CN109181704B - Soil heavy metal and organic pollution remediation agent and preparation and application methods thereof - Google Patents
Soil heavy metal and organic pollution remediation agent and preparation and application methods thereof Download PDFInfo
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Abstract
The invention discloses a soil heavy metal and organic pollution repairing agent and a preparation and application method thereof, wherein the repairing agent comprises the following components: biochar, turfy soil, selenium methionine, bacillus laterosporus, clay minerals, iron-containing compounds, silicon-containing compounds, humic acid and biomass. The restoration agent can obviously reduce the content of heavy metals and organic pollutants in soil or water, does not generate secondary pollution, does not generate soil hardening phenomenon, effectively improves the soil quality, reduces the use amount of chemical fertilizers and pesticides, has simple operation flow, short period and quick effect, and is beneficial to the treatment and restoration application of large-area pollution of soils with different structures, different types of fields, different types of water bodies and the like.
Description
Technical Field
The invention relates to the technical field of soil heavy metal and/or organic pollution remediation agents.
Background
The soil is a source of everything and is the root of human production and life. With the development of modern industry and agriculture, the harmful substances accumulated in soil are increasing continuously, the food safety problem is formed when agricultural production activities are carried out on the polluted soil, the living, the life and the like on the polluted soil can directly harm the health of human beings, besides, part of harmful cost also participates in the natural and ecological system circulation of various forms of solid, liquid, gas and the like, and the harm is caused to human bodies and the nature in a wider range.
Common pollution forms of soil include inorganic pollution and organic pollution, wherein the inorganic pollution is most obvious and most harmful in heavy metal element pollution, and the organic pollution is most obvious and most harmful in chemical fertilizers, pesticides, insecticides and herbicides.
The heavy metal element pollution is typified by five heavy metal elements of lead, cadmium, mercury, arsenic and chromium, and the second is a general heavy metal element with certain toxicity, such as: copper, zinc, nickel, cobalt, tin, and the like. The sources of heavy metal elements in soil, besides the inherent heavy metal components of the soil, the enrichment of industrial waste gas, waste water, dust, waste residue, atmosphere, automobile exhaust, household garbage and the like aggravates the content of the heavy metal elements in the soil. Researches show that after the heavy metal elements enter the soil, the heavy metal elements not only have negative influence on the physical property, the biomass, the population structure, the soil enzyme activity and the whole soil ecosystem, but also interfere the development and the metabolic capability of crops, lead the soil to be hardened, acidified and reduced in fertility, lead the quality and the yield of the crops to be reduced, finally accumulate in the human body continuously through a food chain and cause harm to the health of the human body. Meanwhile, in order to offset the reduction of crop quality, yield, disease resistance and the like caused by heavy metal pollution of soil, a grower often further increases the dosage of pesticides, chemical fertilizers and the like, increases organic pollution, causes the superposition of organic and inorganic pollution, and continuously increases the soil deterioration degree of the polluted soil.
Under the realistic situation of severe inorganic heavy metal pollution and organic pollution, China still faces the problem of non-point source pollution that much of the pollution is difficult to control. The non-point source pollution is also called non-point source pollution, has no fixed pollution discharge place, mainly comprises soil silt particles, nutrient substances such as nitrogen and phosphorus, pesticides, various atmospheric particulates and other various components, enters water, soil or atmospheric environment in the modes of surface runoff, soil erosion, farmland drainage and the like, has the characteristics of randomness, universality, hysteresis, fuzziness, latency and the like, and further increases the difficulty of research, treatment and management policy establishment.
In the prior art, a large amount of research and disclosure are carried out on a soil repairing agent, and the soil repairing agent mainly relates to technical means such as engineering measures, chemical passivation, plant repair and the like. However, the prior art generally has the problems of single repair approach, serious technical homogenization and the like, so that the repair treatment effect is not obvious, the cost is high, the period is long, the application rate is low, and the risk of potential secondary pollution is caused.
For example, the invention patent application CN102559198A discloses a technical scheme of taking low-grade phosphate rock powder as a main raw material to be mixed with ammonium oxalate to prepare a passivator, and the passivator is used for passivating copper, lead and cadmium compound polluted farmlands, although the process is simple and convenient and the cost is low, the phosphate passivator can reduce the pH value of soil in actual use, and when the pH value of the soil is reduced, the exchangeable activity of heavy metals in the soil is enhanced, and the toxicity concentration is increased; the passivation effect of the phosphate passivator on the polluted soil is greatly related to the types of heavy metals, the soil property, the water content and the repair time, the passivation effect of heavy metal elements is often difficult to achieve the expected effect under different soil structures, and the addition of the phosphate has no obvious effect on the adsorption of copper under different soil environments. Besides, researches show that the phosphorus ore powder contains heavy metal cadmium element, and the phosphorus ore powder is used as a main raw material, so that the remediation target is difficult to achieve, and the cadmium enrichment in soil is aggravated. Although the cost of the passivator is low, the repair effect is unstable, the universality is poor, and the risk of secondary pollution is high.
