CN114479875B - Eluting agent for restoring pesticide chemical polluted soil and preparation process thereof - Google Patents
Eluting agent for restoring pesticide chemical polluted soil and preparation process thereof Download PDFInfo
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- CN114479875B CN114479875B CN202210168320.2A CN202210168320A CN114479875B CN 114479875 B CN114479875 B CN 114479875B CN 202210168320 A CN202210168320 A CN 202210168320A CN 114479875 B CN114479875 B CN 114479875B
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- B09C1/08—Reclamation of contaminated soil chemically
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention discloses an eluent for remedying pesticide chemical polluted soil and a preparation process thereof, wherein the eluent comprises 3 groups of eluents which are mutually independent, and the preparation process of the eluent comprises the following steps: s1, preparing aspergillus niger citric acid fermentation liquor: s1-1, preparing a culture medium; s1-2, activating aspergillus niger; s1-3, preparing a suspension; s1-4, inoculating aspergillus niger; s2, preparing a first leacheate; s3, preparing a second leacheate; s4, preparing a third leacheate. The eluent is prepared by compounding 3 different types of eluents, adopts an eluent formula which takes aspergillus niger citric acid fermentation liquor and chloride salt as main components, combines organically modified sepiolite powder with strong adsorbability, makes up the condition of poor leaching effect of a single eluent, and has good removal effect on heavy metal pollutants, organic pollutants o, p' -DDT, alpha-HCH, o-nitrochlorobenzene and the like caused by chemical pesticide residues in soil.
Description
Technical Field
The invention relates to the technical field of pesticide chemical polluted soil treatment, in particular to an eluent for restoring pesticide chemical polluted soil and a preparation process thereof.
Background
At present, the pesticide chemical pollution is increasingly serious, and particularly, heavy metal pollutants or organic pollutants are easy to accumulate and difficult to degrade after entering soil, and have great harm to human health and an ecological system, so that the pesticide chemical pollution soil is urgently repaired. In principle, two ways are available for effectively solving the problem of pesticide chemical pollution of soil: firstly, the occurrence form of the pollutants in the soil is changed from an activated state to a residue state, so that the biotoxicity of the pollutants is reduced; and secondly, directly reducing the content of pollutants in the soil to enable the pollutants to reach the background content.
According to investigation, a large part of the pollution of a pesticide-polluted site is concentrated and enriched in filling soil, sandy soil and cohesive soil containing gravels, the part of the pollution has large soil volume, loose soil quality, poor uniformity and more complex components, plant roots, gravels, bricks and the like are frequently clamped in a shallow part, the part of the pollution is mainly the cohesive soil, the content of organic matters is high, and the pollution is water-soil combined pollution. The remediation technologies such as chemical oxidation and thermal desorption commonly used for remedying the contaminated soil in the pesticide factory have certain limitations in treating the contaminated soil of a filling layer with complex components. In-situ chemical oxidation, rhizomes, gravels and the like of plants in the soil filling layer can form an advantage channel for loss of the repairing medicament, so that cohesive soil which is most prone to enriching pollutants can not contact the repairing medicament; ex-situ chemical oxidation, and the impurities can also cause uneven stirring of the medicament and damage to the repair equipment; the thermal desorption repair technology has the problems of high energy consumption and secondary pollution, and can directly damage the soil structure. Therefore, the grading leaching remediation technology has very important practical significance for solving the soil pollution, on one hand, the subsequent soil remediation amount can be greatly reduced from the source through particle size grading, the remediation efficiency is improved, on the other hand, the soil activity can be maintained, and the washed gravel and the like can be recycled.
The chemical method eluting agent remediation is a commonly used pesticide chemical contaminated soil remediation method, and reduces the harm of pollutants in soil to the ecological environment by changing the chemical forms of the pollutants. The leaching method is to leach the soil by using a leaching agent to wash away pollutants in the soil, and collecting the leaching agent. The soil eluting agent mainly comprises 4 kinds of inorganic eluting agents, chelating agents, non-biological surfactants and biological surfactants, and the action mechanism of the soil eluting agent can be divided into ion exchange action, chelating action and complexing action. Three simple action mechanisms of the soil eluting agent form different eluting effects under different interface conditions, the surfactant promotes the complexing action, and the inorganic eluting agent promotes the ion exchange action.
