Patent Grant
11473013
This application is based upon and claims priority to Chinese Patent Application No.: 202110500856.5, filed on May 8, 2021, the entire contents of which are incorporated herein by reference.
The invention relates to soil remediation technology, in particular to a magnetic soil remediation agent for soil heavy metal pollution and preparation method and use thereof.
With the continuous acceleration of the industrialization process, various pollutants containing heavy metals continue to enter the surrounding farmland soil through various channels such as industrial waste gas, pesticides and fertilizers, sewage irrigation, and waste accumulation and transfer, resulting in serious soil heavy metal pollution (Cd, Pb, As, Cr, and other pollution). Due to the irreversible and non-degradable characteristics of soil heavy metals, these heavy metals will bring huge harm after entering the farmland soil. They not only have a negative impact on the number and population structure of soil microorganisms, but also interfere with the normal metabolism of crops, resulting in reduced crop yield and quality. In addition, after these heavy metals are absorbed and enriched by crops in the soil, their heavy metal content exceeds the standard, and these heavy metals enter the human body through the food chain, and are enriched in different organs of the human body and cannot be discharged. As a result, they will cause irreversible harm to various physiological functions of the human body and bring serious threats to human life and health. Therefore, the restoration and management of soil environment is imminent.
However, since soil heavy metal pollution is not as easy to be detected as air and water pollution, and the harm it produces has a certain concealment; therefore, the discovery of heavy metal pollution in soil often has a certain hysteresis and cannot be repaired and treated in time. Once the harm of heavy metal pollution in farmland soil appears, the difficulty of heavy metal treatment will be intensified, and the treatment of heavy metals in soil will be costly, time-consuming and difficult. These problems all pose a huge challenge to the pollution control of soil heavy metals. Therefore, the pollution of heavy metals in farmland soil should be prevented in advance, and the transfer of heavy metals to agricultural soil should be avoided and prevented in time. At the same time, for soils that are easily polluted by heavy metals, the ability of the soil to passivate heavy metals should be improved as much as possible, so as to reduce the possible harm caused by the toxicity of heavy metals in the soil. Taking appropriate soil remediation measures for different soil heavy metal pollution situations is the main control strategy to reduce soil treatment costs and improve soil remediation efficiency.
At present, the commonly used passivating agents mainly include calcareous materials, phosphorus-containing passivating agents, carbon materials, clay minerals, organic fertilizers, agricultural wastes, etc. Among them, calcareous materials mainly realize the passivation of heavy metals by changing the soil pH, but excessive application will significantly affect the physical and chemical properties of the soil, resulting in the reduction of crop yields. Phosphorus-containing passivators are usually used for lead passivation, but high concentrations of phosphorus can also lead to the leaching of contaminants such as arsenic, increasing their mobility; and, as eutrophic substances, phosphorus-containing passivators are also prone to pollute the surrounding water bodies, so their application scope is limited. Carbon materials mainly use their large specific surface area to fix and passivate heavy metals through adsorption, but such passivators are not stable enough; with the degradation of carbon, the adsorbed metals will be re-released into the soil, resulting in pollution again. Organic fertilizers and agricultural wastes also have similar problems with carbon materials when dealing with soil heavy metal pollution, so their application scope is narrow. Clay minerals also use the characteristics of large specific surface area and charged structural layer to achieve passivation of heavy metals through adsorption, coordination and co-precipitation; however, they have strong adsorption selectivity for heavy metals, and are only suitable for repairing single heavy metal pollution; for the treatment of composite heavy metal-contaminated soil, they need to be used in conjunction with alkaline substances such as lime, and modification treatment is usually used to enhance the adsorption effect, and there is a certain risk of secondary pollution.