The invention has the advantages of no secondary pollution, no soil hardening phenomenon, effective improvement of soil quality, reduction of the use amount of chemical fertilizers and pesticides, simple operation flow, short period and quick response, and is beneficial to the treatment and restoration application of large-area pollution of soils with different structures, different types of fields, different types of water bodies and the like.
The invention aims to provide a soil pollution remediation agent capable of efficiently, continuously and stably converting harmful heavy metals and organic pollution components in soil into harmless states. The repairing agent also has the advantages of no secondary pollution, no soil hardening, no damage to the physical and chemical properties of the soil, effective improvement of the soil quality, reduction of the use amount of chemical fertilizers and pesticides, simple operation, short period and quick response, and is beneficial to the treatment and repairing application of large-area soil environmental pollution.
The invention adopts the following technical scheme:
a soil heavy metal and organic pollution repairing agent is characterized in that: comprises the following components: biochar, turfy soil, selenium methionine, bacillus laterosporus, clay minerals, iron-containing compounds, silicon-containing compounds, humic acid and biomass.
The clay mineral in the above scheme refers to a main mineral which constitutes claystone and soil, such as hydrous silicate mineral containing aluminum, magnesium and other elements.
In the scheme, the biochar refers to a solid product generated by pyrolysis of a biological organic material in an anoxic or anaerobic environment.
The inventor researches and discovers that a great amount of chemical passivation principles are applied to the repairing agent in the prior art, a medium with a strong adsorption effect is partially added, and the heavy metal elements in an active exchange state are solidified and stabilized through the processes of adsorption-precipitation-ion exchange-redox, however, in the process, most of the repairing agents neglect the continuous change of the chemical, physical and biological states of soil in the process and after the soil is added, such as the continuous change of pH value, redox potential, soil micro-ecological environment and the like in different time periods before and after the repairing agent is added, so that part of heavy metals which can be fixed in the repairing process can be caused, the heavy metals can continuously return to a circulation system to form new pollution in the subsequent process, and the new pollution is more difficult to remove due to the soil hardening phenomenon which is easy to occur in the repairing process.
The inventor thinks that the research on the application and repair technology of the heavy metal in the soil firstly needs to master the morphological change and the running track of the heavy metal in the soil in the whole process and deeply knows the mutual transformation relation between the stable state and the exchangeable state of the heavy metal in the soil, so that the soil repairing agent with the effect of perpetual motion can be obtained.
After the components of the invention are cooperated, the repairing agent can adsorb heavy metal elements to concentrate around the repairing agent, and the effective components of the repairing agent can be diffused in the conversion process of harmful substances, the repairing agent and the soil microorganism environment can form dynamic balance, so that the pH value and the oxidation-reduction potential of the repairing agent can be continuously adjusted in the repairing process, the repairing agent and the polluted soil periphery form a biochemical community which continuously converts the state of the harmful substances, so that the harmful components, such as the heavy metal elements, can not only be fixed, but also be converted into harmless components through the biological and chemical synergistic effect.
One preferable embodiment of the above technical solution is that the repairing agent further contains fly ash.
One specific implementation of the above technical scheme is as follows: the clay mineral is one or more selected from kaolin, diatomite, montmorillonite, vermiculite, sepiolite and illite.
Another or further embodiment thereof is: the iron-containing compound is one or more selected from ferrous sulfate, ferric sulfate and polymeric ferric sulfate.
Another or further embodiment thereof is: the silicon-containing compound is one or two selected from calcium silicate, sodium silicate and calcium magnesium silicate.
Another or further embodiment thereof is: the biochar is obtained by carrying out oxygen-cut carbonization on the agricultural and forestry waste straws, and the temperature of the oxygen-cut carbonization is 500-600 ℃.
Another or further embodiment thereof is: the composition comprises the following components in parts by mass: 30-50 parts of biochar, 4-8 parts of turfy soil, 3-7 parts of clay minerals, 1-3 parts of iron-containing compounds, 1-3 parts of black humic acid, 2-5 parts of silicon-containing compounds, 1-3 parts of selenium methionine, 1-3 parts of bacillus laterosporus, 26-46 parts of biomass and preferably 2-5 parts of fly ash.
The invention further provides a preparation method of the technical scheme or the specific implementation mode thereof, which comprises the following steps:
(1) preparing biochar:
carrying out oxygen-cut carbonization on the agricultural and forestry waste straws at the temperature of 500-600 ℃ until the carbonization rate reaches more than 98% to obtain carbide, and processing the carbide into 80-100 meshes to obtain the biochar;
(2) preparation of biomass:
crushing plant wastes to 80-100 meshes, and then decomposing and fermenting to obtain the biomass;
(3) preparation:
and uniformly mixing the biochar, the biomass, turfy soil, clay minerals, iron-containing compounds, black humic acid, silicon-containing compounds, selenium methionine and bacillus laterosporus to obtain the soil heavy metal and organic pollution remediation agent.
