 to 5 is added to contaminated soil to be remediated, and mixed with water.
10. The method for remediating heavy metal-contaminated soil as recited in claim 9, wherein the amount of the heavy metal-contaminated soil remediation material added is 0.2-8% of the weight of the contaminated soil to be remediated, and the amount of the added water is 10-50% of the weight of the contaminated soil to be remediated.
11. The remediation method of claim 9 or 10, wherein the heavy metal in the contaminated soil is at least one of Cr, Mn, Cu, Zn, As, Cd, and Pb.
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