Silicate heavy metal passivator is an important soil heavy metal remediation agent, which can reduce heavy metal activity in soil, inhibit plant uptake and realize the remediation of heavy metal pollution in the soil by forming silicic acid compounds with heavy metals, affecting the rhizosphere redox capacity to reduce the activity of heavy metals, improving soil pH to inhibit the adsorption of heavy metals by plants, changing the form of heavy metals and hindering the migration of heavy metals to the aerial parts of plants, etc. At present, the market price of silicate heavy metal passivators is as high as 5000-10000 RMB/t. Although it can effectively modify the farmland soil polluted by heavy metals, the cost is too high.
The purpose of the present invention is to aim at the above-mentioned problems, and provide a capture-functionalized magnetic soil remediation agent with amino and sulfhydryl groups for heavy metals in soil, which has a significant passivation and fixation effect on heavy metals, and can significantly inhibit the absorption of heavy metals by plants. The specific technical scheme is as follows:
A magnetic soil remediation agent for soil heavy metal pollution is prepared by using remediation agent framework material and magnetic core material as raw materials, and heavy metal collector as modifier;
Preferably, the mass ratio of said framework material, magnetic core material, and modifier is 1 (0.05-0.1):(0.005-0.01).
Preferably, the mass ratio of Fe3O4 and γ-Fe2O3 in said magnetic core material is (1.5-2):1.
Preferably, the mass ratio of EDTA:NTA:EDDS:mercaptoethylamine in said modifier is 1:(0.05-0.1):(0.1-0.2):(0.2-0.3).
Preferably, compared with the unmodified magnetic core material, said magnetic soil remediation agent has characteristic peaks at 26.8°, 35.3° and 62.2° in the XRD pattern, corresponding to SiO2, Fe3O4, γ-Fe2O3; in the infrared spectrum analysis results, it has characteristic peaks at wave values 3461, 1637, 1432, 1090 and 795 cm−1, and the infrared characteristic peaks correspond to silicon-oxygen bond, sulfhydryl and amino functional group.
One aspect of the present invention also provides a method for preparing any one of the above magnetic soil remediation agents, comprising the following steps:
Preferably, in said step (1), the roasting temperature is 800° C., roasting for 30-60 min, and the excess NaOH is washed off with water so that the pH of the framework is 6.5-8.5.
Preferably, in said step (3), the SiO2 framework, the magnetic core material and the modifier solution are uniformly mixed in proportion, precipitated, filtered, heated for drying in a vacuum oven at 50° C. for 2-3 h, and pulverized, then the magnetic soil remediation agent of the present invention is obtained.
Another aspect of the present invention also provides the application of any one of the magnetic soil remediation agents described above in remediating polluted soil;
The last aspect of the present invention provides a method of soil remediation, wherein any one of the magnetic soil remediation agents described above is applied to the polluted soil to be treated, and then mixed and stirred evenly;
The applied amount of said magnetic soil remediation agent ranges from 50 to 200 g/m2, more preferably from 80 to 150 g/m2, and further preferably from 80 to 120 g/m2 or 100 g/m2.
The beneficial effects of the present invention are: the magnetic soil remediation agent for soil heavy metal pollution of the present invention can effectively change the redox potential of the soil for the magnetic function of heavy metals in the soil, and increase the migration ability of the heavy metals in the soil. The amino group and sulfhydryl group of the remediation material can effectively capture a variety of heavy metal elements to form heavy metal complexes on the surface of the magnetic soil remediation agent material. The active silicon-oxygen bond in the silicon dioxide activated by strong alkali can further form a heavy metal silicate structure with heavy metals, which increases the adsorption capacity of the material; moreover, the formed stable heavy metal silicate structure has a significant passivation and fixation effect on heavy metals, reduces their available contents, and can significantly inhibit the absorption of heavy metals by plants.
The present invention will be further described below in conjunction with the examples, but the present invention is not limited thereby.
The experimental methods in the following examples, unless otherwise specified, are conventional methods; the chemical reagents used in each example, unless otherwise specified, are commercially available conventional reagents, which can be obtained through commercial purchase.
