CN111944538A - Stabilizer for repairing soil cadmium, lead and arsenic combined pollution and preparation method thereof - Google Patents
Stabilizer for repairing soil cadmium, lead and arsenic combined pollution and preparation method thereof Download PDFInfo
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- CN111944538A CN111944538A CN202010994234.8A CN202010994234A CN111944538A CN 111944538 A CN111944538 A CN 111944538A CN 202010994234 A CN202010994234 A CN 202010994234A CN 111944538 A CN111944538 A CN 111944538A
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- soil
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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
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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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
Abstract
The invention discloses a stabilizer for remedying the composite pollution of cadmium, lead and arsenic in soil, belonging to the technical field of resource and environment remediation, and the raw material components of the stabilizer comprise heavy calcium carbonate, attapulgite, humic acid raw powder and modified biochar; the invention also discloses a preparation method and application of the stabilizer for repairing the cadmium, lead and arsenic combined pollution of the soil, the stabilizer is convenient and fast to apply to the repairing step of the polluted soil, the components of the medicament contained in the stabilizer are not complex, the operation is simple, the practicability is strong, the stabilizing capability of the soil stabilizer is strong, after the stabilizer is applied to the polluted soil, the pollution of heavy metals of cadmium, lead and arsenic can be obviously reduced, new environmental risks cannot be generated, the stability of cadmium, lead and arsenic in the soil can be ensured for a long time, and the heavy metals of cadmium, lead and arsenic are prevented from being released again; the utilization efficiency of the soil is improved, and a new way is provided for the treatment of the heavy metal pollution of the soil.
Description
Technical Field
The invention belongs to the technical field of resource and environment restoration, and particularly relates to a stabilizer for restoring cadmium, lead and arsenic combined pollution of soil and a preparation method thereof.
Background
With the rapid development of industrial and agricultural industries in China, the problem of heavy metal pollution caused by mining, smelting, pesticide, chemical fertilizer application and other behaviors is becoming more serious, and heavy metals have concealment, difficult degradability and carcinogenicity, can be accumulated in organisms through water, soil, food chains and other ways, influence the safety of agricultural products and further harm human health. Therefore, it is important to find a stabilizer with lower cost and more remarkable effect. Compared with other restoration technologies, the stabilization technology provided by the invention has the advantages of simplicity in operation, low cost, wide application range and the like, and is widely researched and applied to heavy metal contaminated soil.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a stabilizer for repairing the cadmium, lead and arsenic combined pollution of soil and a preparation method thereof, the stabilizer is convenient to apply to the polluted soil, the contained medicament components are not complex, the operation is simple, the practicability is strong, the soil stabilizer has strong stabilizing capability, after the stabilizer is applied to the polluted soil, the pollution of heavy metals of cadmium, lead and arsenic can be obviously reduced, new environmental risks cannot be generated, the stability of cadmium, lead and arsenic in the soil can be ensured for a long time, and the heavy metals of cadmium, lead and arsenic are prevented from being released again; the utilization efficiency of the soil is improved, and a new way is provided for the treatment of the heavy metal pollution of the soil.
In order to realize the purpose, the invention adopts the technical scheme that:
a stabilizer for remedying the soil combined pollution of cadmium, lead and arsenic comprises heavy calcium carbonate, attapulgite, humic acid raw powder and modified biochar.
A stabilizer for repairing soil cadmium, lead and arsenic combined pollution comprises the following raw material components in percentage by mass: 60-70% of heavy calcium carbonate, 10-25% of attapulgite, 10-25% of humic acid raw powder and 2-5% of modified biochar.
A stabilizer for repairing soil cadmium, lead and arsenic combined pollution comprises the following raw material components in percentage by mass: 60% of heavy calcium carbonate, 20% of attapulgite, 18% of humic acid raw powder and 2% of modified biochar.
Furthermore, the main component of the heavy calcium carbonate is limestone, and the purity is more than or equal to 95 percent; the mass percentage content of calcium is more than or equal to 45 percent, and the particle size is less than or equal to 0.450 mm.
Furthermore, the attapulgite is attapulgite crystalline powder, the purity is more than or equal to 80 percent, and the particle size is less than or equal to 0.500 mm.
Furthermore, the humic acid raw powder is brownish black solid powder, the content of organic matters is 30-40%, and the particle size is less than or equal to 0.750 mm.
