CN107649498B - Method for inhibiting plants from absorbing soil fluorine by using activated sludge modified clay mineral - Google Patents
Method for inhibiting plants from absorbing soil fluorine by using activated sludge modified clay mineral Download PDFInfo
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- CN107649498B CN107649498B CN201710718629.3A CN201710718629A CN107649498B CN 107649498 B CN107649498 B CN 107649498B CN 201710718629 A CN201710718629 A CN 201710718629A CN 107649498 B CN107649498 B CN 107649498B
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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
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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
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
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- 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
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a method for inhibiting plants from absorbing soil fluorine by using activated sludge modified clay minerals. The technical scheme of the invention comprises the following steps: the preparation method comprises the steps of measuring clear water, putting the clear water into a container, adding a certain amount of glucose, calcium superphosphate and urea, and fully stirring to dissolve the glucose, the calcium superphosphate and the urea; secondly, collecting activated sludge in a biochemical tank of an urban sewage treatment plant as strains, putting the strains into the container in the step, adding clay minerals, stirring uniformly, and then performing intermittent aeration; after aeration is finished, adding calcium chloride, uniformly stirring, and standing for precipitation; fourthly, collecting the precipitate obtained by separation in the step three, leaching the precipitate with clear water, and then performing high-temperature treatment to obtain the clay mineral modified by the activated sludge; and fifthly, adding the activated sludge modified clay mineral into the plough layer of the fluorine-polluted soil, turning and mixing, and then carrying out conventional planting on plants. The method is simple to operate and low in cost, and can fix the fluorine element in the soil in the space structure of the clay minerals, so that the absorption of plants is effectively inhibited.
Description
Technical Field
The invention belongs to the technical field of soil pollution remediation, and particularly relates to a method for inhibiting plants from absorbing soil fluorine by using activated sludge modified clay minerals.
Background
Fluorine (F) is one of the trace elements in the normal physiological activities of the body, but if it is taken excessively, it can cause fluorosis symptoms such as fluorosis, dental fluorosis, and brain injury, which are called endemic fluorosis, commonly called diflunisal. The disease belongs to a typical geochemical disease, affects a plurality of countries and regions in the world, and is a highly distributed country of the difluoro disease. The diseases caused by the defluorination are generally divided into four major types, namely drinking water type, food type, coal-fired type and mixed type. The defluorination caused by the soil fluorine pollution belongs to a mixed type, namely the soil fluorine pollution can pollute shallow groundwater through the functions of percolation and the like, thereby becoming a source of drinking water type defluorination. Meanwhile, the fluorine pollution of the soil can be accumulated in the plant body due to the absorption of the plant, and the fluorine pollution is ingested by human beings through directly eating vegetable and fruit grains or indirectly eating livestock and meat which feeds the high-fluorine plant, namely, the human health is influenced through a food chain. Therefore, the method has important practical significance for repairing soil fluorine pollution and preventing fluorine from entering a food chain by inhibiting the absorption of plants to fluorine.
At present, research and development of remediation technologies for inorganic pollution in soil are mostly concentrated in the heavy metal field, and related achievements are more. However, heavy metals belong to cations, and fluorine generally exists in an anion form, so that the treatment technology and the application effect are essentially different. Relatively few reports of remediation techniques for soil fluorine pollution are made.
The invention patent CN201510728049.3 discloses a fluorine-contaminated soil repairing agent and a repairing method, wherein modified peat, calcium magnesium phosphate fertilizer, calcium carbonate, calcium oxide, calcium hydroxide and the like are mainly used and prepared into turbid liquid to irrigate soil, and the method can adsorb and precipitate water-soluble fluorine ions and has a good effect on drinking water type fluorine contamination. The invention patent CN201310195260.4 discloses a method for reducing water-soluble fluorine content of soil, which comprises mixing tannin with Al 3+ 、Fe 3+ 、Ce 3+ 、Zr 4+ The water-soluble fluorine adsorbent is prepared by plasma, and is mixed with the NPK-humic acid slow release fertilizer for modification, so that the water-soluble fluorine can be fixed in soil, and the harm to crops is reduced to a certain extent.
The method uses exogenous industrial substances, needs extra attention in the operation process, and has certain secondary pollution risk to soil. In addition, the remediation of the fluorine-contaminated soil mainly aims at water-soluble fluorine, and the absorption of plant roots to nutrient substances in the soil is related to the water-soluble state, but as a biological transmission mode, factors such as molecular chain length, molecular weight, surface group property and the like of an absorption object have great influence.
