CN114479865A - Green heavy metal eluting agent and preparation and use methods thereof - Google Patents
Green heavy metal eluting agent and preparation and use methods thereof Download PDFInfo
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- CN114479865A CN114479865A CN202210085171.3A CN202210085171A CN114479865A CN 114479865 A CN114479865 A CN 114479865A CN 202210085171 A CN202210085171 A CN 202210085171A CN 114479865 A CN114479865 A CN 114479865A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
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- C09K17/32—Prepolymers; Macromolecular compounds of natural origin, e.g. cellulosic materials
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- 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
Abstract
The invention belongs to the technical field of soil remediation, and particularly discloses a green heavy metal eluting agent and a preparation and use method thereof. Extracting herba Kalimeridis twice, the first time with citric acid, adding certain amount of disodium edetate (T1), the second time with complex enzyme, adding certain amount of sodium bicarbonate (T2), and mixing with herba Kalimeridis extractive solution T1 and T2 to obtain eluent; the rice soil is flooded and cultured for 7 days, then the eluting agent is put into the soil according to the proportion, the soil is leached by combining ultrasonic-heat treatment, and finally the straw fermentation liquor is added into the soil again. The eluting agent contains a large amount of amino, hydroxyl, soluble organic matters and natural surfactants, the problems that the traditional chemical eluting agent is easy to cause secondary pollution and a single eluting agent is difficult to remove various pollutants are solved, meanwhile, the eluting mode can effectively improve the eluting efficiency and protect the inherent properties of soil to the maximum extent.
Description
Technical Field
The invention belongs to the technical field of soil remediation, and particularly relates to a green heavy metal eluting agent and a preparation and use method thereof.
Background
Soil is a natural resource on which human beings rely to live, and with the continuous development of industries such as industry, agriculture and the like, heavy metals entering the soil in various ways increase year by year, and heavy metal pollution events occur frequently. The pollutants mainly comprise eight kinds of copper (Cu), cadmium (Cd), lead (Pb), chromium (Cr), nickel (Ni), zinc (Zn) and arsenic (As), and after heavy metals enter soil, the human health is indirectly or directly influenced due to the characteristics of carcinogenicity, concealment, difficulty in natural degradation and the like of the heavy metals. Therefore, repairing heavy metal contaminated soil is always a hot topic in the environmental field.
The soil leaching technology is concerned by numerous scholars due to the advantages of high efficiency, rapidness, simple operation, suitability for large-area polluted soil and the like, and the technology mainly utilizes chemical actions of chelating, dissolving, resolving and the like of leaching liquor on heavy metals to transfer the heavy metals from a solid phase to a liquid phase so as to remove the heavy metals. However, the traditional chemical eluting agent is easy to cause secondary damage to soil, and one eluting agent cannot be effective on various heavy metals.
Disclosure of Invention
The invention aims to solve the problems that the existing single eluting agent can not simultaneously act on various heavy metals and the residual eluting solution is polluted, provides a novel green eluting agent prepared by compounding plant extract, straw fermentation liquor and ethylene diamine tetraacetic acid (EDTA-2Na), and maximizes the removal effect through ultrasonic treatment and heat treatment.
The eluent is prepared by the following specific steps:
(1) taking 5 parts of wild herba Kalimeridis, removing rootstalk, naturally drying in the sun, crushing into powder with the diameter of not more than 0.05mm, adding 100 parts of water (40-60 ℃), oscillating for 24 hours at the oscillation frequency of 150r/min, taking out the mixture, adding 0.5 part of citric acid, centrifuging for 20min at the centrifugal frequency of 5000r/min, collecting supernatant, performing suction filtration, adding EDTA-2Na1 parts, and preparing an extracting solution 1, which is recorded as T-1.
(2) Taking 5 parts of wild malan head rhizome, naturally drying in the sun, crushing into powder with the diameter of not more than 0.05mm, adding 100 parts of water, adding 0.1 part of complex enzyme (xylanase, amylase and beta-glucanase in a mass ratio of 1: 1: 1) at the temperature of 40 ℃, ultrasonically treating the mixture for 30min, oscillating for 24h at the oscillation frequency of 150r/min, inactivating enzyme in a boiling water bath, cooling to room temperature, centrifugally separating for 20min at the centrifugal frequency of 5000r/min, collecting supernatant, and adding 0.5 part of sodium bicarbonate, wherein the solution is an extracting solution 2 and is marked as T-2.