The inventor finds that in part of the prior art, in the preparation process of the biochar, the carbonization temperature is controlled to be 350-450 ℃, the carbonization rate of the obtained product is only about 50-65%, the effective porous density is low, the impurity content is high, the utilization efficiency is low, and the biochar obtained at the carbonization temperature has poor adsorption capacity on harmful substances in soil or water body in actual application and is difficult to popularize. The carbonization rate of the obtained charcoal is more than 98% at the carbonization temperature of 500-600 ℃, the pore density is obviously increased, a porous high-density crystal is formed, the adsorption capacity is strong, and the synergistic effect with other components is obvious.
The agricultural and forestry wastes in the preparation method refer to waste parts generated in the growth process of agricultural crops and forestry crops, and the waste parts are changed into valuable materials, so that resource recycling is effectively realized.
The plant waste in the preparation method refers to waste parts generated in the plant growth process, such as wheat straws, fruit branches, leaves, fruit peels, humic substances, sweet potato vines, melon vines, chinaberry fruits and the like.
One preferred embodiment of the preparation method is as follows: the process of the decomposing fermentation in the step (2) comprises the following steps: and mixing the crushed plant waste with rotten bacteria and water until the water content is 40-50%, then carrying out rotting at the temperature of 60-80 ℃, and continuing to carry out natural fermentation for 5-15 days after the rotting is finished until the water content of the mixture reaches 15-20%.
The invention further provides an application method of the soil heavy metal and organic pollution repairing agent, which comprises the step of using the repairing agent in the soil and/or water body with heavy metal and/or organic pollution.
The application can be used for various targets such as field soil, cultivated land soil, farmland soil, vegetation soil, construction soil, farmland water, chemical discharge water, domestic sewage and the like, and is suitable for various occasions such as production and breeding, mine fields, chemical fields, garbage fields, pesticide fields, grease fields and the like.
In specific application, various treatment technologies such as in-situ repair and ex-situ repair can be matched.
Further, if ex-situ remediation is carried out on a contaminated site, the following specific processes can be adopted:
(1) the method comprises the following steps of (1) defining a site in-situ remediation pollutant stacking site nearby, determining a technical control site, wherein the technical control site requires ground hardening, retaining walls are arranged around the site for isolation, and a dust raising and rain shielding shed frame is built in the air to avoid heavy pollution of dust raising and avoid secondary pollution of underground water caused by rainwater erosion;
(2) the method comprises the following steps of deeply digging by adopting an excavator according to a technical design, rapidly transferring dug polluted soil and solid wastes to a treatment place, carrying out technical safety control, and if underground accumulated water or rainwater appears in a digging site of a polluted site, adopting accumulated water control measures or pumping the accumulated water out of the site to avoid secondary pollution;
(3) sealing and screening the excavated and stacked pollutants, intensively stacking solid wastes and floats in a designated place, and intensively treating the polluted soil;
(4) and (3) mixing the polluted soil with a mixing ratio of 1: 50 (m)3: kg), spraying tap water with sand, stirring uniformly, keeping the humidity at 20%, completing remediation and transformation after 30 days, sampling and detecting, and performing centralized filling after the soil pollution remediation and treatment standard is reached. Or if in-situ remediation is carried out on the polluted cultivated land (dry land), the method can be implemented by the following specific processes:
(1) the dry land soil is divided into different degrees such as severe degree, moderate degree, mild degree, light degree and the like according to the detection result of the content of the pollutants, so that a treatment and restoration scheme is formulated;
(2) according to different degrees, the ratio of 1: 400, respectively; 1: 300, respectively; 1: 200 of a carrier; or 1: 100 (mu: kg) of the repairing agent is put in;
(3) deeply turning the dry land by a machine or manpower for 10-20 cm before throwing, and then uniformly crushing soil by a rotary cultivator; spraying the repairing agent manually or mechanically, uniformly stirring by using a rotary cultivator, and spraying water to the soil to keep the soil humidity at about 20%;
(4) and (4) naturally transforming the soil after the repairing agent is put into the soil for 7-30 days, and then planting crops at will.
If the farmland in-situ remediation is carried out, the same process as the farmland (dry land) in-situ remediation can be selected, and the remediation agent is added according to the proportion of 1: 500, a step of; 1: 400, respectively; 1: 300, respectively; or 1: the fertilizer is put in the fertilizer according to the proportion of 200 (mu: kg).
The invention has the following beneficial effects:
(1) the invention can efficiently, continuously and stably convert harmful heavy metal and organic pollution components in soil or water into harmless states, can ensure that active exchange-state heavy metal ions are completely solidified after conversion, and further can be converted through biochemical action, and then do not enter circulation from the active state any more;
(2) the components of the repairing agent are safe and harmless, and the repairing agent can participate in the soil transformation process in the repairing process, does not produce secondary pollution and does not cause soil hardening, and long-term observation of an inventor shows that after the repairing agent is used, the soil filling power can be continuously maintained or improved, and the soil bulking height is increased by about 1cm every year;
(3) the method has short restoration period and quick response, can plant crops simultaneously in the restoration process, does not generate the enrichment of pollution components in the planted crops, can greatly reduce the vacant time of the land, and improves the economic benefit of agricultural cultivation;
(4) the invention can repair various types and large-area soil or water body pollution, and has higher economic and environmental benefits;
(5) when the soil after being restored by the method is planted, no pesticide or chemical fertilizer is needed to be applied, and the disease resistance of crops can be effectively enhanced, and when the soil is applied to the planting of fruits (grapes and lemons), vegetables and rice, the annual yield of the crops is found to be increased by 10-20% compared with a daily pesticide application treatment mode;
(6) the repairing agent can obviously reduce the contents of various heavy metals and organic pollution components in soil and water, and the content of heavy metal elements can be reduced by nearly 100% under some conditions;
(7) the soil restoration agent has the functions of fixing nitrogen, dissolving phosphorus, dissolving potassium, loosening soil, activating soil microorganisms, increasing soil organic carbon and restoring soil ecosystem while restoring soil.