Therefore, the method has important significance for repairing the soil fluorine pollution and reducing the influence of the soil fluorine pollution on human health, and the related repairing technology has certain limitation at present, and the method for developing and inhibiting the plants from absorbing the soil fluorine has feasibility and application prospect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for effectively inhibiting plants from absorbing soil fluorine by taking clay minerals in natural soil as main components and activating and modifying the surface structure of the clay minerals by utilizing activated sludge as a soil additive. The method is simple to operate, low in cost, friendly to soil environment and free of side effects, and can remarkably reduce the absorption of fluorine elements in the soil by plants, so that the harm of fluorine pollution of the soil to human bodies at the food chain ends is reduced.
The technical scheme of the invention is as follows: a method for inhibiting plants from absorbing soil fluorine by using activated sludge modified clay minerals comprises the following steps:
the preparation method comprises the steps of measuring clear water, putting the clear water into a container, adding a certain amount of glucose, calcium superphosphate and urea, and fully stirring to dissolve the glucose, the calcium superphosphate and the urea;
secondly, collecting activated sludge in a biochemical tank of an urban sewage treatment plant as a strain, putting the strain into the container in the step, adding clay minerals, uniformly stirring, and then carrying out intermittent aeration;
thirdly, after the aeration is finished, adding calcium chloride, uniformly stirring, and standing for precipitation;
fourthly, collecting the precipitate obtained by separation in the step three, leaching the precipitate with clear water, and then performing high-temperature treatment to obtain the clay mineral modified by the activated sludge;
and fifthly, adding a proper amount of the activated sludge modified clay mineral into the plough layer of the fluorine-polluted soil, turning and mixing, and then carrying out conventional planting on plants.
In the method for inhibiting soil fluorine absorption of plants by using activated sludge modified clay minerals, the ratio of raw materials is 1m 3 Adding 200-300 g of glucose, 9-13 g of superphosphate and 30-45 g of urea into clear water.
In the method for inhibiting the plants from absorbing the soil fluorine by using the activated sludge modified clay mineral, the addition amounts of the activated sludge and the clay mineral in the second step are as follows: 1m 3 Adding 1.0-1.5 kg (by dry matter mass) of activated sludge into the clear water, and adding clay ore10-15 kg of the product.
In the method for inhibiting the plants from absorbing the soil fluorine by using the activated sludge modified clay mineral, the clay mineral is preferably calcium-based minerals of montmorillonite family, kaolinite family and vermiculite family.
In the method for inhibiting the activated sludge modified clay minerals from absorbing soil fluorine by plants, intermittent aeration is carried out for 6 to 8 hours at intervals of 2 to 3 hours, the total aeration time is based on the formation of a biological film on the particle surface, preferably 3 to 5 days, the aeration quantity is based on the fluidized state of the activated sludge and the clay minerals, and preferably, the aeration quantity in unit area is 3 to 4m 3 /h。
In the method for inhibiting the plants from absorbing the soil fluorine by using the activated sludge modified clay mineral, the addition amount of calcium chloride in the step three is as follows: at 1m 3 Adding 0.3-0.5 kg of calcium chloride into clear water.
In the method for inhibiting the activated sludge modified clay mineral from absorbing soil fluorine by plants, the precipitate in the step four is collected, rinsed 2-3 times with clear water, and then treated at a high temperature of 120 ℃ for 15-30 min.
In the method for inhibiting the plants from absorbing the soil fluorine by using the activated sludge modified clay mineral, the thickness of the soil tillage layer mixed with the activated sludge modified clay mineral in the step is 15-20 cm, and the volume ratio of the addition amount of the activated sludge modified clay mineral to the soil of the tillage layer is 10-15%.
The invention has the following beneficial effects:
the method has the advantages that the operation is simple, the cost is low, and the fluorine element in the soil can be fixed in a space structure of the clay mineral through the effects of adsorption, chelation and the like, so that the absorption of the fluorine element by plants is effectively inhibited, and the risk that the fluorine element migrates to the inside of a living body through the end of a food chain is reduced;
the clay mineral is a component of natural soil and has good fusion with the soil. The special crystal space structure of the clay mineral enables the clay mineral to have larger surface area, complexing ability and ion exchange ability, not only can react with organic substances to form a complex, but also cations such as Ca, mg and the like in the clay mineral and fluorine ions can form stronger bonding force.
The activated sludge can form a biological film on the surface of the clay mineral and secrete a large amount of extracellular polymers in an aeration aerobic state, the biological molecules can be inserted into the crystal structure of the clay mineral to form an organic complex with a nanoscale effect, and the organic complex has a longer molecular chain combined with fluorine ions, a larger molecular weight and a more stable molecular structure;
the activated sludge of the urban sewage plant is used as the strain, so that the strain is rich in structure types and good in biological performance. By means of bacterial aeration and biofilm formation, a large amount of newly proliferated microorganisms can effectively reduce the risk of high concentration of pollutants such as heavy metals in urban sewage plants and eliminate secondary pollution to soil.