(3) Taking a plurality of mosses, and mixing the mosses according to a mass ratio of 1: 15 adding deionized water, performing ultrasonic treatment at 25 deg.C for 10min, standing, collecting supernatant, and making into microorganism inoculation solution.
(4) Taking 5 parts of straw, preparing into powder with the diameter of not more than 0.05mm, adding 50 parts of glass sand, 10 parts of inoculation liquid and 10 parts of deionized water into a conical flask, placing the conical flask into an incubator at 25 ℃, culturing for 36h, weighing every 12h, adding a proper amount of deionized water to make up for the mass difference (adding deionized water until the total mass of the culture solution is unchanged), after the culture is finished, firstly adding 50 parts of deionized water, oscillating for 2h, wherein the oscillation frequency is 150r/min, after the oscillation is finished, collecting supernatant, carrying out centrifugal separation for 20min, wherein the centrifugal frequency is 5000r/min, taking supernatant, preparing straw fermentation liquor, and storing the straw fermentation liquor at the temperature of below 5 ℃.
(5) And mixing the fermentation liquor with the extracting solutions T1 and T2 in proportion to prepare the environment-friendly high-efficiency soil heavy metal eluting agent.
The green heavy metal eluting agent is prepared by compounding a kalimeris indica head extracting solution T1, a kalimeris indica head extracting solution T2, straw fermentation liquor and a chelating agent; the weight ratio of the Kalimeris indica extract T1 to the Kalimeris indica extract T2 is (1-9): 9-1, wherein the input ratio of the straw fermentation liquor is 0-50% of the total mass of the eluting agent.
Preferably, the mass ratio of the Kalimeris indica head extract T1 to the Kalimeris indica head extract T2 is 4:1, and the input ratio of the straw fermentation liquid is 10% of the total mass of the eluting agent.
The invention also combines ultrasonic and temperature rise to treat the heavy metal in the soil, and the concrete implementation steps are as follows:
step a: taking heavy metal contaminated soil which is typical yellow brown loam in south of the Yangtze river, removing miscellaneous stones, sieving, and determining the content of Cu 2080.22 mg.kg-1、Cd 180.36mg·kg-1、Pb 1986.34mg·kg-1、Cr 2196.68mg·kg-1And performing submerged culture for 7 days.
Step b: mixing the eluting agent with soil, wherein the mixing ratio is 1: and 5-50, and carrying out ultrasonic treatment for 30-90 min under the water bath condition.
Step c: and taking out the soil-water mixture, pouring the soil-water mixture into a high-temperature reaction kettle, and placing the reaction kettle into equipment, wherein the temperature is 50-100 ℃, and the reaction time is 0-160 min.
Step d: and repeatedly washing the leached soil by deionized water until the water is clear.
The detailed flow chart is shown in fig. 1.
Has the advantages that:
in the invention, the moss, the straw and the kalimeris indica are common plants in rural areas and are easy to collect. The plant fermentation liquor contains a large amount of soluble organic matters. Amino acid and carboxyl in T1 generate amino acid under the weak acidic condition, and the amino acid is a natural chelating agent and can chelate most heavy metals; in T2, the malan head contains a large amount of polysaccharide compounds, and the polysaccharide compounds are combined with sodium bicarbonate to form a natural surfactant, so that the stable heavy metal in a soil lattice structure is activated, the removal rate of the heavy metal is increased, the water-soil interfacial tension is reduced, the wetting effect of the eluent in the soil is improved, the infiltration of the eluent in the soil is facilitated, and the cost is reduced to a certain extent. After leaching is finished, the leaching agent can be naturally degraded, so that the leaching agent has both repairing efficiency and environmental protection; the T1 and the T2 are compounded, so that the composition has a certain synergistic effect on heavy metal removal. The eluting agent is a natural degradable chelating agent and has little harm to the environment.
Description of the drawings:
FIG. 1 is a flow chart of the experimental treatment.