However, the types of pollutants in the pesticide chemical polluted soil are complex, the leaching effect of a single leaching agent is often poor, multiple leaching agents are required to be used in a matched mode or used in a matched mode with other methods, for example, chemical leaching repair and electric repair are combined, and the electric repair efficiency can be effectively improved through the leaching agents. CN104289511B discloses an eluent for synchronously removing polychlorinated biphenyl and heavy metals in soil, a preparation method and application thereof. The eluent is formed by mixing citric acid solution and tween80 solution. The method for restoring polychlorinated biphenyl-heavy metal combined polluted soil comprises the following steps: and (3) adding an eluting agent for synchronously removing the polychlorinated biphenyl and the heavy metal in the polychlorinated biphenyl-heavy metal composite polluted soil into the polychlorinated biphenyl-heavy metal composite polluted soil, mixing, oscillating and eluting to finish the restoration of the polychlorinated biphenyl-heavy metal composite polluted soil. The leaching agent reduces the environmental risk after leaching remediation, synchronously removes polychlorinated biphenyl and heavy metals in soil, has good soil remediation effect and high elution rate. However, the eluent has single component, and the repaired polluted soil has certain limitation.
Disclosure of Invention
Aiming at the problems, the invention provides an eluent for repairing pesticide chemical polluted soil and a preparation process thereof.
The technical scheme of the invention is as follows:
the utility model provides an eluent for restoreing pesticide chemical industry contaminated soil, includes 3 independent eluents of group each other, and 3 groups of eluents are in proper order according to adding the order sequencing:
first leacheate: the fermentation broth comprises, by weight, 10-12 parts of aspergillus niger citric acid fermentation broth with the mass fraction of 80-85% and 6-8 parts of NaCl solution with the mass concentration of 0.2-0.3 mol/L;
a second leacheate: comprises 8 to 11 portions of shaddock peel powder, 7 to 9 portions of organic modified sepiolite powder and MgCl with the mass concentration of 0.05 to 0.08mol/L 2 3-7 parts of solution, feCl with the mass concentration of 0.4-0.6mol/L 3 5-6 parts of a solution;
a third leacheate: the fermentation broth comprises, by weight, 3-5 parts of aspergillus niger citric acid fermentation broth with the mass fraction of 75-80%, 5-6 parts of Trition X-100 with the mass fraction of 5%, 4-5 parts of TWEEN with the mass fraction of 3%, 2-3 parts of rhamnolipid and 1-2 parts of saponin active agent.
The preparation process of the eluent for repairing pesticide chemical polluted soil comprises the following steps:
s1, preparing aspergillus niger citric acid fermentation liquor:
s1-1, preparation of a culture medium: preparing a PDA culture medium and a shake flask culture medium;
s1-2, activating aspergillus niger: placing 1-2 rings of Aspergillus niger strains in a PDA culture medium, and culturing in a constant temperature incubator at 32-35 deg.C for 5-7d to obtain activated Aspergillus niger;
s1-3, preparing a suspension: taking out the culture medium, adding deionized water 30-35% of the culture medium, washing out black spores, placing into shake flask, shaking for 30min, counting spores in shake flask with blood counting plate, and adjusting the number concentration of spores in shake flask to 3-4 × 10 6 Obtaining Aspergillus niger spore suspension liquid in each ml;
s1-4, inoculating aspergillus niger: transferring the aspergillus niger spore suspension into a shake flask culture medium, wherein the mass ratio of the aspergillus niger spore suspension to the shake flask culture medium is 1:10, putting the mixture into a constant-temperature shaking table at the temperature of 32-35 ℃ for culturing for 30d to obtain aspergillus niger citric acid fermentation liquor;
s2, preparing a first leacheate: according to the weight parts, taking aspergillus niger citric acid fermentation liquor, adding deionized water into the aspergillus niger citric acid fermentation liquor to adjust the mass fraction of the aspergillus niger citric acid fermentation liquor to 80-85%, and then dropwise adding a NaCl solution into the aspergillus niger citric acid fermentation liquor and continuously stirring to obtain a first leacheate;
s3, preparing a second leacheate: grinding the shaddock peel to the particle size of 50-60 mu m according to the weight parts, mixing the ground shaddock peel with organic modified sepiolite powder to obtain mixed powder, heating the mixed powder for 1h at the temperature of 78-85 ℃, then rapidly cooling the mixed powder by using liquid nitrogen to obtain microspherical particles with microcracks on the surfaces, and then placing the microspherical particles into MgCl 2 In the solution, feCl is added dropwise while stirring continuously 3 Continuously stirring the solution for 30min after the dropwise addition is finished;
s4, preparing a third leacheate: taking aspergillus niger citric acid fermentation liquor according to the weight parts, and adding HNO into the aspergillus niger citric acid fermentation liquor 3 The pH value of aspergillus niger citric acid fermentation liquor is adjusted to 4-5 by the solution, then deionized water is added to adjust the mass fraction of the aspergillus niger citric acid fermentation liquor to 75-80%, then a mixture of Trition X-100, TWEEN80, rhamnolipid and saponin active agent is added, and ultrasonic dispersion is carried out for 30min to obtain third leacheate.
