CN109575925B - Preparation method and application of multifunctional soil cadmium metal passivator - Google Patents
Preparation method and application of multifunctional soil cadmium metal passivator Download PDFInfo
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- CN109575925B CN109575925B CN201811479033.3A CN201811479033A CN109575925B CN 109575925 B CN109575925 B CN 109575925B CN 201811479033 A CN201811479033 A CN 201811479033A CN 109575925 B CN109575925 B CN 109575925B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
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- 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
- C09K2101/00—Agricultural use
Abstract
The invention discloses a preparation method and application of a multifunctional soil cadmium metal passivator, and belongs to the field of farmland soil heavy metal pollution remediation treatment. The main raw materials of the passivator comprise medical stone, sodium hydroxide, sodium carbonate and the like, wherein the mass ratio of the medical stone to the sodium hydroxide to the sodium carbonate is 1: 0.1-0.15: 0.3 to 0.35. The specific preparation process comprises the following steps: 1) firstly, mixing medical stone powder, sodium hydroxide and sodium carbonate according to the proportion, uniformly stirring, carrying out heat treatment for 1-1.5 h at 700-750 ℃, taking out, cooling and grinding; 2) adding the passivating agent into an aqueous solution according to the solid-to-liquid ratio of 1:50, adjusting the pH to 7-8 by using 0.5mol/L diluted hydrochloric acid, drying and grinding to obtain the multifunctional silicate heavy metal passivating agent. The content of effective silicon in the multifunctional silicate heavy metal passivator is up to 30-35.00%, the multifunctional silicate heavy metal passivator can supplement a soil silicon source, adsorb and passivate heavy metal cadmium in soil, and reduce the content of cadmium in plant availability.
Description
Technical Field
The invention relates to the technical field of passivators for treating cadmium-polluted soil, in particular to a silicate passivator capable of reducing the effective cadmium content of acid soil and promoting crop growth, and a use method and application thereof.
Background
Cadmium (Cd) is one of five soil heavy metal pollutants which are mainly monitored and discharged by the nation, and has the characteristics of strong biotoxicity, irreversible property and incapability of being degraded. Investigation shows that the cadmium-polluted soil area in China is as high as 1000 vha. Cadmium mainly enters soil through metal smelting, sewage irrigation, massive use of chemical fertilizers and pesticides and the like, and not only causes soil fertility reduction and crop yield reduction in farmland soil, but also is enriched in organisms through a food chain way, and poses serious threat to human health.
The chemical passivation method is a commonly used soil heavy metal pollution treatment technology, and the method mainly adds a proper passivant into soil to enable the soil to generate a series of reactions such as adsorption, precipitation, complexation, ion exchange and the like with heavy metal ions, thereby changing the occurrence form of the heavy metal in the soil, reducing the absorption and toxicity effects of the heavy metal, and having the characteristics of simple operation, low cost and suitability for large-scale application.
The common passivators comprise phosphates, carbonates, silicates and the like, and compared with the silicate passivators and the silicate passivators, the silicate passivators have the advantages of wide sources, no change of the physical and chemical properties of soil, no introduction of secondary pollution and the like. Silicon fertilizer and clay mineral are common silicate passivators, and silicon fertilizer such as steel slag silicon fertilizer, iron-smelting slag silicon fertilizer and the like has high effective silicon content, is used for passivating soil heavy metals and increasing the effective silicon content of soil, has the advantages of citrate dissolution, slow release, crop growth promotion and the like, but has structural defects, so that the adsorption performance and the ion exchange capacity are influenced, and the application of the silicon fertilizer in cadmium-polluted farmlands is limited. Clay minerals are mostly used for soil heavy metal pollution treatment, silicon element exists in minerals in a stable form and is difficult to be absorbed and utilized by plants, the function is single, and a large amount of silicon is not fully utilized. According to investigation, about 60 percent of cultivated land in China belongs to silicon-deficient soil, more than 70 percent of Yangtze river basin is in silicon deficiency, about 50 percent of Huang-Huai basin and Liaodong peninsula is in silicon deficiency, and the area of the silicon-deficient soil is increased year by year at present.
According to the current situations of heavy metal pollution and silicon shortage of farmland soil in China, the soil heavy metal pollution remediation and crop yield increase are combined, and the multifunctional silicate soil heavy metal passivator which has the functions of adsorption, precipitation and biological inhibition on soil heavy metals and is beneficial to crop growth is developed, and has important significance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a multifunctional soil cadmium metal passivator, which has the advantages of wide raw material source, simple preparation process, small application amount, adsorption, precipitation and biological inhibition functions on soil heavy metals, is beneficial to crop growth, and can effectively solve the technical problems of silicon deficiency and cadmium pollution of soil in China.