Detailed Description
To explore the best conditions for the present eluent, the following experiments were performed:
t1: the compounding ratio of T2 is 1: 9. 2: 8. 3: 7. 4: 6. 5: 5. 6: 4. 7: 3. 8: 2. 9: 1; weighing 2g of soil with the rice straw fermentation liquor input ratio of 10%, adding 20ml of composite eluting agent with the ultrasonic power of 80W, treating for 30min, taking out a soil-water mixture, treating for 60min at the temperature of 80 ℃, repeatedly washing and eluting the leached soil with deionized water, digesting the residual soil, and obtaining the heavy metal removal rate by a subtraction method. Obtaining the compound ratio of the extracting solution.
T1: the compounding ratio of T2 is 4:1, adding fermentation liquor into the soil according to the proportion of 0, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% and 50% of the total leacheate, weighing 2g of soil, adding 20ml of the composite leacheate, treating for 30min with the ultrasonic power of 80W, taking out a soil-water mixture, treating for 120min at the temperature of 80 ℃, repeatedly washing and leaching the leached soil with deionized water, digesting the residual soil, and obtaining the removal rate of heavy metals by a differential method. Obtaining the optimal adding amount of the fermentation liquor.
T1: the compounding ratio of T2 is 4: weighing 2g of soil with the fermentation liquor input ratio of 10%, adding 10ml, 20ml, 40ml, 60 ml, 80 ml and 100ml of composite eluting agent, treating with the ultrasonic power of 80W for 30min, taking out a soil-water mixture, treating for 120min at the temperature of 80 ℃, repeatedly washing and eluting the leached soil with deionized water, digesting the residual soil, and obtaining the heavy metal removal rate by a differential method. And obtaining the optimal soil-water ratio.
T1: the compounding ratio of T2 is 4: weighing 2g of soil with the fermentation liquor input ratio of 10%, adding 20ml of composite eluting agent, carrying out ultrasonic treatment with the ultrasonic power of 0, 50, 60, 70, 80, 90 and 100W for 30min, taking out a soil-water mixture, treating for 120min at the temperature of 80 ℃, repeatedly washing and eluting the leached soil with deionized water, digesting the residual soil, and obtaining the heavy metal removal rate by a differential method. And obtaining the optimal ultrasonic power.
T1: the compounding ratio of T2 is 4: weighing 2g of soil with the fermentation liquor input ratio of 10%, adding 20ml of composite eluting agent, treating for 0, 10, 20, 30, 40, 50, 60, 70 and 80min with the ultrasonic power of 80W, taking out a soil-water mixture, treating for 120min at the temperature of 80 ℃, repeatedly washing and eluting the leached soil with deionized water, digesting the residual soil, and obtaining the removal rate of heavy metals by a differential method. And obtaining the optimal ultrasonic treatment time.
T1: the compounding ratio of T2 is 4: weighing 2g of soil with the fermentation liquor input ratio of 10%, adding 20ml of composite eluting agent, treating for 30min with the ultrasonic power of 80W, taking out a soil-water mixture, treating for 120min at the temperature of 60, 70, 80, 90, 100, 110 and 120 ℃, repeatedly washing and eluting the leached soil with deionized water, digesting the residual soil, and obtaining the heavy metal removal rate by a differential method. And obtaining the optimal experimental temperature.
T1: the compounding ratio of T2 is 4: weighing 2g of soil with the fermentation liquor input ratio of 10%, adding 20ml of composite eluting agent, treating for 30min with the ultrasonic power of 80W, taking out a soil-water mixture, treating for 0, 20, 40, 60, 80, 100, 120, 140 and 160min at the temperature of 80 ℃, repeatedly washing and eluting the leached soil with deionized water, digesting the residual soil, and obtaining the removal rate of heavy metals by a differential method. Obtaining the optimal heat treatment time.
The present invention will be described in detail with reference to the following embodiments in order to make the above objects, features and advantages of the present invention more comprehensible.