Detailed Description
The repair agent is prepared by the following process:
(1) preparing biochar:
carrying out oxygen-cut carbonization on the agricultural and forestry waste straws at the temperature of 500-600 ℃ until the carbonization rate reaches more than 98% to obtain carbide, and processing the carbide into 80-100 meshes to obtain the biochar, wherein the biochar is a porous high-density crystal;
(2) preparation of biomass:
crushing plant wastes to 80-100 meshes, and then decomposing and fermenting to obtain the biomass; (3) preparation:
and uniformly mixing the biochar, the biomass, turfy soil, clay minerals, iron-containing compounds, black humic acid, silicon-containing compounds, selenium methionine and bacillus laterosporus to obtain the soil heavy metal and organic pollution remediation agent.
Wherein:
the process of the decomposing fermentation in the step (2) is preferably as follows: and mixing the crushed plant waste with rotten bacteria and water until the water content is 40-50%, then carrying out rotting at the temperature of 60-80 ℃, and continuing to carry out natural fermentation for 5-15 days after the rotting is finished until the water content of the mixture reaches 15-20%.
The step (9) preferably further comprises raw material fly ash.
The clay mineral is preferably one or more of kaolin, diatomite, montmorillonite, vermiculite, sepiolite and illite.
The iron-containing compound is preferably one or more of ferrous sulfate, ferric sulfate and polymeric ferric sulfate.
The silicon-containing compound is preferably one or two of calcium silicate, sodium silicate and calcium magnesium silicate. The preferred proportion of each raw material is as follows: 30-50 parts of biochar, 4-8 parts of turfy soil, 3-7 parts of clay minerals, 1-3 parts of iron-containing compounds, 1-3 parts of black humic acid, 2-5 parts of silicon-containing compounds, 1-3 parts of selenium methionine, 1-3 parts of bacillus laterosporus, 26-46 parts of biomass and preferably 2-5 parts of fly ash.
On the basis of the above detailed description, the present invention further provides some examples to further illustrate.
Example 1
The repair agent is prepared by the following process:
(1) preparing biochar:
carrying out oxygen-cut carbonization on agricultural and forestry waste straws such as rice, wheat and the like at 500-600 ℃, sampling and detecting carbides until the carbonization rate reaches more than 98%, finishing carbonization, and processing the obtained carbides into 80-100 meshes to obtain the required biochar, wherein the biochar is a porous high-density crystal; (2) preparation of biomass:
mixing and crushing wastes of natural plants such as wheat straws, fruit branches, leaves, fruit peels, rotten plants, sweet potato vines, melon vines, chinaberry fruit drops and the like to 80-100 meshes, then adding rotten bacteria and spraying water for mixing, keeping the water content of the mixture at 40-50%, then carrying out high-temperature rotting at the rotten temperature of 60-80 ℃, carrying out turning and throwing in a reciprocating groove by using an automatic turning and throwing machine, wherein the rotten period is selected according to climate and generally ranges from 7 days to 15 days, and after thoroughly rotten, returning the groove for natural fermentation for 10 days, keeping the water content at 15-20% to obtain the required biomass;
(3) preparation:
and uniformly mixing 30-50 parts of biochar, 26-46 parts of biomass, 4-8 parts of turfy soil, 3-7 parts of montmorillonite, 1-3 parts of ferrous sulfate and ferric sulfate, 1-3 parts of black humic acid, 2-5 parts of sodium silicate, 1-3 parts of selenium methionine, 1-3 parts of bacillus laterosporus and 2-5 parts of fly ash to obtain the soil heavy metal and organic pollution remediation agent.
Example 2
The repair agent is prepared by the following process:
(1) preparing biochar:
carrying out oxygen-cut carbonization on agricultural and forestry waste straws such as rice, wheat and the like at 500-600 ℃, sampling and detecting carbides until the carbonization rate reaches more than 98%, finishing carbonization, and processing the obtained carbides into 80-100 meshes to obtain the required biochar, wherein the biochar is a porous high-density crystal; (2) preparation of biomass:
mixing and crushing wastes of natural plants such as wheat straws, fruit branches, leaves, fruit peels, rotten plants, sweet potato vines, melon vines, chinaberry fruit drops and the like to 80-100 meshes, then adding rotten bacteria and spraying water for mixing, keeping the water content of the mixture at 40-50%, then carrying out high-temperature rotting at the rotten temperature of 60-80 ℃, carrying out turning and throwing in a reciprocating groove by using an automatic turning and throwing machine, wherein the rotten period is selected according to climate and generally ranges from 7 days to 15 days, and after thoroughly rotten, returning the groove for natural fermentation for 10 days, keeping the water content at 15-20% to obtain the required biomass;
(3) preparation:
and uniformly mixing 40 parts of biochar, 36 parts of biomass, 6 parts of turfy soil, 5 parts of kaolin, 2 parts of polyferric sulfate, 2 parts of black humic acid, 3 parts of calcium silicate, 1 part of selenium methionine, 2 parts of bacillus laterosporus and 3 parts of fly ash to obtain the soil heavy metal and organic pollution remediation agent.
