CN115926795A - Passivator for heavy metal cadmium pollution in soil and preparation method and application thereof - Google Patents
Passivator for heavy metal cadmium pollution in soil and preparation method and application thereof Download PDFInfo
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- CN115926795A CN115926795A CN202211441727.4A CN202211441727A CN115926795A CN 115926795 A CN115926795 A CN 115926795A CN 202211441727 A CN202211441727 A CN 202211441727A CN 115926795 A CN115926795 A CN 115926795A
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Abstract
The invention belongs to the technical field of soil heavy metal pollution treatment and restoration, and discloses a passivator for heavy metal cadmium pollution in soil, and a preparation method and application thereof. The passivator is prepared from calcite powder, lime, ceramic waste and steel slag. After the tested soil is treated by the passivator for 10 months, the content of the effective heavy metal cadmium in the soil is reduced by 29.3-29.4%. Namely, the passivating agent obtained by the invention has excellent cadmium passivating effect. The soil passivator disclosed by the invention does not need specific environmental conditions when used for treating soil, and can be used for carrying out in-situ treatment, so that the labor and the cost are reduced. The invention also provides a preparation method of the passivator polluted by heavy metal cadmium in soil, the preparation process is simple, large-scale equipment is not needed, the passivator can be prepared only by calcining, and the energy consumption is reduced.
Description
Technical Field
The invention relates to the technical field of soil heavy metal pollution treatment and restoration, in particular to a passivator for heavy metal cadmium pollution in soil, a preparation method and application thereof.
Background
In the beginning of the twentieth century, cadmium ores are exploited in large quantities for electroplating to prevent steel from rusting, in the beginning of the seventies of the twentieth century, cadmium is widely applied to smelting, battery, chemical and nuclear industries, and waste water, waste gas and waste residues discharged in the production process all contain a large amount of cadmium elements. Various media containing cadmium are diffused to peripheral areas of industrial production through the air, water, soil and the like to form hot areas of cadmium-enriched soil, and the hot areas threaten the local ecological environment and human health. Thus, cadmium pollution in farmland due to natural and artificial activities such as mining, production, smelting and the like and improper fertilizer application in agriculture is becoming serious, and the growth of crops is greatly influenced. Cadmium has the characteristics of high toxicity, nondegradable property, easy biological enrichment and the like, so cadmium can seriously threaten organisms and human beings, and a large number of researches show that cadmium is a nephrotoxic substance and has great damage to kidneys.
The materials of the existing chemical passivators can be divided into organic and inorganic types. The organic passivates comprise chitosan, activated sludge, livestock and poultry manure, agricultural waste and the like, and the inorganic passivates comprise various (clay) minerals, industrial furnace slag and the like. Although the passivators can achieve the effect of fixing heavy metals to a certain extent, the passivators also have some defects, such as high price, complex preparation (chitosan), heavy metal-containing harmful substances (activated sludge, livestock manure and industrial slag), high transportation cost (agricultural waste), poor raw material fixing effect (clay minerals), narrow application range and the like. The Chinese invention patent CN112322304A discloses a passivating agent and a passivating method for soil heavy metal pollution treatment, and the technology needs to add chemical reagents, thereby causing environmental pollution and resource waste. Chinese invention patent CN108659846A discloses a passivation method of construction waste base passivator for soil heavy metal cadmium, although the technology adopts construction waste as the passivator component, which saves resources, the passivation effect of the finally obtained passivator is not good, and simultaneously the passivator needs to make the soil moisture reach more than 40% when being applied, which is very easy to cause the loss of nutrient substances in the soil. Chinese invention patent CN106867945A discloses a microbial passivator for remediating heavy metal pollution of soil, and preparation and application thereof, and because the requirements of microbes on the growth environment are strict, the application of the technology needs to be combined with specific conditions, and is not suitable for being used in a large range. Therefore, the research of a passivating agent which has the advantages of excellent passivation effect, good stability, simple preparation process, no influence on the environment, resource saving and suitability for wide-range application becomes an urgent need in the field.