Further, the PDA culture medium in the step S1-1 comprises the following components in percentage by mass: mixing the above materials, boiling, filtering, sterilizing at 125-130 deg.C for 15-20min in a high temperature sterilizing pot to obtain PDA culture medium. The compatibility of the aspergillus niger fermentation is better, and the materials are easy to obtain and the preparation is convenient.
Further, in the step S1-1, the shake flask culture medium comprises the following components by mass percent: 5-6% of corn flour, 3-4% of peptone, 0.15-0.2% of sodium nitrate, 0.01-0.02% of monopotassium phosphate, 0.005% of magnesium sulfate, 0.4-0.6% of yeast extract and the balance of deionized water, mixing the components, placing the mixture in a high-temperature sterilization pot, and sterilizing the mixture for 15-20min at 125-130 ℃ to obtain the shake flask culture medium. The shake flask culture medium can effectively promote the fermentation of aspergillus niger.
Further, the rotating speed of the shaking table in the step S1-4 is 200-240r/min. Reasonable rotating speed setting can further promote the fermentation of aspergillus niger.
Further, the dropping speed of the NaCl solution in the step S2 is 2-3ml/S, the stirring speed is 100r/min, and the stirring time is 10-15min. The NaCl solution and the aspergillus niger citric acid fermentation liquor are stably mixed to improve the leaching efficiency.
Further, the preparation method of the organic modified sepiolite powder in the step S3 comprises the following steps:
s3-1: grinding the raw sepiolite stone to the particle size of 70-80 μm to obtain raw sepiolite stone powder;
s3-2: mixing sepiolite raw stone powder with deionized water, wherein the mass concentration of the sepiolite raw stone powder is 15-17g/L, then adding sodium hexametaphosphate, controlling the volume concentration of the sodium hexametaphosphate to be 0.5-0.9ml/L, stirring and reacting for 8-10h at 135-140 ℃, and standing for 3h to obtain a hydrothermal modified sepiolite suspension;
s3-3: centrifugally separating the hydrothermal modified sepiolite suspension, drying the precipitate at 70-80 ℃, and grinding the precipitate until the particle size is 20-30 mu m to obtain hydrothermal modified sepiolite powder;
s3-4: mixing hydrothermal modified sepiolite powder with deionized water, wherein the mass concentration of the hydrothermal modified sepiolite powder is 23-26g/L, dropwise adding cetyl trimethyl ammonium bromide into the mixture and continuously stirring the mixture, controlling the volume concentration of the cetyl trimethyl ammonium bromide to be 3.15-3.3ml/L, then continuously dropwise adding sodium dodecyl sulfate into the mixture and continuously stirring the mixture, controlling the volume concentration of the sodium dodecyl sulfate to be 2.75-2.9ml/L, centrifugally separating the mixture after the dropwise adding is finished, and drying the precipitate at the temperature of 60-70 ℃ to obtain the organic modified sepiolite. The organic modified sepiolite has good dispersibility, moderate viscosity and good thermal stability, and can play a good catalytic role in heavy metal ion treatment and chemical wastewater treatment.
Further, feCl in the step S3 3 The dropping speed of the solution is 1-2ml/s, and the stirring speed is 60-70r/min. FeCl 3 The solution has the strongest effect on heavy metals in soil, and can achieve the optimal heavy metal desorption effect by combining with the organic modified sepiolite powder.
Further, the power of the ultrasonic dispersion in the step S4 is 300-350W, and the frequency is 20kHz. The dispersion of the biosurfactant in the aspergillus niger citric acid fermentation liquor is promoted, and the biosurfactant is used as the eluent in the last step, so that the secondary pollution to the soil environment is effectively reduced.
The invention has the beneficial effects that:
(1) According to the invention, 3 different types of eluents are compounded, an eluent formula which takes aspergillus niger citric acid fermentation liquor and chloride as main components is adopted, and organic modified sepiolite powder with strong adsorbability is combined, so that the optimal leaching effect is achieved through a sequential application mode, the condition that a single eluent is poor in leaching effect is made up, the 3 types of eluents are good in adaptability, can not generate a conflict reaction, are small in secondary harm to the environment, and have good removal effects on heavy metal pollutants, organic pollutants o, p' -DDT, alpha-HCH, o-nitrochlorobenzene and the like caused by chemical pesticide residues in soil.