Example 3
The repairing agent obtained in example 1 or 2 is applied to a farmland polluted by heavy metals, and before application, the detection conditions of the polluted soil are shown in the following table:
100kg of the obtained repairing agent is put into a farmland to be repaired of 0.5 mu, the putting process comprises the steps of firstly turning soil of the farmland to be repaired by about 20cm, then crushing the soil, then spraying the repairing agent into the soil for uniformly stirring, then irrigating with shallow water, completing conversion by 24h, then planting rice in the farmland, not applying any pesticide or fertilizer in the rice planting process until the rice is harvested for 120 days in total, forming a repairing period, sending the repaired soil and the harvested rice to a third party for heavy metal and organic pollution content testing, wherein the detection results are respectively as follows:
(1) and (3) detecting the soil after remediation:
(2) and (3) rice detection results:
| detecting items | Detection method | Unit of measurement | The result of the detection | Standard requirements |
| Glyphosate | GB/T23750-2009 | mg/kg | Not detected out | / |
| Protein | GB5009.5-2010 | mg/kg | 6.97 | / |
| Dripping nasal discharge | GB/T19648-2006 | mg/kg | Not detected out | ≤0.05 |
| Calcium carbonate | DB53/T288-2009 | mg/kg | 31.3 | / |
| Cadmium (Cd) | SN/T0448-2011 | mg/kg | Not detected out | ≤0.2 |
| Chromium (Cr) | DB53/T288-2009 | mg/kg | Not detected out | ≤1.0 |
| Mercury (Hg) | GB5009.17-2014 | mg/kg | Not detected out | ≤0.02 |
| Six | GB/T19648-2006 | mg/kg | Not detected out | ≤0.05 |
| Sodium salt | DB53/T288-2009 | mg/kg | 22.1 | / |
| Energy of | GB28050-2011 | KJ/100G | 1510 | / |
| Lead (Pb) | SN/T0448-2011 | mg/kg | Not detected out | ≤0.2 |
| Carbohydrate compound | GB28050-2011 | ％ | 79.7 | / |
| Selenium | GB/T5009.93-2010 | mg/kg | 0.33 | / |
| Zinc | DB53/T288-2009 | mg/kg | 11.1 | / |
| Fat | GB/T5009.6-2003 | ％ | 1.0 | / |
| Total arsenic (As) | SN/T0448-2011 | mg/kg | 0.13 | ≤0.15 |
From the results, the main heavy metal elements in the soil are remarkably reduced, wherein the content of cadmium (Cd) is reduced by 75.3%, the content of arsenic (As) is reduced by 74.7%, the content of lead (Pb) is reduced by 100%, the content of chromium (Cr) is reduced by 99.7%, the content of mercury (Hg) is reduced by 97.6%, the heavy metal elements are basically not detected in the planted rice, and the content of the nutrient components is high.
Example 4
The inventor participates in 3 groups of soil environmental pollution remediation and treatment test point projects of Pengzhou city Conghuangtangtaicun, wherein a field to be remediated is arranged in front of a street and has serious cadmium (Cd) pollution, the total amount is 0.9 mu, the inventor divides the field into two adjacent areas, 0.5 mu is a test field, 0.4 mu is a control field, the test field and the control field are respectively sampled and detected, and the detection results are shown in the following table:
and then 90kg of the repairing agent obtained in the embodiment 1 of the invention is put into 0.5 mu of test field, the putting process comprises the steps of firstly turning the soil of the farmland to be repaired by about 20cm, then crushing the soil, then spraying the repairing agent into the soil to be uniformly mixed, then irrigating with shallow water, completing conversion by 24h, carrying out the same operation on the control field, but not putting the repairing agent, then planting the rice in the control field and the test field, not applying any pesticide or fertilizer in the rice planting process until the rice is harvested, totaling 120 days, forming a repairing period, and then sending the soil after two groups of fields, the harvested rice and the harvested straws to a third party for heavy metal and organic pollution content tests, wherein the detection results are respectively:
(1) and (3) detecting the heavy metal content in the soil and the straws after a restoration period:
(2) the detection result of the heavy metal content in the rice after one restoration period is as follows:
from the comparison, the cadmium (Cd) content of the soil in the test field is reduced by 63 percent after the soil in the test field is restored, the cadmium content in the cadmium middle and heavy polluted areas is changed into national second-level soil, the cadmium content in the rice obtained by planting is reduced by 73 percent, while the heavy metal content of the rice obtained by the unrepaired control field is not changed, and the cadmium content of the rice obtained by planting reaches 0.37mg/kg, which is seriously overproof relative to the national rice cadmium pollution limit value of 0.2 mg/kg.