And the application thereof in passivating the cadmium polluted farmland soil,
in order to achieve the purpose, the invention adopts the following technical scheme:
the multifunctional soil cadmium metal passivator comprises the following raw material components of medical stone, sodium hydroxide and sodium carbonate in a mass ratio of 1: (0.1-0.15): (0.3-0.35).
The preparation method of the multifunctional silicate passivator comprises the following steps:
1) firstly, mixing medical stone powder, sodium hydroxide and sodium carbonate according to a mass ratio of 1: (0.1-0.15): (0.3-0.35), uniformly stirring, carrying out heat treatment at 700-750 ℃ for 1-1.5 h, taking out, cooling and grinding;
2) passivating agent is added according to the solid-liquid ratio of 1:50, adding an aqueous solution, adjusting the pH value to 7-8 by using 0.5mol/L diluted hydrochloric acid, drying at 70-80 ℃, and grinding to obtain the multifunctional silicate heavy metal passivator.
In the preparation method of the multifunctional silicate passivator, in the step 1), the medical stone powder is Chinese medical stone powder which is produced in Tongliao city of inner Mongolia and has a particle size of less than 0.1 mm; the effective silicon content of the multifunctional silicate passivator is 30.0-35.0%.
The application method of the multifunctional silicate passivator comprises the steps of applying the multifunctional silicate passivator serving as a base fertilizer into contaminated soil before planting, wherein the application amount is 3-5 g/kg of the contaminated soil, and applying the passivator when a vegetable crop nursery grows for 5-10 cm, wherein the application amount is 1g/kg of the contaminated soil.
According to the application method of the multifunctional silicate passivator, the polluted soil is subacid farmland soil polluted by medium and light cadmium, the concentration of effective cadmium in the farmland soil is 3-5 mg/kg, and the pH value of the soil is 5.5-6.0.
The multifunctional soil cadmium metal passivator is applied to subacid moderate and light cadmium polluted farmland soil; the concentration of the effective cadmium in the farmland soil is 3-5 mg/kg, the pH value of the soil is 5.5-6.0, the pH value of the soil after remediation is 5.90-6.97, and compared with a control, the effective cadmium content of the soil after remediation is reduced by 16.63% -31.20%.
The multifunctional soil cadmium metal passivator has the following advantages and beneficial effects:
1) the multifunctional silicate passivator for cadmium pollution of farmland soil has wide raw material sources, is economic and efficient, has no pollution, can improve acid soil, and is an environment-friendly silicate passivator;
2) the invention has higher effective silicon content, can replace silicon fertilizer and passivator to be applied to polluted soil, promotes the crop yield increase, passivates soil heavy metal, and reduces the application cost;
3) the invention adopts natural minerals as raw materials, has high utilization rate of silicon element, simple preparation process, convenient application, slow release, high efficiency and the like, and is suitable for large-scale popularization and application.
Detailed Description
In order to better understand the present invention, the following further illustrates the present invention by combining the contents of the effect test examples with specific preferred embodiments, but the present invention is not limited to the following examples.
The invention discloses a preparation method and application of a multifunctional soil cadmium metal passivator, wherein the passivator is prepared from the main raw materials of medical stone, sodium hydroxide and sodium carbonate, wherein the mass ratio of the medical stone to the sodium hydroxide to the sodium carbonate is 1: (0.1-0.15): (0.3-0.35).
In the invention, the medical stone is Chinese medical stone which is produced in Tongliao city of inner Mongolia, the particle size is less than 0.1mm, and the used sodium hydroxide and sodium carbonate are all industrial pure and do not contain crystal water.
The effective silicon content of the soil cadmium metal passivator reaches 30.0-35.0%, so that a soil silicon source can be supplemented, heavy metal cadmium in soil can be adsorbed and passivated, and the cadmium content in plant availability can be reduced; after the effective silicon is absorbed by plants, the biomass can be increased, the plants can be promoted to secrete hormones such as antioxidant enzyme and the like, the absorption rate of the plants to heavy metals and the migration conversion rate of the heavy metals in the plants are reduced, and the toxic action of the heavy metals to the plants is relieved.
The invention can be used for treating mildly or moderately polluted acidic farmland soil with cadmium pollution, has the characteristics of simple formula process, economy, high efficiency, no secondary pollution, convenient application and the like, and is suitable for large-scale popularization and application.
The following percentages are mass percentages.