(2) The preparation method of the eluent is efficient and reasonable, the selected culture medium has good compatibility to aspergillus niger fermentation, the materials are easy to obtain, the preparation is convenient, the fermentation of aspergillus niger can be effectively promoted, and by mixing aspergillus niger citric acid fermentation liquor and chloride salt, better eluent effect can be achieved compared with a single eluent, and the dosage of the eluent is saved.
(3) The preparation method of the eluent obtains the organically modified sepiolite powder through the repeated modification of the sepiolite, has stronger adsorbability to pollutants in soil, and is quenched by liquid nitrogen and then mixed with FeCl 3 The solution combination can effectively promote the desorption of heavy metal pollutants in soil, the organic modified sepiolite has good dispersibility, moderate viscosity and good thermal stability, and can play a good catalytic role in the treatment of heavy metal ions and the treatment of pesticide residues.
Drawings
FIG. 1 is a process flow diagram of a method of preparing an eluent in accordance with the present invention.
Detailed Description
Example 1
The utility model provides an eluent for repairing pesticide chemical industry pollutes soil, includes 3 independent eluents of group, and 3 groups of eluents are in proper order according to adding the order sequencing:
first leacheate: the fermentation liquor comprises 11 parts by weight of aspergillus niger citric acid fermentation liquor with the mass fraction of 82% and 7 parts by weight of NaCl solution with the mass concentration of 0.25 mol/L;
a second leacheate: comprises 9 portions of shaddock peel powder, 8 portions of organic modified sepiolite powder and MgCl with the mass concentration of 0.06mol/L 2 5 parts of solution, feCl with the mass concentration of 0.5mol/L 3 6 parts of a solution;
a third leacheate: the aspergillus niger and aspergillus niger fermentation broth comprises, by weight, 4 parts of aspergillus niger citric acid fermentation broth with the mass fraction of 77%, 5 parts of Trition X-100 parts of Triton with the mass fraction of 5%, 80 parts of TWEEN with the mass fraction of 3%, 2.5 parts of rhamnolipid and 1.5 parts of saponin active agent.
The preparation process of the eluent for repairing pesticide chemical polluted soil comprises the following steps:
s1, preparing aspergillus niger citric acid fermentation liquor:
s1-1, preparation of a culture medium: preparing a PDA culture medium and a shake flask culture medium, wherein the PDA culture medium comprises the following components in percentage by mass: 17% of starch, 2% of glucose, 3% of agar and the balance of deionized water, mixing the above components, boiling, filtering, placing in a high-temperature sterilization pot, sterilizing at 128 ℃ for 18min to obtain a PDA culture medium, wherein the shake flask culture medium comprises the following components in percentage by mass: mixing 5% of corn flour, 4% of peptone, 0.18% of sodium nitrate, 0.01% of monopotassium phosphate, 0.005% of magnesium sulfate, 0.5% of yeast extract and the balance of deionized water, placing the mixture into a high-temperature sterilization pot, sterilizing for 18min at 128 ℃, wherein the high-temperature sterilization pot is a commercially available BIOBASE high-temperature sterilization pot, and obtaining a shake flask culture medium;
s1-2, activating aspergillus niger: placing the 1-ring aspergillus niger strain in a PDA culture medium, and placing the PDA culture medium in a constant-temperature incubator at 34 ℃ for culturing for 6d to obtain activated aspergillus niger;
s1-3, preparing a suspension: taking out the culture medium, adding deionized water 33% of the culture medium, washing out black spores, placing in a shake flask, shaking at 230r/min, and subjecting the spores in the shake flask to hemacytometerCounting is carried out, and the number concentration of spores in the shake flask is adjusted to be 3.5 multiplied by 10 6 Obtaining Aspergillus niger spore suspension liquid in each ml;
s1-4, inoculating aspergillus niger: transferring the aspergillus niger spore suspension into a shake flask culture medium, wherein the mass ratio of the aspergillus niger spore suspension to the shake flask culture medium is 1:10, putting the mixture into a constant-temperature shaking table at 34 ℃ for culturing for 30d to obtain aspergillus niger citric acid fermentation liquor;
s2, preparing a first leacheate: taking aspergillus niger citric acid fermentation liquor according to parts by weight, adding deionized water into the aspergillus niger citric acid fermentation liquor to adjust the mass fraction of the aspergillus niger citric acid fermentation liquor to 83%, then dropwise adding a NaCl solution into the aspergillus niger citric acid fermentation liquor and continuously stirring the solution, wherein the dropwise adding speed of the NaCl solution is 2ml/s, the stirring speed is 100r/min, and the stirring time is 12min to obtain first leacheate;