Example 5
The inventor participates in 3 groups of soil environment cadmium (Cd) pollution remediation and test point projects of Mianzhu Fujicun, wherein the area of a field to be remediated is planned to be 1.7 mu, the cadmium pollution is serious, the inventor divides the field into two adjacent areas, wherein 1 mu is a test field, 0.7 mu is a control field, the test field and the control field are respectively sampled and detected, and the detection results are shown in the following table:
then, 200kg of the repairing agent obtained in the embodiment 2 of the invention is put into 1 mu of test field, the putting process comprises the steps of firstly turning the soil of the test field to be repaired by about 20cm, then crushing the soil, then spraying the repairing agent into the soil to be uniformly mixed, then irrigating with shallow water, completing the conversion by 24h, carrying out the same operation on the control field, but not putting the repairing agent, then planting the rice in the control field and the test field, not applying any pesticide or fertilizer in the rice planting process until the rice is harvested, totaling 120 days, forming a repairing period, then sending the soil after two fields, the harvested rice and the harvested straws to a third party for heavy metal and organic pollution content tests, wherein the detection results are respectively as follows:
(1) the detection results of the heavy metal content and the pH value in the soil after one restoration period are as follows:
(2) the detection result of the heavy metal content in the rice and the straws after one restoration period is as follows:
from the comparison, the cadmium (Cd) content of the soil in the test field is reduced by 70% after the soil is restored, the cadmium heavily polluted area is changed into national second-level soil, the cadmium content of the rice obtained by planting is reduced by 81%, while the heavy metal content of the rice obtained by the non-restored control field is not changed, and the cadmium content of the rice obtained by planting reaches 0.38mg/kg, which is seriously overproof relative to the national rice cadmium pollution limit value of 0.2 mg/kg.
Example 6
The soil polluted by heavy metal and organic matters in a lemon base in a certain county is repaired, tests before repair show that the cadmium element content in the soil is 0.89mg/kg, the safety index of the soil is nearly 3 times higher than that of the national agricultural land 0.3mg/kg, the soil is heavily polluted by cadmium, the arsenic content in the soil is measured to be more than 5 times higher than that of the safety index, and the content of glyphosate, pyridaben, poison card, 920 hormone and the like in the soil exceeds 10 times to dozens of times of the national organic pollution residual standard.
According to the following steps: 50. 1: 100. 1: the repairing agent is put into the polluted soil at different putting ratios of 200 (mu: kg), and samples are taken after 4 months of repairing period and sent to a third party for detection, and the results are as follows:
(1) according to the following steps: compared with the use of the repairing agent of the invention, the adding ratio of 50 reduces the cadmium content in the soil from 0.89mg/kg to 0.45mg/kg by nearly 50 percent, and reduces the organic pollution value by 1.5 times compared with the value before repairing;
(2) according to the following steps: compared with the use of the repairing agent in the 100-dosage ratio, the cadmium content in the soil is reduced to 0.38mg/kg from 0.89mg/kg, the cadmium content is reduced by 57%, the organic matter pollution value is reduced by 1.5 times compared with the content before repairing, meanwhile, the arsenic content in the soil is reduced by 2.3 times compared with the content before repairing, and the organic matter pollution value in the soil is reduced by 4.8 times compared with the content before repairing;
(3) according to the following steps: compared with the use of the repairing agent of the invention in the feeding ratio of 200, the cadmium content in the soil is reduced from 0.89mg/kg to 0.30mg/kg and reduced by 66%, the organic matter pollution value is reduced by 1.5 times compared with that before repairing, meanwhile, the arsenic content in the soil is reduced to 0.2mg/kg, the organic matter pollution value in the soil is reduced by 4.8 times compared with that before repairing, and the soil reaches the green or organic safety standard.
Example 7
The heavy metal and organic polluted soil in the site and periphery of a thermal power plant in a certain city is repaired, and tests before repair show that the cadmium content in the soil is 0.85mg/kg, the chromium content is 0.56mg/kg, the lead content is 15.5mg/kg, the fluoride content is 6.5mg/kg, the cyanide (calculated by CN) content is 3.2mg/kg, and the heavy metal and organic polluted soil also has higher phenol and grease pollution concentration.
Meanwhile, the pollution depth of the field is 13 meters after geological drilling, the area is 3 mu, the total is 8500 cubic meters, the repairing difficulty is large, the inventor carries out ex-situ treatment on the field according to the requirements of the owner, and the in-situ filling treatment method carries out repairing by using the repairing agent.
The improvement process includes carrying out large-scale machine excavation to the place, digs out soil, solid waste and stone comprehensively to appointed technical management and control place pile, then after spreading the selection strictly, will pollute soil according to 1: 50 (m)3: kg), then evenly mixing, watering and mixing to keep the humidity of the mixed soil at about 20%, and sealing and converting for 30 days to finish the restoration.