Disclosure of Invention
In view of the above, the invention provides a passivator for heavy metal cadmium pollution in soil, and a preparation method and an application thereof, so as to solve the problems of environmental pollution, resource waste, harsh application conditions and poor passivation effect of the existing passivator.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a passivator for heavy metal cadmium pollution in soil, which comprises the following raw materials in parts by weight:
110 to 130 portions of calcite powder
100 to 120 portions of lime
110 to 140 portions of ceramic waste
90-110 parts of steel slag.
Preferably, the particle size of the calcite powder is 6 to 10 μm, and the content of calcium carbonate in the calcite is 90 to 95%.
Preferably, the lime is hydrated lime, the particle size of the lime is 5-6 mu m, and the content of magnesium oxide in the lime is less than or equal to 3 percent.
Preferably, the ceramic waste has a particle size of 2 to 5 μm, and the steel slag has a particle size of 2 to 4 μm.
The invention also provides a preparation method of the soil heavy metal cadmium polluted passivator, which comprises the following steps:
mixing calcite powder, lime, ceramic waste and steel slag, calcining the mixture, and cooling to obtain the passivator.
Preferably, the mixing is carried out under stirring conditions, the rotation speed of the mixing is 1200 to 2000r/min, and the mixing time is 20 to 30min.
Preferably, the calcining temperature is 800-1200 ℃, the calcining time is 30-40 min, and the calcining temperature rise rate is 4-6 ℃/min.
Preferably, the calcination is carried out under a protective atmosphere, which is helium, nitrogen or hydrogen.
Preferably, the cooling is air cooling to room temperature.
The invention also provides application of the passivator for heavy metal cadmium pollution in soil, and the passivator is applied to the soil; the application amount of the passivator is 1-2 mg per gram of soil.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the passivator for preventing cadmium pollution is prepared from calcite powder, lime, ceramic waste and steel slag, the ceramic waste and the steel slag are used as raw materials for producing the passivator, so that resources are saved, the obtained passivator has good passivation effect, and the conditions required by use are wide;
(2) The preparation process is simple, large-scale equipment is not needed, and the preparation of the passivating agent can be completed only by calcining, so that the energy consumption is reduced.
Detailed Description
The invention provides a passivator for heavy metal cadmium pollution in soil, which comprises the following raw materials in parts by weight:
110 to 130 portions of calcite powder
100 to 120 portions of lime
110 to 140 portions of ceramic waste
90-110 parts of steel slag.
In the invention, the passivating agent preferably comprises 115-125 parts of calcite powder, and more preferably comprises 118-120 parts of calcite powder; the passivating agent preferably comprises 105-115 parts of lime, and more preferably comprises 110-113 parts of lime; the passivating agent preferably comprises 120-135 parts of ceramic waste, and more preferably comprises 125-130 parts of ceramic waste; the passivating agent preferably comprises 95 to 105 parts of steel slag, and more preferably comprises 100 to 104 parts of steel slag.
In the present invention, the particle size of the calcite powder is preferably 6 to 10 μm, and more preferably 7 to 9 μm; the content of calcium carbonate in calcite is preferably 90 to 95%, and more preferably 91 to 94%.
In the present invention, the lime is preferably slaked lime; the particle size of lime is preferably 5 to 6 μm, and more preferably 5.5 to 5.8 μm; the content of magnesium oxide in lime is preferably not more than 3%, and more preferably not more than 2%.
In the present invention, the particle size of the ceramic waste is preferably 2 to 5 μm, and more preferably 3 to 4 μm; the particle size of the steel slag is preferably 2 to 4 μm, and more preferably 2.5 to 3.5. Mu.m.
The invention adopts two solid wastes of steel slag and ceramic waste, thereby not only saving resources, but also reducing the environmental pollution caused by the accumulation of the solid wastes; the main components of the steel slag are calcium, iron, silicon, magnesium, aluminum, manganese, phosphorus and the like, and the elements correspond to trace elements in soil; the steel slag can supplement the content of trace elements in the soil, and further improve the quality of the soil; the main components of the ceramic waste are alumina and silica, the alumina and the silica can improve the pH value of soil, increase the variable negative charges on the soil surface and enhance the cadmium ion adsorption capacity, and meanwhile, the ceramic waste has a pore structure to further improve the cadmium adsorption effect. The interaction of the steel slag and the ceramic waste improves the cadmium passivation capability on one hand, improves the soil fertility on the other hand, and is more beneficial to the growth of plants.
