CN110283599B - Heavy metal contaminated soil remediation agent and preparation method thereof - Google Patents
Heavy metal contaminated soil remediation agent and preparation method thereof Download PDFInfo
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Abstract
The invention provides a heavy metal contaminated soil remediation agent which is prepared from the following raw materials in parts by mass: 50-65 parts of modified biomass carbon, 20-30 parts of organic matters, 6-15 parts of composite microbial agent, 5-10 parts of polyacrylamide, 12-20 parts of organic fertilizer and 6-12 parts of iron powder; wherein the modified biomass charcoal is obtained by mixing and modifying biomass charcoal and sodium sulfide; the organic matter is obtained by mixing humic acid, potassium humate and potassium fulvate according to the mass ratio of 2-4: 6-8: 3. The invention also discloses a preparation method of the heavy metal contaminated soil remediation agent. The heavy metal contaminated soil remediation agent disclosed by the invention is simple in preparation process, mild in conditions, high in removal rate of heavy metals in the soil after remediation, good in remediation effect on the soil, and higher in practical significance.
Description
Technical Field
The invention relates to a soil pollution repairing agent, in particular to a heavy metal polluted soil repairing agent.
Background
The soil is an important component of human environment, is an indispensable and non-renewable natural resource, is an important basis on which all organisms live, and is an important place for exchanging and circulating substances and energy of the earth ecosystem. With the rapid development of industrialization and urbanization in China, the discharge of a large amount of pollutants, the use of unqualified agricultural substances, the unreasonable exploitation of mineral resources and the like, heavy metals continuously enter the soil environment, and when the heavy metals are accumulated to exceed a certain amount, the soil pollution is caused, so that the environmental pollution problem of the soil is gradually serious, especially the heavy metal pollution problem of the soil. The heavy metal pollution of the soil has concealment, long-term property and irreversibility, the residence time of pollutants in the soil is long, plants or microorganisms are difficult to degrade, the soil degradation and crop damage can be caused, and the life health of human beings can be directly threatened. In recent years, the heavy metal pollution problem of soil is also showing a trend of increasing complexity along with the increasing of the environmental deterioration. A large number of polluted plots have serious metal pollution and serious toxic organic pollution, and bring serious threats to surrounding residents and ecological environment.
At present, the repair technology for heavy metal contaminated soil mainly comprises the following steps: the soil replacement method has the advantages of large construction amount, high investment cost, damage to soil body structure, secondary pollution prevention only by properly treating the replaced soil, and is not suitable for treating large-area polluted soil; in-situ or ex-situ chemical leaching, the method has high cost, and the reagent for leaching the soil enters the soil to cause secondary pollution; the thermal desorption method can only be used for treating volatile heavy metals such as mercury and the like, and a large amount of energy is consumed in the treatment process, so that the economic cost is high; the vitrification restoration method has high restoration efficiency, but the restored soil needs to be buried, the restoration cost is high, and the restored soil can not be used for agriculture.
The method for repairing the soil polluted by the heavy metals has various defects that some heavy metals in the soil cannot be completely and thoroughly eliminated, and some new pollutants even brought by the heavy metals, so that the method is necessary to design a soil repairing agent which has a good heavy metal removing effect and does not generate new pollution aiming at the current situation.
Disclosure of Invention
The invention aims to solve the technical defects and provide a heavy metal contaminated soil remediation agent, which combines the modified biomass charcoal, organic matters and a compound microbial agent for use, so that heavy metals in soil can be adsorbed and fixed, the soil structure can be improved, new pollutants are not generated in the remediation process, and the remediation effect is good.
In order to achieve the purpose, the invention adopts the technical scheme that:
the heavy metal contaminated soil remediation agent is prepared from the following raw materials in parts by mass:
50-65 parts of modified biomass carbon, 20-30 parts of organic matters, 6-15 parts of composite microbial agent, 5-10 parts of polyacrylamide, 12-20 parts of organic fertilizer and 6-12 parts of iron powder;
the modified biomass charcoal is obtained by mixing and modifying biomass charcoal and sodium sulfide;
the organic matter is obtained by mixing humic acid, potassium humate and potassium fulvate according to the mass ratio of 2-4: 6-8: 3;
the compound microbial agent is prepared from the following raw materials in parts by mass: 1-4 parts of bacillus cereus, 1-3 parts of clostridium perfringens, 1-5 parts of bacillus mycoides, 2-3 parts of bacillus mucilaginosus, 5-12 parts of white rot fungi, 2-5 parts of bacillus citrate, 3-5 parts of streptomyces oyster gray and 1-4 parts of pseudomonas aeruginosa.