Further, the modified biochar raw material is corn straw, the raw biochar is prepared by smashing the corn straw and then pyrolyzing the smashed raw biochar for 3 hours in a closed environment at 400 ℃, and then the volume ratio of the smashed raw biochar to the raw biochar is 20: 1H2O/OH-Soaking in the solution for 24h, washing with deionized water to neutrality, and oven drying at 95 deg.C to obtain the final product with particle size of less than or equal to 2.00 m.
A preparation method of a stabilizer for remedying the soil cadmium, lead and arsenic combined pollution comprises the steps of weighing and uniformly mixing heavy calcium carbonate, attapulgite, humic acid raw powder and modified biochar according to the mass percentage to obtain the stabilizer.
The application of the stabilizer for remedying the cadmium, lead and arsenic combined pollution of the soil comprises the following steps: the prepared stabilizer is uniformly mixed with the cadmium, lead and arsenic compound contaminated soil to form stabilized soil, the humidity of the stabilized soil is adjusted to 15-25%, and finally the stabilized soil is stabilized for 120 hours in a closed environment to obtain the repaired soil.
And further, when the humidity of the stabilized soil does not reach 15% -25%, adding deionized water into the stabilized soil for regulation.
Preferably, the stabilized soil humidity is 20%.
Furthermore, the addition amount of the stabilizer is 3-5% of the mass of the cadmium, lead and arsenic combined polluted soil.
The invention has the beneficial effects that: (1) the stabilizer prepared by the invention is convenient to apply to the contaminated soil remediation step, the contained medicament components are not complex, the operation is simple, the practicability is strong, the soil stabilizer has strong stabilization capability, the pollution of heavy metals such as cadmium, lead and arsenic can be obviously reduced after the stabilizer is applied to the contaminated soil, new environmental risks cannot be generated, the stability of cadmium, lead and arsenic in the soil can be ensured for a long time, and the heavy metals such as cadmium, lead and arsenic are prevented from being released again; the utilization efficiency of the soil is improved, and a new way is provided for the treatment of the heavy metal pollution of the soil;
(2) the stabilizer has larger specific surface area, rich pores and a large number of functional groups, accelerates the adsorption of heavy metal pollutants through surface adsorption, electrostatic action and complexing action, can effectively fix heavy metal ions, and adopts heavy calcium carbonate, modified biochar and other raw materials with wide sources and low price, wherein the attapulgite and humic acid raw powder are common in the nature, are easy to obtain and have simple proportioning;
(3) the humic acid in the humic acid raw powder adopted by the invention is a high-molecular organic acid consisting of a plurality of functional groups, so that not only can the acidity of the soil be adjusted and the structure of the soil be improved, but also the CEC content of the soil can be increased and the cohesiveness of soil colloid can be enhanced; the biochar is rich in a porous structure, and provides a large specific surface area, so that the number of binding sites of heavy metal ions such as cadmium, lead and arsenic can be greatly increased, the mobility of the heavy metal ions is reduced, the graphite-like structure of the biochar can promote electron transfer, so that oxidation or reduction of heavy metal pollutants is promoted, and meanwhile, a large amount of soil aggregates are easily formed in soil after the biochar is added, so that the adsorption capacity of the heavy metal ions is improved.
The invention adopts the stabilization reaction principle of four raw materials: after being mixed with soil, the ground calcium carbonate, the attapulgite are hydrated or activated, and then part of the mixture is added with CaO-MgO-SiO2-Al2O3-H2O form exists, and therefore by releasing large amounts of exchangeable Ca into the soil2+、Mg2+、Al3+Etc. capable of reacting with heavy metal ions R2+(Cd2+、Pb2+、As2+Etc.) to perform ion exchange on the surface of soil particles, suspension and pore canal positions, and in addition, the addition of heavy calcium carbonate and attapulgite ensures that OH in the soil environment-Increase of ions, OH in solution-The increased hydrolysis reaction is represented by the following formula:
CaCO3+CaMg(CO3)2+3H2O→2Ca2++Mg2++3HCO3-+3OH-
or CaO + MgO + SiO2+Al2O3+7H2O→Ca2++Mg2++2Al3++H4SiO4+10OH-
The soil solution is gradually changed to be neutral or alkaline, and heavy metal ions R2+The method is carried out according to the following precipitation reaction formula:
R2++2OH-→Me(OH)2
SiO4 4-+CO3 2-+3R2+→RCO3+R2SiO4
me (OH) in the above precipitation reaction formula2、RCO3、R2SiO4Continuously generate to promote the balance of hydrolysis reaction to shift right, OH-Increase, further accelerate precipitation reaction and fix and stabilize heavy metal ions.