Main reagents:
1. Preparation of the Magnetic Soil Remediation Agent of the Present Invention
Taking magnetic materials Fe3O4 and γ-Fe2O3 as the magnetic core material, taking ethylenediaminetetraacetic acid (EDTA) as heavy metal collector, taking nitrilotriacetic acid trisodium salt (NTA), (S,S)-ethylenediamine-N, N-disuccinic acid trisodium salt (EDDS) and mercaptoethylamine as modifier, and taking the silicon dioxide activated by strong alkali as framework material, capture-functionalized magnetic soil remediation agent with amino and sulfhydryl groups was prepared.
The magnetic soil remediation agent of the present invention was prepared according to the following steps:
Four experimental groups of magnetic soil remediation agent products of the present invention were prepared according to the above method, and the specific components and dosages of each experimental group are shown in Table 1.
2. Product Composition Analysis and XRD Characterization
The products prepared in experimental groups 1-4 were taken for component analysis and XRD characterization, and the results of component analysis are shown in Table 2.
It can be seen from Table 2 that some organic matter is attached to the product, and the TOC content of the organic matter is about 1-2%, indicating that the amino and sulfhydryl groups in the modifier were compounded in the magnetic material by modification in the present invention.
The XRD characterization of the product is shown in
Infrared detection of the product was performed, and infrared (FTIR, Nicolet 6700) analysis conditions were: the magnetic soil remediation agent was mixed with KBr particles and made into tablets, and the scanning resolution was 0.4 cm−1, and the scanning range was 4000-650 cm−1.
1. Research on Pot Experiment of Soil Remediation Agent Product of the Present Invention
In order to study the effect of the soil remediation agent of the present invention on the remediation effect of soil heavy metal pollution and the influence on the absorption of heavy metals by plants, a farmland experiment was carried out with Chinese cabbage as the object. The morphological changes of heavy metals Pb, Cu, Cr, Cd, Hg, As in soil and their effects on crop growth were mainly analyzed.
Experimental Method:
A polluted farmland in a large lead-zinc mine was selected for field plot experiments, and soil was collected for cultivation experiments and pot experiments. Two treatments were prepared in this experiment: the control group (without adding the magnetic soil remediation agent of the present invention) and the magnetic soil remediation agent treatment group (different dosages were set: 50 g/m2, 80 g/m2, 100 g/m2, 120 g/m2, 150 g/m2, 200 g/m2). Each treatment contained 4 replicate plots, each with an area of 20 m2 (4 m×5 m), and the plots were randomly arranged. One week before sowing, the magnetic soil remediation agent was added in the experimental field of the treatment group, the magnetic soil remediation agent (particle diameter <2 mm) of the experimental group 1 in Example 1 was added to the soil, and thoroughly mixed with topsoil (0-10 cm depth) by hand tillage; one week later, the pakchoi variety “si yue man” was sown, and daily management was carried out according to the conventional field management methods of pakchoi. Fertilization management was as follows: before planting pakchoi, nitrogen and phosphorus compound fertilizer was applied at a rate of 225 kg/ha as base fertilizer, and nitrogen fertilizer was applied within 1 month after planting. Soil samples collection: the soil samples were collected before the application of the magnetic soil remediation agent and after the pakchoi was matured, and the pakchoi samples were collected after the pakchoi was matured.
2. The influence of the application of the soil remediation agent of the present invention on soil heavy metals
(1) Changes of Available and Residual States of Heavy Metals in Soil
The available state and residual state of soil heavy metals Pb, Cu, Cr, Cd, Hg, As after different application dosages of soil remediation agent were detected.
The detection method of available state of heavy metals in soil was as follows: the available Pb, Cu, Cr, Cd, Hg and As in the soil were determined by leaching with DTPA solution (0.005 mol/L diethyltriaminepentaacetic acid DTPA+0.01 mol/L CaCl2+0.1 mol/L triethanolamine TEA), the pH of the solution was adjusted to 7.3±0.05, and the solution was shaken at 180 rpm for 2 h at room temperature; the extract solution was adjusted to volume with 5 g/L tartaric acid and filtered through a 0.45 um aqueous membrane, the contents of Pb, Cu, Cr and Cd were determined by flame atomic absorption spectrophotometer, and the contents of Hg and As were determined by atomic fluorescence spectrometer.