Calcium carbonate in the calcite powder and calcium hydroxide in the lime are hydrolyzed to ensure that OH in soil - Increased concentration of CO in 3 2- And OH - Under the action of the catalyst, the exchange state cadmium can be reacted with CO 3 2- A carbonate complex with low solubility is generated through coprecipitation, so that the passivation amount of cadmium is improved; cd on the other hand 2+ With OH - Acting to generate Cd (OH) with stronger affinity with soil + So that most of the exchange cadmium is converted into carbonate, and the CdCO is promoted under the continuous strengthening action 3 、Cd(OH) 2 And insoluble precipitates are generated, so that the amount of adsorbed and fixed cadmium ions is further increased.
The invention also provides a preparation method of the soil heavy metal cadmium polluted passivator, which comprises the following steps:
mixing calcite powder, lime, ceramic waste and steel slag, calcining the mixture, and cooling to obtain the passivator.
In the invention, the mixing is carried out under the stirring condition, and the rotating speed of the mixing is preferably 1200-2000 r/min, and more preferably 1500-1800 r/min; the mixing time is preferably 20 to 30min, and more preferably 25 to 28min.
In the invention, the calcination temperature is preferably 800-1200 ℃, and more preferably 900-1100 ℃; the calcination time is preferably 30 to 40min, and more preferably 32 to 38min; the heating rate for calcination is preferably 4 to 6 ℃/min, and more preferably 5 ℃/min.
In the present invention, the calcination is preferably performed under a protective atmosphere, and the protective atmosphere is preferably helium, nitrogen, or hydrogen, and more preferably nitrogen or hydrogen.
In the present invention, the cooling is preferably air-cooled to room temperature.
In the invention, after cooling, the obtained product is washed and dried in sequence to obtain a passivating agent;
the washing reagent is preferably water; the number of washing is preferably 2 to 4, more preferably 3; the drying temperature is preferably 70-90 ℃, and more preferably 75-85 ℃; the drying time is preferably 20 to 40min, and more preferably 30 to 35min.
The invention also provides application of the passivator polluted by heavy metal cadmium in soil, and the passivator is applied to the soil; the application amount of the passivator is preferably 1-2 mg per gram of soil, and more preferably 1.2-1.8 mg per gram of soil.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The raw materials used in this example and their parts by mass were: 110 parts of calcite powder, 100 parts of lime, 110 parts of ceramic waste and 90 parts of steel slag; wherein the particle size of the calcite powder is 7 μm, and the content of calcium carbonate is 90%; the lime is hydrated lime, the particle size is 5 mu m, and the content of magnesium oxide is 3 percent; the grain size of the ceramic waste is 2 mu m; the grain size of the steel slag is 3 μm.
The preparation method comprises the following steps: adding the calcite powder, the lime, the ceramic waste and the steel slag in parts by mass into a mortar, mixing for 20min at a stirring speed of 1200r/min, then putting the mixed powder into a calcining furnace, introducing nitrogen, heating to 800 ℃ at a heating rate of 4 ℃/min, preserving heat for 30min, immediately taking out of the furnace, air cooling to room temperature, washing the product cooled to the room temperature with water for 3 times, then putting into a drying oven, and drying at 70 ℃ for 20min to obtain the passivator.
Example 2
The raw materials used in this example and their parts by mass were: 115 parts of calcite powder, 105 parts of lime, 112 parts of ceramic waste and 100 parts of steel slag; wherein the particle size of the calcite powder is 8 μm, and the content of calcium carbonate is 90%; the lime is hydrated lime, the grain diameter is 5.5 mu m, and the content of magnesium oxide is 3 percent; the grain size of the ceramic waste is 3 mu m; the grain size of the steel slag is 4 μm.