Example 1
A preparation method of a multifunctional soil cadmium metal passivator adopts the following process steps:
1) firstly, medical stone powder (the particle size is less than 0.1mm), sodium hydroxide and sodium carbonate are mixed according to the weight ratio of 1: 0.1: 0.3, mixing, uniformly stirring, carrying out heat treatment at 700 ℃ for 1h, taking out, cooling and grinding;
2) passivating agent is added according to the solid-liquid ratio of 1:50, adding an aqueous solution, adjusting the pH to 7-8 by using 0.5mol/L diluted hydrochloric acid, drying at 70-80 ℃, and grinding to prepare the multifunctional silicate heavy metal passivator. The content of effective silicon in the multifunctional silicate passivator is 30.0 percent.
Example 2
A preparation method of a multifunctional soil cadmium metal passivator adopts the following process steps:
1) firstly, medical stone powder (the particle size is less than 0.1mm), sodium hydroxide and sodium carbonate are mixed according to the weight ratio of 1: 0.15: 0.35, uniformly stirring, carrying out heat treatment at 750 ℃ for 1.5h, taking out, cooling and grinding;
2) passivating agent is added according to the solid-liquid ratio of 1:50, adding an aqueous solution, adjusting the pH to 7-8 by using 0.5mol/L diluted hydrochloric acid, drying at 70-80 ℃, and grinding to prepare the multifunctional silicate heavy metal passivator. The content of effective silicon in the multifunctional silicate passivator is about 35.0 percent.
Example 3
A preparation method of a multifunctional soil cadmium metal passivator adopts the following process steps:
1) firstly, medical stone powder (the particle size is less than 0.1mm), sodium hydroxide and sodium carbonate are mixed according to the weight ratio of 1: 0.12: 0.32, uniformly stirring, carrying out heat treatment at 730 ℃ for 1.2h, taking out, cooling and grinding;
2) passivating agent is added according to the solid-liquid ratio of 1:50, adding an aqueous solution, adjusting the pH to 7-8 by using 0.5mol/L diluted hydrochloric acid, drying at 70-80 ℃, and grinding to prepare the multifunctional silicate heavy metal passivator. The content of effective silicon in the multifunctional silicate passivator is about 33.0 percent.
The following are contents of the effect test examples.
Effect test example 1
The soil is collected from the surface soil (0-25 cm) of a certain vegetable near Cen village in Tian river area of Guangzhou city, Guangdong province, is naturally air-dried, is cleaned of impurities, and is ground and then is screened by a 2mm screen for later use.
The pH value of the soil is 5.71 (water: soil is 2.5: 1), and the organic matter content is 13.2g/kg-1Total nitrogen 0.78g/kg-1Available phosphorus 39.0mg/kg-1Quick-acting potassium of 127mg/kg-1The total cadmium content is 0.25mg/kg-1。
By adding Cd (NO)3)2·4H2The O solution makes the cadmium concentration of the soil to be 3 mg-kg-1Uniformly stirring, after the soil is air-dried, respectively filling the soil into flowerpots with the specification of 300 x 140 x 120mm according to the proportion of 5 kg/pot, uniformly stirring, adding water every three days, keeping the water content to be 70% of the maximum field water holding capacity, and then placing for later use under natural conditions.
After the cadmium-polluted soil is prepared, the multifunctional silicate passivator is added to the experimental group at the tenth day, the application amount of the multifunctional silicate passivator is 3g/kg of the polluted soil, and the passivator is added to the polluted soil at the rate of 1g/kg after 15 days of seedling emergence (adopting black leaf pakchoi). And 5 groups of parallel samples are set by a pilot, the pakchoi is harvested 35 days after planting, and the pakchoi is cleaned and tested.
The growth parameters of the pakchoi and the soil remediation condition are tested, and are shown in the following table 1:
table 1 effects example 1 results
From the results of table 1 above, it can be seen that: the effective state of the Cd in the treated soil can be reduced from 93.3% to 64.21%, and the reduction amplitude can reach 31.20%. In addition, the average weight gain of each Chinese cabbage can reach 107.37 percent maximally; the Cd content (fresh weight) of the pakchoi can be reduced to 0.03mg/kg from 0.09mg/kg when the pakchoi is not added, the reduction range can reach 64.29%, and the Cd content of the overground part of the pakchoi after treatment reaches the national standard of food safety (GB 2762-2012).