Preferably, the effective viable count of each bacterium in the compound microbial agent is 1 × 109～3×109CFU/g。
Preferably, the organic fertilizer is a mature fertilizer prepared by fermenting domestic garbage and kitchen garbage mixed with livestock and poultry manure.
The invention also provides a preparation method of the heavy metal contaminated soil remediation agent, which comprises the following steps:
soaking biomass charcoal in a sodium sulfide solution for 35-40 h, washing, filtering, drying, calcining at 500-600 ℃ for 1-3 h in an inert gas atmosphere, and preserving heat for 1-2 h to obtain modified biomass charcoal for later use;
mixing humic acid, potassium humate and potassium fulvate according to the mass ratio of 2-4: 6-8: 3 to obtain organic matters for later use;
mixing 1-4 parts of bacillus cereus, 1-3 parts of clostridium perfringens, 1-5 parts of bacillus mycoides, 2-3 parts of bacillus mucilaginosus, 5-12 parts of white rot fungi, 2-5 parts of bacillus citrate, 3-5 parts of streptomyces oyster gray and 1-4 parts of pseudomonas aeruginosa by mass part to obtain a composite microbial agent;
step two, weighing 60-65 parts of the modified biomass charcoal obtained in the step one, 20-30 parts of organic matters obtained in the step one, 6-15 parts of a compound microbial agent, 5-10 parts of polyacrylamide, 12-20 parts of an organic fertilizer and 6-12 parts of iron powder for later use;
step three, mixing the compound microbial inoculum weighed in the step two with water according to the volume ratio of 1: 170-190 to obtain a compound microbial inoculum, uniformly mixing the compound microbial inoculum with the modified biomass charcoal weighed in the step two, and performing ultrasonic drying to obtain a mixture;
and step four, uniformly mixing the organic matters, polyacrylamide, organic fertilizer and iron powder weighed in the step two with the mixture obtained in the step three to obtain the heavy metal polluted soil remediation agent.
Preferably, in the first step, the mass fraction of the sodium sulfide solution is 10-30%.
Preferably, in the step one, the preparation process of the biomass charcoal comprises: mixing a biomass raw material and calcium oxide according to a mass ratio of 20-22: 1, pyrolyzing the mixture for 1-3 hours at 600-800 ℃ in an inert gas atmosphere, and cooling to obtain biomass charcoal.
Preferably, the biomass raw material is one or more of crop straws, peanut shells, de-seeded sunflower discs, willow leaves, rice hulls, animal wastes and wood chips.
Preferably, in the third step, the ultrasonic drying conditions are as follows: the ultrasonic power is 100-200W, and the ultrasonic frequency is 20 kHz.