Example 1
Firstly, taking 14.4ml of T1 solution and 3.6ml of T2 solution, adding 2ml of fermentation liquor, and adjusting the pH value to 4.0; then, taking the soil after the flooding culture, and measuring the elution rates of the deionized water on Cu, Cd, Pb and Cr as follows in sequence: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluting agent, carrying out ultrasonic treatment for 30min at the ultrasonic power of 80W, and measuring the elution rates of Cu, Cd, Pb and Cr in the soil after the submerged culture by ultrasonic treatment in turn as follows: 46.32%, 55.10%, 43.82%, 49.57%.
And finally, placing the soil-water mixture subjected to ultrasonic treatment into a reaction kettle, and treating for 120min at the temperature of 80 ℃, wherein the elution rates of Cu, Cd, Pb and Cr in the soil subjected to ultrasonic washing by high-temperature treatment are as follows in sequence: 87.25%, 88.37%, 85.49%, 77.96%.
The total elution rates of Cu, Cd, Pb and Cr after treatment in the steps are as follows in sequence: 93.25%, 95.32%, 92.67%, 89.82%.
Example 2
Example 2 is similar to example 1, except that the composition of the extract used is different.
Firstly, 3ml of T1 solution and 15ml of T2 solution are taken from group 1, 2ml of fermentation liquor is added, 10ml of T1 solution is taken from group 2, 2ml of fermentation liquor is added into 8ml of T2 solution, 9ml of T1 solution is taken from group 3, and 2ml of fermentation liquor is added into 9ml of T2 solution, the pH value is adjusted to 4.0, then soil after flooding culture is taken, and the elution rates of deionized water on Cu, Cd, Pb and Cr are measured and sequentially: 1.12%, 3.22%, 2.52% and 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluting agent, carrying out ultrasonic treatment for 30min at the ultrasonic power of 80W, and measuring the elution rates of Cu, Cd, Pb and Cr in the soil after the submerged culture by ultrasonic treatment in turn as follows: 41.21%, 49.13%, 38.62%, 43.06%; 45.54%, 54.45%, 43.96%, 48.73%; 39.68%, 48.36%, 37.39%, 42.29%.
And finally, placing the soil-water mixture subjected to ultrasonic treatment into a reaction kettle, and treating for 120min at the temperature of 80 ℃, wherein the elution rates of Cu, Cd, Pb and Cr in the soil subjected to ultrasonic washing by high-temperature treatment are as follows in sequence: 82.78%, 82.88%, 83.05%, 72.65%; 86.96%, 87.80%, 84.94%, 77.46%; 81.45%, 82.50%, 79.81%, 72.78%.
The total elution rate of Cu, Cd, Pb and Cr after treatment in each step is as follows: 89.95%, 92.42%, 87.31%, 84.22%; 92.86%, 94.86%, 90.02%, 88.47; 83.95%, 85.78%, 82.51% and 80.84%.
Example 3
Example 3 is similar to example 1 except that the amount of fermentation broth added is different.
Firstly, taking 15.8ml of T1 solution and 3.2ml of T2 solution from group 1, adding 1ml of fermentation liquor, taking 10.5ml of T1 solution from group 2, adding 6ml of fermentation liquor into 3.5ml of T2 solution, adjusting the pH to 4.0, then taking soil after flooding culture, and measuring the elution rates of deionized water on Cu, Cd, Pb and Cr: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluting agent, carrying out ultrasonic treatment for 30min at the ultrasonic power of 80W, and measuring the elution rates of Cu, Cd, Pb and Cr in the soil after the submerged culture by ultrasonic treatment in turn as follows: 42.61%, 51.61%, 40.31%, 45.61%; 45.76%, 54.73%, 43.29%, 48.96%.
And finally, placing the soil-water mixture subjected to ultrasonic treatment into a reaction kettle, and treating for 120min at the temperature of 80 ℃, wherein the elution rates of Cu, Cd, Pb and Cr in the soil subjected to ultrasonic washing by high-temperature treatment are as follows in sequence: 80.27%, 81.31%, 78.65%, 71.72; 86.13%, 87.31%, 84.25%, 76.98%.
The total elution rate of Cu, Cd, Pb and Cr after treatment in each step is as follows: 87.65%, 89.60%, 86.17%, 84.43%; 92.24%, 95.27%, 90.66%, 88.83%.