Detailed Description
For a better understanding of the present invention, embodiments of the present invention are described in detail below with reference to examples, but those skilled in the art will understand that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
Example 1:
a stabilizer for repairing soil cadmium, lead and arsenic combined pollution comprises the following raw material components in percentage by mass: 60% of heavy calcium carbonate, 20% of attapulgite, 18% of humic acid raw powder and 2% of modified biochar.
Example 2:
a stabilizer for repairing soil cadmium, lead and arsenic combined pollution comprises the following raw material components in percentage by mass: 70% of heavy calcium carbonate, 15% of attapulgite, 10% of humic acid raw powder and 5% of modified biochar.
Example 3:
a stabilizer for repairing soil cadmium, lead and arsenic combined pollution comprises the following raw material components in percentage by mass: 60% of heavy calcium carbonate, 25% of attapulgite, 12% of humic acid raw powder and 3% of modified biochar.
Example 4:
a stabilizer for repairing soil cadmium, lead and arsenic combined pollution comprises the following raw material components in percentage by mass: 65% of heavy calcium carbonate, 15% of attapulgite, 16% of humic acid raw powder and 4% of modified biochar.
Example 5:
a stabilizer for repairing soil cadmium, lead and arsenic combined pollution comprises the following raw material components in percentage by mass: 60% of heavy calcium carbonate, 10% of attapulgite, 25% of humic acid raw powder and 5% of modified biochar.
In order to prove the universality of the stabilizing agent of the invention in stabilizing and immobilizing the cadmium, lead and arsenic combined contaminated soil, the stabilizing agent provided in example 1 is further described as follows:
1. soil sample for testing
The soil to be tested is respectively numbered M, N, Q, M soil sample is collected from a certain abandoned chemical plant in Changle region of Fuzhou city in Fujian province, N soil sample is collected from the vicinity of a certain metal processing plant in Fuzhou city, Minhou county in Fujian province, Q soil sample is collected from the vicinity of a certain chemical plant in Jinjiang city in Fujian province, impurities are removed after collection, the soil is placed in a clean vessel, and the soil is dried in the shade and then screened by a 20-mesh screen for later use.
2. Stabilization treatment
Respectively taking M, N, Q soil samples in three parts, measuring the water content of each part, weighing 200g of each part, and placing the part in a clean 1000mL beaker; wherein the numbers CK-M, CK-N, CK-Q are respectively blank treatment of M, N, Q soil samples; numbering M-3%, N-3% and Q-3%, respectively adding 6g of stabilizer into M, N, Q soil samples, uniformly mixing, adding a proper amount of deionized water according to the water content of M, N, Q soil samples until the water content of M, N, Q soil samples is 20%, stabilizing the stabilized soil in a semi-dry and semi-wet state, and stabilizing for 120 hours in a closed environment; the numbers of M-5%, N-5% and Q-5% are that 10g of stabilizer is respectively added into M, N, Q soil samples, according to the water content of M, N, Q soil samples, a proper amount of deionized water is added until the water content of M, N, Q soil samples is about 20%, the stabilized soil is in a semi-dry and semi-wet state, and the stabilized soil is stabilized for 120 hours in a closed environment.
3. Test method
M, N, Q the leaching of heavy metal concentration of cadmium, lead and arsenic of soil sample adopts DTPA-CaCl2-TEA leaching method (GB/T23739-2009), leaching CK-M, CK-N, CK-Q, M%, N-3%, Q-3%, M-5%, N-5% and Q-5% of the soil sample, determining heavy metal content leaching liquid by adopting an inductive coupling plasma mass spectrometer (ICP-MS, Ultimate 3000-i CAP QC) to detect cadmium, lead and arsenic, and performing quality control experiment by adopting standard substance SRMs-2586 to detect pH value of the leaching liquid. The leaching concentration and pH detection data of heavy metals cadmium, lead and arsenic before and after three kinds of soil treatment are shown in Table 1, wherein the stabilization rate is (leaching concentration of heavy metals in soil without adding stabilizer-leaching concentration of heavy metals in soil after adding stabilizer)/leaching concentration of heavy metals in soil without adding stabilizer multiplied by 100%.