The soluble organic complex and surface ions are removed through the leaching effect, so that negative effects on biological effectiveness after the soluble organic complex and the surface ions are combined with the fluorine in the soil are reduced. Meanwhile, through high-temperature treatment and addition of exogenous calcium chloride, more active groups such as carboxyl, hydroxyl, aldehyde and the like are exposed from biomembrane cells and extracellular secretions, the surface binding sites of the modified clay mineral are increased, and more fluorine ions and fluorides are chelated through the bridge action of cations.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
A method for inhibiting plants from absorbing soil fluorine by using activated sludge modified clay minerals comprises the following steps:
measuring clear water 10m 3 Putting the mixture into a water tank, adding 2300g of glucose, 120g of calcium superphosphate and 430g of urea, and fully stirring to dissolve the glucose, the calcium superphosphate and the urea;
adding 13kg of activated sludge (calculated by dry matter mass) in a biochemical tank of an urban sewage treatment plant into the water tank to serve as a strain, and stirring uniformly, wherein 120kg of clay mineral is added; the aeration rate per unit area is 3.8m 3 A blower fan for continuously aerating for 6 hours every 2.5 hours and 5 days laterStopping aeration;
adding 4.3kg of calcium chloride into the water tank, uniformly stirring, standing for precipitation,
fourthly, collecting the precipitate, then rinsing the precipitate for 3 times with clear water, and treating the precipitate at the high temperature of 120 ℃ for 25min to obtain activated sludge modified clay mineral;
fifthly, adding the activated sludge modified clay mineral to 15cm of the cultivated layer of the fluorine-polluted soil to enable the thickness of the activated sludge modified clay mineral to be about 1.5cm, enabling the volume of the activated sludge modified clay mineral to be about 10% of the volume of the cultivated layer soil, turning soil, mixing, and planting vegetables and fruits.
In addition, the activated sludge modified clay mineral is not added to the fluorine-polluted soil, the same crops are directly planted to serve as blank control, and the treatment modes and the use amounts of watering, fertilizing and the like at the later stage are consistent. And (3) detecting the fluorine content of the edible parts of the plants after harvesting as follows:
example 2
Measuring clear water 10m 3 Putting the mixture into a water tank, adding 2800g of glucose, 100g of calcium superphosphate and 380g of urea, and fully stirring to dissolve the glucose, the calcium superphosphate and the urea;
adding 12kg of activated sludge (calculated by dry matter mass) in a biochemical tank of an urban sewage treatment plant as a strain and 130kg of clay mineral, and uniformly stirring; the aeration rate per unit area is 3.5m 3 The blower is used for continuously aerating for 8 hours every 2 hours, and the aeration is stopped after 4 days;
adding 3.5kg of calcium chloride into the three-dimensional ground substance, uniformly stirring, and standing for precipitation;
fourthly, collecting the precipitate, then leaching the precipitate with clear water for 2 times, and treating the precipitate at the high temperature of 120 ℃ for 30min to obtain activated sludge modified clay minerals;
fifthly, adding the activated sludge modified clay mineral into the tillage layer 20cm of the fluorine-polluted soil to enable the volume of the activated sludge modified clay mineral to be about 15% of the volume of the tillage layer soil, turning and mixing the soil, and planting crops.
In addition, the activated sludge modified clay mineral is not added to the fluorine-contaminated soil, the same crops are directly planted to serve as blank control, and the treatment modes and the use amounts of watering, fertilizing and the like at the later stage are consistent. And (3) detecting the fluorine content of the edible parts of the plants after harvesting as follows:
example 3
Measuring clear water 10m 3 Putting into a water pool, adding 2100g of glucose, 95g of calcium superphosphate and 320g of urea, and fully stirring to dissolve the glucose, the calcium superphosphate and the urea;
adding 11kg of activated sludge (calculated by dry matter mass) in a biochemical tank of an urban sewage treatment plant as a strain and 150kg of clay mineral, and uniformly stirring; the aeration rate per unit area is 4.0m 3 The blower fan is used for continuously aerating for 7 hours every 3 hours, and the aeration is stopped after 3 days;
adding 4kg of calcium chloride into the three-dimensional ground substance, uniformly stirring, standing and precipitating;
fourthly, collecting the precipitate, then rinsing the precipitate for 3 times by using clear water, and treating the precipitate at the high temperature of 120 ℃ for 20min to obtain activated sludge modified clay mineral;
fifthly, adding the activated sludge modified clay mineral into a 15cm tillage layer of unpolluted soil to enable the volume of the activated sludge modified clay mineral to be about 13% of the volume of the soil of the tillage layer, turning and mixing soil, planting vegetables and fruits, and irrigating with a fluorine-polluted water source.