Example 4
Firstly, taking 14.4ml of T1 solution and 3.6ml of T2 solution, adding 2ml of fermentation liquor, and adjusting the pH value to 4.0; then, taking the soil after the flooding culture, and measuring the elution rates of the deionized water on Cu, Cd, Pb and Cr as follows in sequence: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 10ml and 40ml of eluting agent, carrying out ultrasonic treatment for 30min at the ultrasonic power of 80W, and measuring the elution rates of Cu, Cd, Pb and Cr in the soil after the submerged culture by ultrasonic treatment in turn as follows: 38.34%, 49.35%, 37.54%, 43.26%%; 46.05%, 54.95%, 42.96% and 49.12%.
And finally, placing the soil-water mixture subjected to ultrasonic treatment into a reaction kettle, and treating for 120min at the temperature of 80 ℃, wherein the elution rates of Cu, Cd, Pb and Cr in the soil subjected to ultrasonic washing by high-temperature treatment are as follows in sequence: 85.34%, 86.54%, 86.74%, 75.68%; 86.05%, 88.17%, 85.09%, 77.56%.
The total elution rates of Cu, Cd, Pb and Cr after treatment in the steps are as follows in sequence: 88.76%, 90.16%, 84.07%, 82.23%; 92.86%, 95.82%, 90.67%, 88.74%.
Example 5
Example 5 is similar to example 1, except that the sonication time is different.
Firstly, taking 14.4ml of T1 solution and 3.6ml of T2 solution, adding 2ml of fermentation liquor, adjusting the pH to 4.0, then taking soil after flooded culture, and measuring the elution rates of deionized water on Cu, Cd, Pb and Cr: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluting agent, carrying out ultrasonic treatment for 20min and 80min, and measuring the elution rates of Cu, Cd, Pb and Cr in the soil after the submerged culture by ultrasonic treatment in turn as follows: 42.78%, 49.63%, 40.62%, 44.87%; 45.62%, 54.14%, 42.99%, 49.13%.
And finally, placing the soil-water mixture subjected to ultrasonic treatment into a reaction kettle, treating for 120min at the temperature of 120 ℃, wherein the elution rates of Cu, Cd, Pb and Cr in the soil subjected to ultrasonic washing by high-temperature treatment are as follows in sequence: 83.21%, 82.92%, 81.66%, 73.44%; 86.29%, 87.39%, 84.54%, 77.11%.
The total elution rates of Cu, Cd, Pb and Cr after treatment in the steps are as follows in sequence: 89.45%, 88.11%, 86.71%, 84.76%; 92.41%, 94.46%, 90.75%, 88.38%.
Example 6
Example 6 is similar to example 1 except that the sonication power is different.
Firstly, taking 14.4ml of T1 solution and 3.6ml of T2 solution, adding 2ml of fermentation liquor, adjusting the pH to 4.0, then taking soil after flooded culture, and measuring the elution rates of deionized water on Cu, Cd, Pb and Cr: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluting agent, carrying out ultrasonic treatment for 30min at the power of 50W and 100W, and measuring the elution rates of Cu, Cd, Pb and Cr in the soil after the submerged culture by ultrasonic treatment in turn as follows: 42.68%, 50.63%, 41.62%, 43.74%; 46.64%, 55.03%, 42.99%, 49.04%.
And finally, placing the soil-water mixture subjected to ultrasonic treatment into a reaction kettle, and treating for 120min at the temperature of 120 ℃, wherein the high-temperature treatment sequentially has the following elution rates of Cu, Cd, Pb and Cr in the soil subjected to ultrasonic washing: 83.21%, 82.92%, 81.66%, 73.44%; 86.29%, 87.39%, 84.54%, 77.11%.
The total elution rate of Cu, Cd, Pb and Cr after treatment in each step is as follows: 88.34%, 89.34%, 85.68%, 84.76%; 92.57%, 94.94%, 90.56%, 88.15%.
Example 7
Example 7 is similar to example 1 except that the treatment temperature is different.
Firstly, taking 14.4ml of T1 solution and 3.6ml of T2 solution, adding 2ml of fermentation liquor, adjusting the pH to 4.0, then taking soil after flooded culture, and measuring the elution rates of deionized water on Cu, Cd, Pb and Cr: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluting agent, carrying out ultrasonic treatment for 30min at the ultrasonic power of 80W, and measuring the elution rates of Cu, Cd, Pb and Cr in the soil after the submerged culture by ultrasonic treatment in turn as follows: 46.32%, 55.10%, 43.82%, 49.57%.