The detection method of residual state of heavy metals in soil was as follows: 0.2000-0.5000 g of air-dried residual soil which passed a 100-mesh sieve was put into the digestion tank, concentrated nitric acid (6 mL), concentrated hydrochloric acid (2 mL), and 30% hydrogen peroxide (2 mL) were added sequentially; after the bubbles in the digestion tank were eliminated, the lid was put on and tightened, then the tank was put into the microwave digestion apparatus. The temperature was programmed according to the program, and the digestion was carried out at 200° C. for 30 min. After the heating was completed, the digestion tank was opened after cooling to room temperature; the digestion solution was transferred into a 50 mL colorimetric tube, adjusted to volume with 5 g/L tartaric acid, shaken well, left to stand, and passed through a 0.45 um aqueous filter; the contents of Pb, Cu, Cr and Cd were determined by flame atomic absorption spectrophotometer, and the contents of Hg and As were determined by atomic fluorescence spectrometer.
The experimental results showed that: with the application amount of the remediation agent in the range of 50-150 g/m2, among the six different metals, the available states of Pb, Cu, Cr, Cd, Hg, and As showed a decreasing trend with the increase of the applied amount, and the decreasing amplitude of the available state gradually increased; while the content of residual state increased gradually with the increase of the application amount of the remediation agent, and the larger the application amount, the greater the increase. It can be seen that the remediation agent had a significant passivation and fixation effect on heavy metals.
At the same time, it was found that when the application amount of the remediation agent was above 150 g/m2, the passivation and fixation effect no longer increased, but showed a slow decline trend. Therefore, the application amount of the remediation agent can be in the range of 50-200 g/m2, and the better range is 80-150 g/m2. Considering the cost and effect, the optimal range is 80-120 g/m2 or 100 g/m2.
Thereinto, the test results of the experimental groups with application amounts of 0, 50 g/m2, 100 g/m2 and 200 g/m2 are shown in Table 3-Table 8
It can be seen from Table 3-8 that among the six different metals, the contents of available states of Pb, Cu, Cr, Cd, Hg and As, with the addition of soil remediation agent, showed a downward trend within a certain range of application rates; and the greater the amount of soil remediation agent added, the greater the decrease. The contents of the residual states gradually increased with the addition of the remediation agent, and the larger the amount added, the greater the increase; thereinto, 100 g/m2 had the best effect. It can be seen that the remediation agent had a significant passivation and fixation effect on heavy metals.
(2) Changes of Heavy Metal Forms in Soil
In order to further study the speciation changes of soil heavy metals Pb, Cu, Cr, Cd, Hg, and As after different amounts of remediation agent applied, the various forms of heavy metals were detected:
Methods of analyzing various forms of heavy metals: the speciation analysis of Pb, Cu, Cr, Cd and Hg in soil was determined by Tessier method, and the exchangeable state was extracted with 1 mol/L MgCl2 with pH 7 at room temperature with shaking for 1 h; the carbonate-bound state was extracted with 1 mol/L NaAc solution with pH 5 at room temperature with shaking for 6 h; the oxidation state of iron and manganese was extracted with a mixed solution of 0.04 mol/L NH2OH.HCl and 25% (v/v) HOAc at 96±3° C. with shaking for 6 h; for the organically bound state extraction, 0.02 mol/L HNO3+30% H2O2(pH=2) was used for shaking at 85±2° C. for 2 h, then 30% H2O2 was added to shake at 85±2° C. for 3 h, and then 3.2 mol/L of 20% (v/v) HNO3 was added to shake for 30 min; the residual state was analyzed by microwave digestion with 3 mL of nitric acid and 9 mL of hydrochloric acid.