The content of each heavy metal in the soil after remediation is changed as follows:
(1) the cadmium concentration is reduced from 0.85mg/kg to 0.3mg/kg by 65 percent;
(2) the chromium concentration is reduced from 0.56mg/kg to 0.28mg/kg by 50 percent;
(3) the lead concentration is reduced from 15.5mg/kg to 0.33mg/kg, and is reduced by 98 percent;
(4) the fluoride concentration is reduced from 6.5mg/kg to 4.5mg/kg, which is reduced by 31 percent;
(5) the concentration of cyanide (calculated by CN) is reduced from 3.2mg/kg to 0.6mg/kg, and the reduction is 81 percent; (6) the pollution concentration of phenols and grease is reduced to the organic pollution index range of national second-level safe soil.
After restoration, all the indexes reach the limit index range of national second-level safe soil and organic pollution.
Example 8 comparative example
The repair agent is prepared by the following process:
(1) preparing biochar:
carrying out oxygen-cut carbonization on agricultural and forestry waste straws such as rice, wheat and the like at 500-600 ℃, sampling and detecting carbides until the carbonization rate reaches more than 98%, finishing carbonization, and processing the obtained carbides into 80-100 meshes to obtain the required biochar, wherein the biochar is a porous high-density crystal; (2) preparation of biomass:
mixing and crushing wastes of natural plants such as wheat straws, fruit branches, leaves, fruit peels, rotten plants, sweet potato vines, melon vines, chinaberry fruit drops and the like to 80-100 meshes, then adding rotten bacteria and spraying water for mixing, keeping the water content of the mixture at 40-50%, then carrying out high-temperature rotting at the rotten temperature of 60-80 ℃, carrying out turning and throwing in a reciprocating groove by using an automatic turning and throwing machine, wherein the rotten period is selected according to climate and generally ranges from 7 days to 15 days, and after thoroughly rotten, returning the groove for natural fermentation for 10 days, keeping the water content at 15-20% to obtain the required biomass;
(3) preparation:
uniformly mixing the biochar, the biomass and other raw materials of the repairing agent according to the proportion to obtain different repairing agents,
wherein the raw materials of different repairing agents are as shown in the following table:
1 mu of field and 1 mu of dry land are selected in a certain heavy metal compound pollution area and are respectively divided into 10 test groups, each group contains 0.1 mu of field and dry land, and the 10 different repairing agents are used for repairing and comparing.
The repairing process comprises the following steps:
adding the repairing agent into dry land and a field according to the using amount of 20 kg/group (namely 200 kg/mu), fully and uniformly stirring the repairing agent and soil by adopting a manual or machine, then performing irrigation and watering, keeping the flooding water of the field to an average water level of 3cm, fully watering the dry land to keep the soil at an average humidity of 15-18%, repairing each group after 30 days, and then performing inspection and testing on the soil of each group to test the heavy metal content.
Before repairing, sampling and testing the heavy metal content of the field and the dry land, wherein the detection result is as follows:
after the restoration, the heavy metal content of the field and the dry land is tested again, and the detection result is as follows:
dry land group:
field group:
from the comparison of the formulas, the heavy metal content in the repaired soil is reduced more obviously from the formula 7, the pH value of the soil is adjusted more obviously, the heavy metal content of the formula 10 is reduced most obviously relative to other formulas, and the pH value of the soil is adjusted to be increased more obviously.
Example 9 application in a body of Water
The test is carried out in a paddy field seriously polluted by heavy metal, the paddy field of 1 mu is divided into two parts, 50cm ridges are tied in the middle of the paddy field for separating the paddy field so as to prevent mutual water crossing or water turning, 50cm ridges are tied at the periphery of the paddy field simultaneously, the whole paddy field is square, one half of the paddy field is used as a test field, the other half of the paddy field is used as a control field, and the heavy metal content of the two fields and an irrigation channel is tested before the test, which is shown in the following table:
irrigating water into the treated paddy field until the water level is kept at 20cm, binding a water inlet, tamping to recover 50cm to be parallel to ridges, directly putting 120kg of the repairing agent into the water body of the test field, then using a rotary cultivator to suspend the center of the high water body and uniformly stirring until the water body is turbid, completing repairing after 30 days, carrying out the same operation on the control field without putting the repairing agent, and then respectively sampling 2L of each water body for detection, wherein the detection results are as follows:
from the results, the heavy metal content in the water body of the test field is obviously reduced after the remediation, wherein the cadmium content is reduced by 65%, the mercury content is reduced by 84%, the lead content is reduced by 42%, the arsenic content is reduced by 51%, the chromium content is reduced by 34%, and the pH value of the water body is increased by 30%.
It is to be understood that the above-described embodiments are merely illustrative of some of the presently preferred embodiments of the invention, and that the present invention is not limited to the processes, operations, and parameters provided by the above-described embodiments.