And finally, placing the soil-water mixture subjected to ultrasonic treatment into a reaction kettle, and treating for 120min at the temperature of 50 ℃ and 100 ℃, wherein the elution rates of Cu, Cd, Pb and Cr in the soil subjected to ultrasonic washing by high-temperature treatment are as follows in sequence: 80.78%, 82.74%, 77.67%, 73.92%; 87.01%, 87.09%, 84.94%, 76.88%.
The total elution rates of Cu, Cd, Pb and Cr after treatment in the steps are as follows in sequence: 89.65%, 93.17%, 87.82%, 86.72%; 93.07%, 95.66% and 89.25%.
Example 8
Example 8 is similar to example 1, except that the high temperature treatment time is different
Firstly, taking 14.4ml of T1 solution and 3.6ml of T2 solution, adding 2ml of fermentation liquor, adjusting the pH to 4.0, then taking soil after flooding culture, and measuring the elution rates of deionized water on Cu, Cd, Pb and Cr, which are sequentially as follows: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluting agent, carrying out ultrasonic treatment for 30min at the ultrasonic power of 80W, and measuring the elution rates of Cu, Cd, Pb and Cr in the soil after the submerged culture by ultrasonic treatment in turn as follows: 46.32%, 55.10%, 43.82%, 49.57%.
And finally, placing the soil-water mixture subjected to ultrasonic treatment into a reaction kettle, and treating for 30min and 140min at the temperature of 80 ℃, wherein the elution rates of Cu, Cd, Pb and Cr in the soil subjected to ultrasonic washing by high-temperature treatment are as follows in sequence: 81.48%, 82.72%, 77.94%, 73.92%; 87.01%, 87.97%, 84.92% and 76.85%. The total elution rates of Cu, Cd, Pb and Cr after treatment in the steps are as follows in sequence: 88.64%, 91.62%, 87.11%, 85.31%; 92.51%, 95.55%, 90.94%, 89.10%
Comparative example 1
Comparative example 1 is similar to example 1, except that no plant fermentation broth was used
Firstly, taking 16ml of T1 solution and 4ml of T2 solution, adjusting the pH value to 4.0, then taking soil after flooding culture, and measuring the elution rates of deionized water on Cu, Cd, Pb and Cr as follows: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluting agent, carrying out ultrasonic treatment for 30min at the ultrasonic power of 80W, and measuring the elution rates of Cu, Cd, Pb and Cr in the soil after the submerged culture by ultrasonic treatment, wherein the elution rates are as follows in sequence: 44.12%, 51.10%, 40.24%, 44.52%.
And finally, placing the soil-water mixture subjected to ultrasonic treatment into a reaction kettle, and treating for 120min at the temperature of 80 ℃, wherein the elution rates of Cu, Cd, Pb and Cr in the soil subjected to ultrasonic washing by high-temperature treatment are as follows in sequence: 87.25%, 82.74%, 81.16%, 70.12%.
The total elution rates of Cu, Cd, Pb and Cr after treatment in the steps are as follows in sequence: 89.64%, 90.62%, 86.11%, 80.31%.
Comparative example 2
Comparative example 2 is similar to example 1 except that T1 extract was not used
Firstly, taking 18ml of T2 solution, adding 2ml of fermentation liquor, taking soil after flooding culture, and measuring the elution rates of deionized water on Cu, Cd, Pb and Cr, which are sequentially as follows: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluting agent, carrying out ultrasonic treatment for 30min at the ultrasonic power of 80W, and measuring the elution rates of Cu, Cd, Pb and Cr in the soil after the submerged culture by ultrasonic treatment in turn as follows: 24.56%, 26.35%, 26.24%, 20.52%.
And finally, placing the soil-water mixture subjected to ultrasonic treatment into a reaction kettle, and treating for 120min at the temperature of 80 ℃, wherein the elution rates of Cu, Cd, Pb and Cr in the soil subjected to ultrasonic washing by high-temperature treatment are as follows in sequence: 32.25%, 12.47%, 16.38%, 30.65%.