Compared with the prior art, the invention has the following beneficial effects:
1. the biomass charcoal is obtained by pyrolyzing biomass in inert atmosphere, the biomass charcoal prepared in inert atmosphere has high porosity and good adsorption performance, and the addition of calcium oxide in the preparation process of the biomass charcoal can effectively promote the yield increase and rich pore channels of the biomass charcoal and can also improve the pH value of soil, thereby increasing the negative charge on the surface of the soil, increasing the affinity of the soil to heavy metals and promoting the heavy metals in the soil to form hydroxides or combined-state precipitates or coprecipitations; in addition, the biomass carbon is subjected to sulfur modification, the number of sulfur-containing functional groups on the surface of the biomass carbon is obviously increased, the adsorption force on heavy metals is enhanced, and the sulfur-containing functional groups can promote the reduction of hexavalent cadmium, have extremely high stability and cannot generate secondary pollution;
2. the invention takes the biomass such as crop straws and the like as the raw materials, fully utilizes resources, avoids environmental pollution caused by burning, combines the modified biomass charcoal with the organic fertilizer, and has the functions of improving the physical and chemical properties of soil, adjusting the pH value of the soil and improving the fertility of the soil, so that the repairing agent not only repairs heavy metals, but also improves the properties of the soil;
3. according to the invention, the modified biomass charcoal and the organic matter are combined for use, so that heavy metal can be adsorbed and solidified; heavy metal species are present in soil in a variety of forms, for example cadmium includes soluble cadmium ion forms, insoluble cadmium sulfide and cadmium salts; the organic matter comprises humic acid, potassium humate and potassium fulvate, the potassium humate can lead soluble cadmium ions to form cadmium hydroxide to be passivated in soil, meanwhile, a potash fertilizer is released, the humic acid can adsorb insoluble cadmium sulfide and cadmium salt, and at the moment, the modified biomass charcoal can adsorb the cadmium hydroxide in the soil; meanwhile, humic acid has the plant growth stimulation effect, and potassium fulvate has the effects of improving the soil structure, loosening the soil, improving the soil fertility, fixing nitrogen, activating potassium and strengthening the plant root system adhesion and rapid absorption capacity;
4. according to the invention, by adding the compound microbial agent, heavy metals such as cadmium, lead, zinc and the like can be effectively absorbed; the iron powder can reduce cadmium, chromium and other substances into a low-toxicity or non-toxic state; the polyacrylamide is a high-molecular polymer, has good water solubility, is non-toxic and non-corrosive, can improve the physical properties of soil, increase the number of large aggregates in the soil, improve the water conductivity and water content of the soil, slow down the loss of the soil and ensure that the soil is fully contacted with the passivator; in addition, polyacrylamide has active groups such as carboxyl groups and amide groups, and can form coordinate bonds with metal ions on the surface of soil particles, thereby having a synergistic effect of stabilizing chromium ions.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments. The scope of the invention is not limited to the specific embodiments.
Example 1
The embodiment provides a heavy metal contaminated soil remediation agent which is prepared from the following raw materials in parts by mass:
57 parts of modified biomass carbon, 25 parts of organic matters, 10 parts of compound microbial agent, 7 parts of polyacrylamide, 16 parts of organic fertilizer and 9 parts of iron powder;
wherein the organic matter is obtained by mixing humic acid, potassium humate and potassium fulvate according to the mass ratio of 3:7: 3;
the compound microbial agent is prepared from the following raw materials in parts by mass: 2.5 parts of bacillus cereus, 2 parts of clostridium perfringens, 3 parts of bacillus mycoides, 2.5 parts of bacillus mucilaginosus, 8.5 parts of white rot fungi, 3.5 parts of bacillus citrate, 4 parts of streptomyces oyster gray and 2.5 parts of pseudomonas aeruginosa; the effective viable count of each bacterium in the compound microbial agent is 1 multiplied by 109CFU/g。
The embodiment also provides a preparation method of the repairing agent, which comprises the following steps:
mixing crop straws and calcium oxide according to a mass ratio of 20:1, pyrolyzing the mixture for 2 hours at 700 ℃ under the protection of argon, and cooling the pyrolysis product to obtain biomass charcoal; soaking the biomass charcoal in a sodium sulfide solution with the mass fraction of 20% for 37.5h, washing with water, filtering, drying, calcining at 550 ℃ for 2h in an argon atmosphere, and preserving heat for 1h to obtain modified biomass charcoal for later use;
mixing humic acid, potassium humate and potassium fulvate according to the mass ratio of 3:7:3 to obtain organic matters for later use;
step two, weighing 57 parts of the modified biomass charcoal obtained in the step one, 25 parts of organic matters obtained in the step one, 10 parts of compound microbial agents, 7 parts of polyacrylamide, 16 parts of organic fertilizers and 9 parts of iron powder for later use;
step three, mixing the compound microbial inoculum weighed in the step two with water according to the volume ratio of 1:180 to obtain compound microbial inoculum, uniformly mixing the compound microbial inoculum with the modified biomass charcoal weighed in the step two, and performing ultrasonic drying to obtain a mixture;
and step four, uniformly mixing the organic matters, polyacrylamide, organic fertilizer and iron powder weighed in the step two with the mixture obtained in the step three to obtain the heavy metal polluted soil remediation agent.