The preparation method comprises the following steps: adding the calcite powder, the lime, the ceramic waste and the steel slag in parts by mass into a mortar, mixing for 22min at a stirring speed of 1600r/min, then putting the mixed powder into a calcining furnace, introducing nitrogen, heating to 900 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 30min, immediately taking the mixed powder out of the furnace, air-cooling to room temperature, washing the product cooled to the room temperature with water for 3 times, and then putting the product into a drying box, and drying at 70 ℃ for 20min to obtain the passivator.
Example 3
The raw materials used in the present example and their parts by mass are: 120 parts of calcite powder, 115 parts of lime, 112 parts of ceramic waste and 110 parts of steel slag; wherein the particle size of the calcite powder is 10 μm, and the content of calcium carbonate is 92%; the lime is hydrated lime, the particle size is 5.7 mu m, and the content of magnesium oxide is 2 percent; the grain size of the ceramic waste is 5 mu m; the grain size of the steel slag is 3 μm.
The preparation method comprises the following steps: adding the calcite powder, the lime, the ceramic waste and the steel slag in parts by mass into a mortar, mixing for 25min at a stirring speed of 1800r/min, then putting the mixed powder into a calcining furnace, introducing nitrogen, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat for 35min, immediately taking out of the furnace, air cooling to room temperature, washing the product cooled to the room temperature with water for 3 times, then putting into a drying oven, and drying at 75 ℃ for 20min to obtain the passivator.
Example 4
The raw materials used in the present example and their parts by mass are: 125 parts of calcite powder, 120 parts of lime, 120 parts of ceramic waste and 110 parts of steel slag; wherein the particle size of the calcite powder is 10 μm, and the content of calcium carbonate is 95%; the lime is hydrated lime, the particle size is 6 mu m, and the content of magnesium oxide is 2 percent; the grain size of the ceramic waste is 5 mu m; the grain size of the steel slag is 3 μm.
The preparation method comprises the following steps: adding the calcite powder, the lime, the ceramic waste and the steel slag in parts by mass into a mortar, mixing at a stirring speed of 1800r/min for 20min, then putting the mixed powder into a calcining furnace, introducing nitrogen, heating to 1000 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 30min, immediately taking out of the furnace, air-cooling to room temperature, washing the product cooled to the room temperature with water for 3 times, and then putting the product into a drying box, and drying at the temperature of 75 ℃ for 20min to obtain the passivator.
Example 5
The raw materials used in the present example and their parts by mass are: 130 parts of calcite powder, 115 parts of lime, 140 parts of ceramic waste and 110 parts of steel slag; wherein the particle size of the calcite powder is 10 μm, and the content of calcium carbonate is 94%; the lime is hydrated lime, the particle size is 6 mu m, and the content of magnesium oxide is 2 percent; the grain size of the ceramic waste is 5 mu m; the grain size of the steel slag is 3 μm.
The preparation method comprises the following steps: adding the calcite powder, the lime, the ceramic waste and the steel slag in parts by mass into a mortar, mixing for 30min at a stirring speed of 1800r/min, then putting the mixed powder into a calcining furnace, introducing nitrogen, heating to 1000 ℃ at a heating rate of 6 ℃/min, keeping the temperature for 38min, immediately taking out of the furnace, air-cooling to room temperature, washing the product cooled to the room temperature with water for 3 times, and then putting into a drying oven, and drying for 25min at the temperature of 70 ℃ to obtain the passivator.
The performance of the passivates obtained in examples 1 to 5 was tested:
the soil used in the following tests was naturally contaminated and was selected from the soil surrounding a copper mine industrial plant in Guiyang City; the total cadmium content in the soil to be tested is 850 mu g/kg, the effective cadmium content is 301 mu g/kg, and the pH value is 5.01.