The total elution rates of Cu, Cd, Pb and Cr after treatment in the steps are as follows in sequence: 49.64%, 32.22%, 36.44%, 50.56%.
Comparative example 3
Comparative example 3 is similar to example 1 except that no T2 extract was added.
Firstly, taking 18ml of T1 solution, adding 2ml of fermentation liquor, then taking soil after flooding culture, and measuring the elution rates of deionized water on Cu, Cd, Pb and Cr, which are sequentially as follows: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluting agent, carrying out ultrasonic treatment for 30min at the ultrasonic power of 80W, and measuring the elution rates of Cu, Cd, Pb and Cr in the soil after the submerged culture by ultrasonic treatment in turn as follows: 44.34%, 51.15%, 40.39%, 41.75%.
And finally, placing the soil-water mixture subjected to ultrasonic treatment into a reaction kettle, and treating for 120min at the temperature of 80 ℃, wherein the elution rates of Cu, Cd, Pb and Cr in the soil subjected to ultrasonic washing by high-temperature treatment are as follows in sequence: 82.18%, 82.48%, 79.67%, 64.15%.
The total elution rates of Cu, Cd, Pb and Cr after treatment in the steps are as follows in sequence: 90.05%, 89.72%, 85.82%, 79.31%.
Comparative example 4
Comparative example 4 is similar to example 1 except that an EDTA-CA built eluent was used.
Firstly, 10ml of each of 0.08mol/LEDTA-2Na and 0.2mol/LCA is adjusted to pH 4.0, then soil after flooded culture is taken, and the elution rates of deionized water on Cu, Cd, Pb and Cr are measured to be as follows: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluting agent, carrying out ultrasonic treatment for 30min at the ultrasonic power of 80W, and measuring the elution rates of the soil Cu, Cd, Pb and Cr after the flooded culture by ultrasonic treatment in turn as follows: 46.12%, 55.10%, 42.24%, 47.52%.
And finally, placing the soil-water mixture subjected to ultrasonic treatment into a reaction kettle, and treating for 120min at the temperature of 80 ℃, wherein the elution rates of Cu, Cd, Pb and Cr in the soil subjected to ultrasonic washing by high-temperature treatment are as follows in sequence: 87.25%, 82.74%, 81.16%, 70.12%.
The total elution rates of Cu, Cd, Pb and Cr after treatment in the steps are as follows in sequence: 92.64%, 93.62%, 90.11%, 86.31%.
Comparative example 5
Comparative example 5 is similar to example 1 except that no ultrasound was used.
Firstly, taking 14.4ml of T1 solution and 3.6ml of T2 solution, adding 2ml of fermentation liquor, then taking soil after flooding culture, and measuring the elution rates of deionized water on Cu, Cd, Pb and Cr: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluent, placing the contaminated soil into a reaction kettle, treating for 120min at the temperature of 80 ℃, wherein the elution rates of Cu, Cd, Pb and Cr in the soil after flooding culture by high-temperature treatment are as follows in sequence: 85.85%, 86.27%, 83.73%, 76.34%.
The total elution rates of Cu, Cd, Pb and Cr after treatment in the steps are as follows in sequence: 86.05%, 86.52%, 84.15%, 76.66%.
Comparative example 6
Comparative example 6 is similar to example 1 except that high temperature treatment was not used.
Firstly, taking 14.4ml of T1 solution and 3.6ml of T2 solution, adding 2ml of fermentation liquor, then taking soil after flooding culture, and measuring the elution rates of deionized water on Cu, Cd, Pb and Cr: 1.12%, 3.22%, 2.52%, 1.02%.
And then, taking 2g of contaminated soil, adding 20ml of eluting agent, carrying out ultrasonic treatment for 30min at the ultrasonic power of 80W, and measuring the elution rates of Cu, Cd, Pb and Cr in the soil after the submerged culture by ultrasonic treatment in turn as follows: 46.51%, 54.95%, 43.12%, 48.75%.