Table 1: leaching concentration and pH detection value of heavy metal cadmium, lead and arsenic before and after three kinds of soil treatment
As can be seen from Table 1, the concentrations of heavy metals of cadmium, lead and arsenic extracted from M, N, Q soil after 3% of the stabilizer in example 1 is added can reach more than 76.6% in the stabilization rate; after 5% of the stabilizer in the embodiment 1 is added, the concentrations of heavy metals of cadmium, lead and arsenic extracted from M, N, Q soil by leaching are all higher than 84.7%, wherein the cadmium stabilization rate of M, N, Q soil is respectively 93.9%, 92.6% and 94.0%, the lead stabilization rate is respectively 84.7%, 88.7% and 90.8%, and the arsenic stabilization rate is respectively 93.6%, 90.8% and 89.9%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.
Claims (10)
1. The stabilizer for repairing the soil combined pollution of cadmium, lead and arsenic is characterized by comprising the raw material components of ground limestone, attapulgite, humic acid raw powder and modified biochar.
2. The stabilizer for remedying the cadmium, lead and arsenic combined pollution of the soil according to claim 1, which is characterized by comprising the following raw material components in percentage by mass: 60-70% of heavy calcium carbonate, 10-25% of attapulgite, 10-25% of humic acid raw powder and 2-5% of modified biochar.
3. The stabilizer for remedying the cadmium, lead and arsenic combined pollution of the soil according to claim 1, which is characterized by comprising the following raw material components in percentage by mass: 60% of heavy calcium carbonate, 20% of attapulgite, 18% of humic acid raw powder and 2% of modified biochar.
4. The stabilizer for remedying the soil combined pollution of cadmium, lead and arsenic according to claim 1, wherein the heavy calcium carbonate mainly comprises limestone with a purity of more than or equal to 95%; the mass percentage content of calcium is more than or equal to 45 percent, and the particle size is less than or equal to 0.450 mm.
5. The stabilizer for remediating the soil combined pollution of cadmium, lead and arsenic as claimed in claim 1, wherein the attapulgite is attapulgite crystalline powder, the purity is not less than 80%, and the particle size is not more than 0.500 mm.
6. The stabilizer for remedying the soil combined pollution of cadmium, lead and arsenic according to claim 1, wherein the humic acid raw powder is brown black solid powder, the content of organic matters is 30-40%, and the grain size is less than or equal to 0.750 mm.
7. The stabilizer for remedying the soil polluted by cadmium, lead and arsenic as per claim 1Characterized in that the modified biochar raw material is corn straw, the raw biochar is prepared by crushing and pyrolyzing the crushed raw biochar for 3 hours in a closed environment at 400 ℃, and then the volume ratio of the raw biochar to the modified biochar is 20: 1H2O/OH-Soaking in the solution for 24h, washing with deionized water to neutrality, and oven drying at 95 deg.C to obtain the final product with particle size of less than or equal to 2.00 m.
8. The preparation method of the stabilizer for remedying the soil combined pollution of cadmium, lead and arsenic according to any one of claims 1 to 7, wherein the stabilizer is obtained by respectively weighing and uniformly mixing the ground limestone, the attapulgite, the humic acid raw powder and the modified biochar according to the mass percentage.
9. The application of the stabilizer for remedying the soil combined pollution of cadmium, lead and arsenic according to claim 1 is characterized in that the application method comprises the following steps: the prepared stabilizer is uniformly mixed with the cadmium, lead and arsenic compound contaminated soil to form stabilized soil, the humidity of the stabilized soil is adjusted to 10-25%, and finally the stabilized soil is stabilized for 120 hours in a closed environment to obtain the repaired soil.
10. The application of the stabilizer for remedying the cadmium, lead and arsenic combined pollution of the soil according to claim 9, wherein the addition amount of the stabilizer is 3-5% of the mass of the cadmium, lead and arsenic combined pollution soil.
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| CN112852432A (en) * | 2021-01-21 | 2021-05-28 | 湖南凯迪工程科技有限公司 | Stabilizer prepared from organic waste and using method thereof |
| CN112916602A (en) * | 2021-01-20 | 2021-06-08 | 西南科技大学 | Method for treating arsenic pollution by using waste calcium bloom |
| CN112940731A (en) * | 2021-01-19 | 2021-06-11 | 广西壮族自治区亚热带作物研究所（广西亚热带农产品加工研究所） | Heavy metal composite pollution site treatment and restoration agent |
| CN113265256A (en) * | 2021-04-16 | 2021-08-17 | 兰州大学 | Soil conditioner and preparation method and application thereof |
| CN115228925A (en) * | 2022-07-26 | 2022-10-25 | 湖南凯迪工程科技有限公司 | Stabilizer for repairing soil heavy metal combined pollution and preparation and application thereof |
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