1. The performance of the passivating agents obtained in examples 1 to 5 for passivating cadmium was tested.
The test method comprises the following steps:
600g of the soil to be tested was taken and equally divided into 6 portions and placed in a beaker, which were designated as samples 1 to 6, respectively. Samples 1 to 5 were sequentially added to 100mg of the passivators obtained in examples 1 to 5, respectively, to prepare test groups; sample 6 was used as a blank control. Adjusting the soil moisture content of the samples 1-6 to be 20%, then placing the samples 1-6 in a thermostat, keeping the temperature at 25 ℃, sampling in 1 month, 2 months, 3 months, 4 months, 5 months, 6 months and 10 months respectively, and determining the content of the effective heavy metal cadmium in the soil of the samples 1-6. The results obtained are shown in table 1.
TABLE 1 passivation Effect of passivators obtained in examples 1 to 5
As can be seen from Table 1, the content of the effective heavy metal cadmium in the soil treated by the passivator is obviously reduced, and the content of the effective heavy metal cadmium in the soil is reduced by 29.3-29.4% in 10 months after the tested soil is treated by the passivator. Namely, the passivating agent obtained by the invention has excellent cadmium passivating effect.
2. The stability of the deactivant obtained in example 1 was tested.
The test method comprises the following steps:
300g of soil to be tested was taken, and the soil was equally divided into 3 portions and placed in a beaker, and designated as samples 7 to 9, respectively. Samples 7 to 9 were added to 100mg of the deactivators obtained in example 1, respectively. Keeping the soil moisture of the samples 7-9 at 20%, sampling in 1, 2, 3, 4, 5, 6 and 10 months respectively, and determining the content of the effective heavy metal cadmium in the soil of the samples 7-9. The results are shown in Table 2.
Table 2 results of stability test of passivator obtained in example 1
As can be seen from Table 2, the passivator obtained by the invention can carry out in-situ treatment without passivating cadmium in soil under specific conditions, thereby reducing labor and cost.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. The passivator for heavy metal cadmium pollution in soil is characterized by comprising the following raw materials in parts by weight:
2. the passivator for soil polluted by heavy metal cadmium according to claim 1, wherein the particle size of the calcite powder is 6-10 μm, and the content of calcium carbonate in the calcite is 90-95%.
3. The soil passivator for heavy metal cadmium pollution according to claim 2, wherein the lime is hydrated lime, the particle size of the lime is 5-6 μm, and the content of magnesium oxide in the lime is less than or equal to 3%.
4. The soil passivating agent polluted by heavy metal cadmium according to any one of claims 1 to 3, wherein the particle size of the ceramic waste is 2 to 5 μm, and the particle size of the steel slag is 2 to 4 μm.
5. The preparation method of the passivator for the soil polluted by the heavy metal cadmium as claimed in any one of the claims 1 to 4 is characterized by comprising the following steps:
mixing calcite powder, lime, ceramic waste and steel slag, calcining the mixture, and cooling to obtain the passivator.
6. The preparation method of the passivator for soil polluted by heavy metal cadmium as claimed in claim 5, wherein the mixing is carried out under stirring conditions, the rotation speed of the mixing is 1200-2000 r/min, and the mixing time is 20-30 min.
7. The preparation method of the passivator polluted by heavy metal cadmium in soil according to claim 5 or 6, wherein the calcining temperature is 800-1200 ℃, the calcining time is 30-40 min, and the calcining temperature rise rate is 4-6 ℃/min.
8. The preparation method of the passivator for the soil polluted by heavy metal cadmium as claimed in claim 7, wherein the calcination is carried out in a protective atmosphere, wherein the protective atmosphere is helium, nitrogen or hydrogen.
9. The method for preparing the passivator for passivating the soil polluted by heavy metal cadmium according to claim 8, wherein the cooling is air cooling to room temperature.
10. Use of a soil passivator contaminated with cadmium as a heavy metal according to any of claims 1 to 4 wherein the passivator is applied to the soil; the application amount of the passivator is 1-2 mg per gram of soil.
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| CN202211441727.4A CN115926795A (en) | 2022-11-17 | 2022-11-17 | Passivator for heavy metal cadmium pollution in soil and preparation method and application thereof |
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| CN202211441727.4A CN115926795A (en) | 2022-11-17 | 2022-11-17 | Passivator for heavy metal cadmium pollution in soil and preparation method and application thereof |
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