The total elution rates of Cu, Cd, Pb and Cr after treatment in the steps are as follows in sequence: 47.09%, 56.34%, 44.55%, 49.25%.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
TABLE 1 basic Properties of soil before and after washing
Claims (8)
1. A green heavy metal eluting agent is characterized in that the green heavy metal eluting agent is prepared by compounding a Kalimeris indica extract T1, a Kalimeris indica extract T2 and a straw fermentation liquid; wherein the mass ratio of the Kalimeris indica head extract T1 to the Kalimeris indica head extract T2 is 1-9: 9-1, wherein the input ratio of the straw fermentation liquor is 0-50% of the total mass of the eluting agent.
2. The green heavy metal eluent as claimed in claim 1, wherein the mass ratio of the Kalimeris indica extract T1 to the Kalimeris indica extract T2 is 4:1, and the input ratio of the straw fermentation liquid is 10% of the total mass of the eluent.
3. The preparation method of the green heavy metal eluting agent is characterized by comprising the following steps:
(1) taking 5 parts of wild herba Kalimeridis, removing rootstalk, naturally drying in the sun, crushing into powder with the diameter of not more than 0.05mm, adding 100 parts of water, mixing and oscillating at 40-60 ℃ for 24 hours, wherein the oscillation frequency is 150r/min, taking out the mixture, adding 0.05 part of citric acid, centrifugally separating for 20min, wherein the centrifugal frequency is 5000r/min, collecting supernatant, performing suction filtration, adding 1 part of EDTA-2Na, and preparing into an extracting solution which is marked as T-1;
(2) taking 5 parts of wild herba Kalimeridis rhizome, naturally drying in the sun, crushing into powder with the diameter of not more than 0.05mm, adding 100 parts of water, adding 0.1 part of complex enzyme, oscillating for 24 hours with the oscillation frequency of 150r/min, inactivating enzyme in a boiling water bath, cooling to room temperature, removing precipitate, taking clear liquid, centrifugally separating for 20min with the centrifugation frequency of 5000r/min, collecting supernatant, adding 0.5 part of sodium bicarbonate, and marking as an extracting solution 2 as T-2;
(3) taking moss, and carrying out the following steps: 15, adding deionized water, performing ultrasonic treatment at 25 ℃ for 10min, standing, and taking supernatant to prepare microorganism inoculation liquid;
(4) taking 5 parts of straws, preparing into powder with the diameter of not more than 0.05mm, adding 50 parts of glass sand, 10 parts of inoculation liquid and 10 parts of deionized water into a conical flask, placing the conical flask in an incubator at 25 ℃, culturing for 36h, weighing every 12h, adding deionized water to make up for the mass difference, after the culture is finished, adding 50 parts of deionized water, oscillating for 2h at the oscillation frequency of 150r/min, after the oscillation is finished, collecting supernatant, centrifugally separating for 20min at the centrifugal frequency of 5000r/min, taking the supernatant, preparing into straw fermentation liquid, and storing at the temperature of below 5 ℃;
(5) mixing the straw fermentation liquor with the extracting solution T1 and T2 in proportion to prepare the heavy metal eluting agent.
4. The preparation method of the green heavy metal eluting agent as claimed in claim 3, wherein the compound enzyme in the step (2) is prepared by mixing the components in a mass ratio of 1: 1: 1, xylanase, amylase and beta-glucanase.
5. An application method of a green heavy metal eluting agent is characterized by comprising the following steps:
(1) mixing the polluted soil after flooding culture with an eluting agent;
(2) carrying out ultrasonic treatment on the soil-water mixture, and standing to room temperature after the treatment is finished;
(3) carrying out heat treatment on the soil-water mixture; centrifugally separating the soil from the liquid, and repeatedly washing the soil by deionized water.
6. The method for applying the green heavy metal eluting detergent as claimed in claim 5, wherein the contaminated soil in the step (1) is flooded and cultured for 7 days, and the soil-water ratio of the soil to the eluting detergent is 1: 5 to 50.
7. The application method of the green heavy metal eluting agent according to claim 5, wherein the ultrasonic power in the step (2) is 50-100W, and the ultrasonic time is 0-80 min.
8. The method for applying the green heavy metal eluting agent according to claim 5, wherein the heat treatment temperature in the step (3) is 60 to 120 ℃ and the treatment time is 0 to 160 min.
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