In addition, the activated sludge modified clay mineral is not added to the soil, the same crops are directly planted to serve as blank control, and the treatment modes and the use amounts of watering, fertilizing and the like at the later stage are consistent. And (3) detecting the fluorine content of the edible parts of the plants after harvesting as follows:
Claims (8)
1. a method for inhibiting plants from absorbing soil fluorine by using activated sludge modified clay minerals is characterized by comprising the following steps:
(1) Weighing clear water, putting into a container, adding a certain amount of glucose, calcium superphosphate and urea, and fully stirring to dissolve;
(2) Collecting activated sludge in a biochemical tank of an urban sewage treatment plant as a strain, putting the strain into the container in the step (1), adding clay minerals, uniformly stirring, and then carrying out intermittent aeration, wherein the intermittent aeration adopts a mode of continuously aerating for 6-8 hours at intervals of 2-3 hours, the total aeration time is limited by forming a biological film on the surface of particles, and the aeration quantity is limited by ensuring that the activated sludge and the clay minerals are in a fluidized state;
(3) After aeration is finished, adding calcium chloride, uniformly stirring, and standing for precipitation;
(4) Collecting the precipitate obtained in the step (3), leaching with clear water, and performing high-temperature treatment to obtain activated sludge modified clay minerals;
(5) Adding a proper amount of the activated sludge modified clay mineral into a plough layer of the fluorine-polluted soil, turning and mixing, and then carrying out conventional planting on plants.
2. The method for inhibiting the absorption of soil fluorine by plants by using the activated sludge modified clay mineral as claimed in claim 1, wherein the ratio of raw materials in the step (1) is 1m 3 Adding 200-300 g of glucose, 9-13 g of calcium superphosphate and 30-45 g of urea into clear water.
3. The method for inhibiting the plants from absorbing the soil fluorine by using the activated sludge modified clay mineral according to the claim 1 or 2, wherein the adding amount ratio of the activated sludge to the clay mineral in the step (2) is as follows: 1m 3 1.0-1.5 kg of activated sludge and 10-15 kg of clay minerals are added into the clear water by dry matter mass.
4. The method for inhibiting soil fluorine absorption by plants according to claim 3, wherein the clay mineral is one or more of calcium-based minerals of montmorillonite group, kaolinite group and vermiculite group.
5. The method for inhibiting the absorption of fluorine in soil by plants through activated sludge modified clay mineral according to claim 1, wherein the aeration amount per unit area is 3 to 4m 3 The aeration time is 3 to 5 days.
6. The method for inhibiting the absorption of soil fluorine by plants by using the activated sludge modified clay mineral according to claim 1 or 2, wherein the addition amount of the calcium chloride in the step (3) is as follows: at 1m 3 Adding 0.3-0.5 kg of calcium chloride into clear water.
7. The method for inhibiting the plants from absorbing the soil fluorine by using the activated sludge modified clay mineral according to the claim 1 or 2, characterized in that the precipitate in the step (4) is collected, rinsed with clear water for 2-3 times, and then treated at a high temperature of 120 ℃ for 15-30 min.
8. The method for inhibiting the absorption of soil fluorine by plants according to claim 1 or 2, wherein the thickness of the soil plough layer mixed with the activated sludge modified clay mineral in the step (5) is 15-20 cm, and the ratio of the addition amount of the activated sludge modified clay mineral to the soil volume of the plough layer is 10-15%.
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| CN110055075A (en) * | 2019-04-12 | 2019-07-26 | 中节能大地环境修复有限公司 | A kind of compound drug and its application method for acidic fluoride contaminated soil |
| CN113020242A (en) * | 2021-03-11 | 2021-06-25 | 中铝环保生态技术(湖南)有限公司 | Fluorine-contaminated soil remediation agent and laboratory application method |
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| CN102225870B (en) * | 2011-04-21 | 2013-06-12 | 合肥工业大学 | Attapulgite clay porous ceramsite, and preparation method and purpose thereof |
| CN103242110B (en) * | 2013-05-23 | 2015-03-04 | 四川师范大学 | Method for reducing content of water-soluble fluorine in soil |
| CN105419804B (en) * | 2015-10-30 | 2018-09-25 | 深圳市铁汉生态环境股份有限公司 | The renovation agent and a kind of restorative procedure of fluoride pollution soil of a kind of fluoride pollution soil |
| CN105498683A (en) * | 2015-12-01 | 2016-04-20 | 长江水资源保护科学研究所 | Preparation method of modified clay mineral material for purification of fluorine-containing sewage |
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