The speciation of As in the soil was analyzed by the Wenel continuous extraction method, and the non-specific adsorption state of As was extracted with 0.05 mol/L (NH4)2SO4 solution with shaking for 4 h; the obligate adsorption state of As was extracted with 0.05 mol/L (NH4)H2PO4 solution with shaking for 16 h; the amorphous and weakly crystalline hydrated iron-aluminum oxide binding state of As was extracted with 0.2 mol/L (NH4)2C2O4 buffer (pH=3.25) under dark shaking for 4 h, washed with 0.2 mol/L (NH4)2C2O4 buffer (pH=3.25) with shaking for 10 min in the dark after centrifugation and filtration, and the supernatant was collected; the crystalline hydrated iron-aluminum oxide binding state of As was extracted with 0.2 mol/L (NH4)2C2O4 and 0.1 mol/L ascorbic acid solution at 96° C. for 30 min in a water bath, washed with 0.2 mol/L (NH4)2C2O4 buffer (pH=3.25) after centrifugation and filtration, and shaken for 10 min in the dark; the residual state was analyzed by microwave digestion with 3 mL of nitric acid and 9 mL of hydrochloric acid.
The experimental results showed that among the six different heavy metals, for the exchangeable state and carbonate-bound state of the forms of Pb, Cu, Cr, Cd, Hg, and As, which were migrable, transformable and easily absorbed by plants, the distribution rate showed a downward trend as the added amount increased, and the larger the added amount, the greater the decrease of distribution rate, with the remediation agent application amount in the range of 50-150 g/m2.
At the same time, it was found that when the application amount of the remediation agent was above 150 g/m2, the distribution rate of the exchangeable and carbonate-bound states of heavy metals no longer decreased. Therefore, the same conclusion was drawn from the change experiment of “changes of available and residual states of heavy metals in soil”; the application amount of the remediation agent of the present invention can be in the range of 50-200 g/m2, and the better range is 80-150 g/m2. Considering the cost and effectiveness, the optimal range is 80-120 g/m2 or 100 g/m2. Thereinto, the test results of the experimental groups with the application amount of 0, 50 g/m2, 100 g/m2 and 200 g/m2 are shown in Table 9-Table 14.
As can be seen from Table 9-14, among the six different metals, for the exchangeable state and carbonate-bound state of the forms of Pb, Cu, Cr, Cd, Hg, and As, which were migrable, transformable and easily absorbed by plants, the distribution rate showed a downward trend as the addition of the remediation agent within a certain range of application amount, and the larger the added amount, the greater the decrease of distribution rate; thereinto, 100 g/m2 worked best.
It can be seen that the remediation agent of the present invention has a significant passivation and fixation effect on heavy metals, and can repair heavy metal-contaminated soil.
3. Effects of the Remediation Agent on Heavy Metal Content of Crops
The content of heavy metals Pb, Cr, Cd, Hg and As in plants with different application amounts of remediation agent was detected. The detection method was as follows: the sample was carried out microwave digestion in nitric acid and 30% H2O2, and after cooling to room temperature, made up to 50 mL with 5 g/L tartaric acid; the contents of Pb, Cr and Cd were determined by flame atomic absorption spectrometer, and the contents of Hg and As were determined by fluorescence photometer.
The test results are shown in Table 15.
It can be seen from Table 15 that the contents of Pb, Cr, Cd, Hg, and As in Chinese cabbage decreased significantly after the soil remediation agent was added. Moreover, with the increase of the addition amount of the remediation agent, within a certain application amount range, its decreasing range gradually increased. In the experimental group with an application amount of about 100 g/m2, the heavy metals contents of the plants dropped below the qualified limits. It shows that the soil remediation agent of the present invention can significantly inhibit the absorption of heavy metals by plants.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202110500856.5 | May 2021 | CN | national |
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