Example 2
The embodiment provides a heavy metal contaminated soil remediation agent which is prepared from the following raw materials in parts by mass:
50 parts of modified biomass carbon, 20 parts of organic matters, 6 parts of compound microbial agent, 5 parts of polyacrylamide, 12 parts of organic fertilizer and 6 parts of iron powder;
wherein the organic matter is obtained by mixing humic acid, potassium humate and potassium fulvate according to the mass ratio of 2:6: 3;
the compound microbial agent is prepared from the following raw materials in parts by mass: 1 part of bacillus cereus, 1 part of clostridium perfringens, 1 part of bacillus mycoides, 2 parts of bacillus mucilaginosus, 5 parts of white rot fungi, 2 parts of bacillus citrate, 3 parts of streptomyces oyster gray and 1 part of pseudomonas aeruginosa; the effective viable count of each bacterium in the compound microbial agent is 2 multiplied by 109CFU/g。
The embodiment also provides a preparation method of the repairing agent, which comprises the following steps:
mixing crop straws and calcium oxide according to a mass ratio of 22:1, pyrolyzing the mixture for 3 hours at 600 ℃ under the protection of argon, and cooling the pyrolysis product to obtain biomass charcoal; soaking biomass charcoal in a sodium sulfide solution with the mass fraction of 10% for 40h, washing, filtering, drying, calcining for 3h at 500 ℃ in an argon atmosphere, and preserving heat for 2h to obtain modified biomass charcoal for later use;
mixing humic acid, potassium humate and potassium fulvate according to the mass ratio of 2:6:3 to obtain organic matters for later use;
step two, weighing 50 parts of the modified biomass charcoal obtained in the step one, 20 parts of organic matters obtained in the step one, 6 parts of compound microbial agents, 5 parts of polyacrylamide, 12 parts of organic fertilizers and 6 parts of iron powder for later use;
step three, mixing the compound microbial inoculum weighed in the step two with water according to the volume ratio of 1:170 to obtain compound microbial inoculum, uniformly mixing the compound microbial inoculum with the modified biomass charcoal weighed in the step two, and performing ultrasonic drying to obtain a mixture;
and step four, uniformly mixing the organic matters, polyacrylamide, organic fertilizer and iron powder weighed in the step two with the mixture obtained in the step three to obtain the heavy metal polluted soil remediation agent.
Example 3
The embodiment provides a heavy metal contaminated soil remediation agent which is prepared from the following raw materials in parts by mass:
65 parts of modified biomass carbon, 30 parts of organic matters, 15 parts of compound microbial agents, 10 parts of polyacrylamide, 20 parts of organic fertilizers and 12 parts of iron powder;
wherein the organic matter is obtained by mixing humic acid, potassium humate and potassium fulvate according to the mass ratio of 4:8: 3;
the compound microbial agent is prepared from the following raw materials in parts by mass: 4 parts of bacillus cereus, 3 parts of clostridium perfringens, 5 parts of bacillus mycoides, 3 parts of bacillus mucilaginosus, 12 parts of white rot fungi, 5 parts of bacillus citrate, 5 parts of streptomyces oyster gray and 4 parts of pseudomonas aeruginosa; the effective viable count of each bacterium in the compound microbial agent is 3 multiplied by 109CFU/g。
The embodiment also provides a preparation method of the repairing agent, which comprises the following steps:
mixing crop straws and calcium oxide according to a mass ratio of 22:1, pyrolyzing the mixture for 1 hour at 800 ℃ under the protection of argon, and cooling the pyrolysis product to obtain biomass charcoal; soaking the biomass charcoal in a sodium sulfide solution with the mass fraction of 30% for 35 hours, washing with water, filtering, drying, calcining at 600 ℃ for 1 hour in an argon atmosphere, and preserving heat for 2 hours to obtain modified biomass charcoal for later use;
mixing humic acid, potassium humate and potassium fulvate according to the mass ratio of 4:8:3 to obtain organic matters for later use;
step two, weighing 65 parts of the modified biomass charcoal obtained in the step one, 30 parts of organic matters obtained in the step one, 15 parts of compound microbial agents, 10 parts of polyacrylamide, 20 parts of organic fertilizers and 12 parts of iron powder for later use;
step three, mixing the compound microbial inoculum weighed in the step two with water according to the volume ratio of 1:190 to obtain compound microbial inoculum, uniformly mixing the compound microbial inoculum with the modified biomass charcoal weighed in the step two, and performing ultrasonic drying to obtain a mixture;
and step four, uniformly mixing the organic matters, polyacrylamide, organic fertilizer and iron powder weighed in the step two with the mixture obtained in the step three to obtain the heavy metal polluted soil remediation agent.