Claims (8)
1. A soil heavy metal and organic pollution repairing agent is characterized in that: the composition comprises the following components in parts by mass: 30-50 parts of biochar, 4-8 parts of turfy soil, 3-7 parts of clay minerals, 1-3 parts of iron-containing compounds, 1-3 parts of black humic acid, 2-5 parts of silicon-containing compounds, 1-3 parts of selenium methionine, 1-3 parts of bacillus laterosporus, 26-46 parts of biomass and 2-5 parts of fly ash; the biomass is obtained by crushing plant wastes to 80-100 meshes, and then decomposing and fermenting.
2. The soil heavy metal and organic pollution remediation agent of claim 1, wherein: the clay mineral is one or more selected from kaolin, diatomite, montmorillonite, vermiculite, sepiolite and illite.
3. The soil heavy metal and organic pollution remediation agent of claim 1, wherein: the iron-containing compound is one or more selected from ferrous sulfate, ferric sulfate and polymeric ferric sulfate.
4. The soil heavy metal and organic pollution remediation agent of claim 1, wherein: the silicon-containing compound is one or two selected from calcium silicate, sodium silicate and calcium magnesium silicate.
5. The soil heavy metal and organic pollution remediation agent of claim 1, wherein: the biochar is obtained by carrying out oxygen-cut carbonization on the agricultural and forestry waste straws, and the temperature of the oxygen-cut carbonization is 500-600 ℃.
6. The method for preparing the soil heavy metal and organic pollution remediation agent as claimed in any one of claims 1 to 5, wherein the method comprises the following steps: the method comprises the following steps:
(1) preparing biochar:
carrying out oxygen-cut carbonization on the agricultural and forestry waste straws at the temperature of 500-600 ℃ until the carbonization rate reaches more than 98% to obtain carbide, and processing the carbide into 80-100 meshes to obtain the biochar;
(2) preparation of biomass:
crushing plant wastes to 80-100 meshes, and then decomposing and fermenting to obtain the biomass;
(3) preparation:
and uniformly mixing the biochar, the biomass, turfy soil, clay minerals, iron-containing compounds, black humic acid, silicon-containing compounds, selenium methionine, bacillus laterosporus and fly ash to obtain the soil heavy metal and organic pollution remediation agent.
7. The method of claim 6, wherein: the process of the decomposing fermentation in the step (2) comprises the following steps: and mixing the crushed plant waste with rotten bacteria and water until the water content is 40-50%, then carrying out rotting at the temperature of 60-80 ℃, and continuing to carry out natural fermentation for 5-15 days after the rotting is finished until the water content of the mixture reaches 15-20%.
8. The method for applying the soil heavy metal and organic pollution remediation agent as claimed in any one of claims 1 to 5, wherein the method comprises the following steps: the soil heavy metal and organic pollution remediation agent is applied to soil and/or water body with heavy metal and/or organic pollution.
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| CN109575934B (en) * | 2019-01-25 | 2021-01-19 | 湖南新九方科技有限公司 | Heavy metal contaminated soil remediation agent and preparation method and application thereof |
| CN109678626B (en) * | 2019-01-28 | 2022-03-18 | 湖南恒凯环保科技投资有限公司 | Soil conditioner for mercury-polluted farmland remediation and preparation method and application thereof |
| CN110144221B (en) * | 2019-04-28 | 2020-09-29 | 北京建工环境修复股份有限公司 | Modifier and preparation method and application thereof |
| CN110016350A (en) * | 2019-04-29 | 2019-07-16 | 深圳润康生态环境股份有限公司 | Arable land heavy-metal contaminated soil preparation for repairing and preparation method thereof |
| IL289346B2 (en) | 2019-07-04 | 2023-04-01 | Incitec Fertilizers Pty Ltd | Improved fertiliser |
| CN110387244A (en) * | 2019-07-29 | 2019-10-29 | 山东胜伟盐碱地科技有限公司 | A kind of organic polluted soil renovation agent and its production method and application |
| CN110452705A (en) * | 2019-07-31 | 2019-11-15 | 安徽禾美环保集团有限公司 | A kind of heavy metal pollution of soil renovation agent and preparation method thereof |
| CN110591724A (en) * | 2019-09-26 | 2019-12-20 | 湖南博惢巳环境科技有限公司 | Conditioner for treating heavy metal contaminated soil and preparation method and application thereof |
| CN110950709A (en) * | 2019-11-11 | 2020-04-03 | 江西普瑞丰生态科技有限公司 | Conditioner for repairing heavy metal soil and preparation method thereof |
| CN111154503A (en) * | 2020-01-09 | 2020-05-15 | 复旦大学 | Method for reducing high toxic substances in biochar |
| CN111394101B (en) * | 2020-03-13 | 2021-04-27 | 江苏和合环保集团有限公司 | Preparation method of biomass long-acting heavy metal passivator |
| CN113046089A (en) * | 2021-03-19 | 2021-06-29 | 代彦霞 | Heavy metal restoration agent for soil and preparation method thereof |
| CN115156281A (en) * | 2022-06-28 | 2022-10-11 | 广东德济环境发展有限公司 | Method for repairing soil polluted by heavy metal |
| CN115124384A (en) * | 2022-06-28 | 2022-09-30 | 张珈毓 | Pesticide-contaminated soil remediation agent, preparation method and application thereof, and method for remediating pesticide-contaminated soil |
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