Effect test example 2
Soil near a certain smelting plant is selected as experimental soil, and the total cadmium content in the soil is determined to be about 5mg/kg-1The effective state proportion is 35 percent, the soil is dried in the air and then is subpackaged in flowerpots with the specification of 300 x 140 x 120mm according to the proportion of 5 kg/pot, the mixture is uniformly stirred, water is added every three days, the water content is kept to be 70 percent of the maximum water holding capacity in the field, and then the mixture is placed for standby under the natural condition. And respectively adding 5g/kg of the multifunctional silicate passivator to the experimental groups on the tenth day, and adding 1g/kg of the passivator to the polluted soil 15 days after seedlings emerge (black leaf pakchoi is adopted). And 5 groups of parallel samples are set by a pilot, the pakchoi is harvested 35 days after planting, and the pakchoi is cleaned and tested.
Table 2 effects example 2 results
As can be seen from Table 2, the effective state reduction amplitude of the Cd in the treated soil is as low as 16.64%, and the average weight gain of each plantlet of the Chinese cabbage is as low as 77.80%; the Cd content (fresh weight) of the pakchoi can be reduced to 0.05mg/kg from 0.09mg/kg when not added, the reduction range is at least 12.57%, and the Cd content of the overground part of the pakchoi after treatment reaches the national food safety standard (GB 2762-2012).
Compared with the effect test example 1 and the effect test example 2, the multifunctional soil passivator disclosed by the invention is prepared from medical stone serving as a raw material by adding an activating agent to prepare the multifunctional soil heavy metal passivator with high effective silicon content, and can realize double effects of passivating soil heavy metal and promoting crop growth.
The multifunctional silicate passivator disclosed by the invention is simple in preparation process, wide in raw material source, free of secondary pollution, capable of achieving the purpose of high efficiency and economy, and capable of providing an identification experience for the development of a soil heavy metal passivator.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, so that any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (4)
1. The multifunctional soil cadmium metal passivator is characterized by comprising the following raw materials of medical stone, sodium hydroxide and sodium carbonate in a mass ratio of 1: (0.1-0.15): (0.3 to 0.35);
the preparation method of the multifunctional soil cadmium metal passivator comprises the following steps:
1) firstly, mixing medical stone powder, sodium hydroxide and sodium carbonate according to a mass ratio of 1: (0.1-0.15): (0.3-0.35), uniformly stirring, carrying out heat treatment at 700-750 ℃ for 1-1.5 h, taking out, cooling and grinding; 2) mixing clinker with a solid-liquid ratio of 1:50, adding an aqueous solution, adjusting the pH value to 7-8 by using 0.5mol/L diluted hydrochloric acid, drying at 70-80 ℃, and grinding to obtain the multifunctional silicate heavy metal passivator.
2. The multifunctional soil cadmium metal passivator of claim 1, wherein: in the step 1), the medical stone powder is Chinese medical stone powder produced in Tongliao city of inner Mongolia, and the particle size is less than 0.1 mm; the effective silicon content of the multifunctional silicate passivator is 30.0-35.0%.
3. The use method of the multifunctional soil cadmium metal passivator as claimed in claim 1, wherein: the multifunctional silicate passivator is applied to polluted soil as a base fertilizer before planting, the application amount is 3-5 g/kg of the polluted soil, and 1g/kg of the passivator product of the polluted soil is applied when a vegetable crop nursery grows to 5-10 cm.
4. The use method of the multifunctional soil cadmium metal passivator of claim 3, wherein:
the polluted soil is subacid farmland soil polluted by medium and light cadmium, the concentration of the effective cadmium in the farmland soil is 3-5 mg/kg, and the pH value of the soil is 5.5-6.0.
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| CN104761332B (en) * | 2015-03-16 | 2017-04-05 | 济南覆陇肥料科技有限公司 | The water-soluble mineral siliceous fertilizer of Maifanitum |
| CN108531186A (en) * | 2018-05-21 | 2018-09-14 | 广东中金岭南环保工程有限公司 | A kind of soil heavy metal passivant and its preparation method and application |
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| JP4610912B2 (en) * | 2004-03-09 | 2011-01-12 | カワサキプラントシステムズ株式会社 | Greening material composition using waste as a raw material and greening material using the same |
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Effective date of registration: 20210805 Address after: Room 3005 (b), management committee building, 23 Chuangye Road, industrial transfer industrial park, Zhenjiang District, Shaoguan City, Guangdong Province, 512023 Patentee after: GUANGDONG ZHONGJIN LINGNAN ENVIRONMENTAL PROTECTION ENGINEERING Co.,Ltd. Address before: 510006 Institute of environmental research, South China Normal University, 378 Waihuan West Road, Panyu District, Guangzhou City, Guangdong Province Patentee before: SOUTH CHINA NORMAL University |