Comparative example 1
The same composition and preparation method as in example 1 were followed, except that the complex microbial agent was not added.
Comparative example 2
The same composition and preparation method as in example 1 were used, except that biomass char was added, that is, the biomass char was not subjected to modification treatment.
Comparative example 3
The biomass char of example 1.
Comparative example 4
Modified biomass char of example 1.
The repairing agents of the examples 1 to 3 of the present invention have good repairing effects, and we performed repairing experiments on the samples of the examples 1 to 3 and the samples of the comparative examples 1 to 4.
Firstly, a remediation experiment of heavy metal contaminated soil is carried out, the heavy metal contaminated soil is placed in 7 identical containers respectively, then samples of examples 1-3 and comparative examples 1-4 are applied according to the mass of 5% of the weight of the soil respectively, deionized water is added after the samples are fully mixed to enable the humidity of the soil to be 30-40%, then water is added every day to enable the humidity of the experimental soil to be unchanged, a soil sample is collected after 30 days, and a heavy metal content test is carried out. Table 1 is a table of heavy metal content data of soil samples after remediation by different samples.
Table 1 table of heavy metal content data of soil sample after remediation with different samples
As can be seen from Table 1, the heavy metal soil remediation agent of the invention has good remediation effect on heavy metal contaminated soil.
The experiment of the influence of the repaired soil on the growing plants is carried out at the same time, and the specific process is as follows: preparing 400mg/kg cadmium contaminated soil from sieved fine soil, fully mixing, filling into flowerpots with 500g of soil per pot, adding deionized water to ensure that the water content is 30% of the field water capacity, balancing for one month, and then respectively applying the soil remediation agents of the examples 1-3 and the comparative examples 1-4. Then, complete, healthy and full wheat seeds are selected, 30 seeds are sowed in each pot, and the sowing depth is 2 cm. Culturing 7 flowerpots in an intelligent artificial climate plant box, wherein the temperature is 25 +/-2 ℃ in the daytime, the full illumination is realized, the temperature is 18 +/-2 ℃ at night, the darkness is realized, the humidity in the whole day is 60-70%, and water is poured once every other day. Thinning after one week of growth, and reserving 15 seedlings in each pot. After 30 days of growth, plant and root soil samples are collected, and the content of heavy metal cadmium in the plant and root soil is measured, and the result is shown in table 2.
TABLE 2 cadmium content of soil-planted wheat after remediation
As can be seen from Table 2, the repairing agent of the invention has significant influence on the effective state of cadmium in soil, and the repairing agent of the invention can effectively reduce the cadmium content in wheat bodies.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (6)
1. The preparation method of the heavy metal contaminated soil remediation agent is characterized by comprising the following raw materials in parts by mass:
50-65 parts of modified biomass carbon, 20-30 parts of organic matters, 6-15 parts of composite microbial agent, 5-10 parts of polyacrylamide, 12-20 parts of organic fertilizer and 6-12 parts of iron powder;
the modified biomass charcoal is obtained by mixing and modifying biomass charcoal and sodium sulfide;
the organic matter is obtained by mixing humic acid, potassium humate and potassium fulvate according to the mass ratio of 2-4: 6-8: 3;
the compound microbial agent is prepared from the following raw materials in parts by mass: 1-4 parts of bacillus cereus, 1-3 parts of clostridium perfringens, 1-5 parts of bacillus mycoides, 2-3 parts of bacillus mucilaginosus, 5-12 parts of white rot fungi, 2-5 parts of bacillus citrate, 3-5 parts of streptomyces oyster gray and 1-4 parts of pseudomonas aeruginosa;
the preparation method of the heavy metal contaminated soil remediation agent comprises the following steps:
soaking biomass charcoal in a sodium sulfide solution for 35-40 h, washing, filtering, drying, calcining at 500-600 ℃ for 1-3 h in an inert gas atmosphere, and preserving heat for 1-2 h to obtain modified biomass charcoal for later use;
mixing humic acid, potassium humate and potassium fulvate according to the mass ratio of 2-4: 6-8: 3 to obtain organic matters for later use;
mixing 1-4 parts of bacillus cereus, 1-3 parts of clostridium perfringens, 1-5 parts of bacillus mycoides, 2-3 parts of bacillus mucilaginosus, 5-12 parts of white rot fungi, 2-5 parts of bacillus citrate, 3-5 parts of streptomyces oyster gray and 1-4 parts of pseudomonas aeruginosa by mass part to obtain a composite microbial agent;
step two, weighing 60-65 parts of modified biomass charcoal obtained in the step one, 20-30 parts of organic matters obtained in the step one, 6-15 parts of compound microbial agent obtained in the step one, 5-10 parts of polyacrylamide, 12-20 parts of organic fertilizer and 6-12 parts of iron powder for later use;
step three, mixing the compound microbial inoculum weighed in the step two with water according to the volume ratio of 1: 170-190 to obtain a compound microbial inoculum, uniformly mixing the compound microbial inoculum with the modified biomass charcoal weighed in the step two, and performing ultrasonic drying to obtain a mixture;
step four, uniformly mixing the organic matters, polyacrylamide, organic fertilizer and iron powder weighed in the step two with the mixture obtained in the step three to obtain a heavy metal polluted soil remediation agent;
the preparation process of the biomass charcoal comprises the following steps: mixing a biomass raw material and calcium oxide according to a mass ratio of 20-22: 1, pyrolyzing the mixture for 1-3 hours at 600-800 ℃ in an inert gas atmosphere, and cooling to obtain biomass charcoal.
2. The method for preparing a soil remediation agent for heavy metal contaminated soil as claimed in claim 1, wherein the effective viable count of each bacterium in the compound microbial agent is 1 × 109～3×109CFU/g。
3. The method for preparing a heavy metal contaminated soil remediation agent as claimed in claim 1, wherein the organic fertilizer is a fermented mature fertilizer prepared from domestic garbage and kitchen garbage mixed with livestock and poultry manure.
4. The method for preparing a heavy metal contaminated soil remediation agent as claimed in claim 1, wherein in the first step, the sodium sulfide solution is present in an amount of 10-30% by weight.
5. The method of claim 1, wherein the biomass material is one or more of crop straw, peanut hulls, de-seeded sunflower discs, willow leaves, rice hulls, animal wastes, and wood chips.
6. The method for preparing a heavy metal contaminated soil remediation agent of claim 1, wherein in the third step, the ultrasonic drying conditions are as follows: the ultrasonic power is 100-200W, and the ultrasonic frequency is 20 kHz.
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| CN106978185A (en) * | 2017-05-16 | 2017-07-25 | 山东创业环保科技发展有限公司 | A kind of heavy-metal contaminated soil repairs conditioner and its application |
| CN107446585A (en) * | 2017-06-27 | 2017-12-08 | 浦江县元寿农业科技有限公司 | A kind of compound biological soil improver and preparation method thereof |
| CN108165276A (en) * | 2018-01-18 | 2018-06-15 | 河南清水源科技股份有限公司 | A kind of composite conditioner suitable for northern alkaline soil heavy metal pollution |
| CN109233846A (en) * | 2018-08-22 | 2019-01-18 | 山西华欣久泰科技有限公司 | A kind of heavy-metal contaminated soil renovation agent and its application |
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