s3, preparing a second leacheate: grinding pomelo peel to 55 mu m in particle size according to parts by weight, mixing the pomelo peel and the organically modified sepiolite powder to obtain mixed powder, heating the mixed powder for 1h at the temperature of 81 ℃, then rapidly cooling the mixed powder by using liquid nitrogen to obtain microspherical particles with microcracks on the surfaces, and then placing the microspherical particles into MgCl 2 FeCl is added dropwise into the solution while stirring continuously 3 Solutions, feCl 3 The dropping speed of the solution is 1ml/s, the stirring speed is 65r/min, and the stirring is continued for 30min after the dropping is finished;
the preparation method of the organic modified sepiolite powder comprises the following steps:
s3-1: grinding the raw sepiolite stone to the particle size of 75 mu m to obtain raw sepiolite stone powder;
s3-2: mixing sepiolite raw stone powder with deionized water, controlling the mass concentration of the sepiolite raw stone powder to be 16g/L, then adding sodium hexametaphosphate, controlling the volume concentration of the sodium hexametaphosphate to be 0.7ml/L, stirring and reacting for 9 hours at the temperature of 138 ℃, and standing for 3 hours to obtain a hydrothermal modified sepiolite suspension;
s3-3: centrifugally separating the hydrothermal modified sepiolite suspension, drying the precipitate at 75 ℃, and grinding the precipitate until the particle size is 26 mu m to obtain hydrothermal modified sepiolite powder;
s3-4: mixing hydrothermal modified sepiolite powder with deionized water, wherein the mass concentration of the hydrothermal modified sepiolite powder is 24g/L, dropwise adding cetyl trimethyl ammonium bromide into the mixture and continuously stirring the mixture, controlling the volume concentration of the cetyl trimethyl ammonium bromide to be 3.2ml/L, then continuously dropwise adding sodium dodecyl sulfate into the mixture and continuously stirring the mixture, controlling the volume concentration of the sodium dodecyl sulfate to be 2.8ml/L, centrifugally separating the mixture after the dropwise adding is finished, and drying the precipitate at the temperature of 65 ℃ to obtain the organic modified sepiolite;
s4, preparing a third leacheate: taking aspergillus niger citric acid fermentation liquor according to the weight portion, adding HNO into the aspergillus niger citric acid fermentation liquor 3 The pH value of aspergillus niger citric acid fermentation liquor is adjusted to 4.5 by the solution, deionized water is added to adjust the mass fraction of the aspergillus niger citric acid fermentation liquor to 77%, a mixture of Trition X-100, TWEEN80, rhamnolipid and saponin active agent is added, ultrasonic dispersion is carried out for 30min, the power of ultrasonic dispersion is 330W, and the frequency is 20kHz, and third leacheate is obtained.
The application of the eluent is applied to the eluent for repairing pesticide chemical polluted soil, and the application method comprises the following steps: the three leacheate are sequentially applied to the pesticide chemical polluted soil every m 3 The total amount of the three leacheate applied in the soil was 850L, the first leacheate was 239L, the second leacheate was 371L, and the third leacheate was 240L.
Example 2
The present embodiment is different from embodiment 1 in that: the eluent has different component ratios.
First rinse solution: the fermentation liquor comprises 10 parts by weight of aspergillus niger citric acid fermentation liquor with the mass fraction of 80% and 6 parts by weight of NaCl solution with the mass concentration of 0.2 mol/L;
a second leacheate: comprises 8 parts by weight of shaddock peel powder, 7 parts by weight of organic modified sepiolite powder and MgCl with the mass concentration of 0.05mol/L 2 3 parts of solution, feCl with the mass concentration of 0.4mol/L 3 5 parts of a solution;
a third leacheate: the fermentation broth comprises, by weight, 3 parts of aspergillus niger citric acid fermentation broth with the mass fraction of 75%, 5% of Trition X-100 parts, 3% of TWEEN80 parts, 2 parts of rhamnolipid and 1 part of saponin active agent.
The application of the eluent is applied to the eluent for repairing pesticide chemical polluted soil, and the application method comprises the following steps: the three leacheate are sequentially applied to the pesticide chemical polluted soil every m 3 The total amount of three leachates applied in the soil was 850L, the first leachate was 247L, the second leachate was 355L, and the third leachate was 248L.
Example 3
The present embodiment is different from embodiment 1 in that: the component ratios of the first leacheate were different.
First rinse solution: the fermentation liquor comprises 12 parts by weight of aspergillus niger citric acid fermentation liquor with the mass fraction of 85% and 8 parts by weight of NaCl solution with the mass concentration of 0.3 mol/L;
a second leacheate: comprises 11 parts by weight of shaddock peel powder, 9 parts by weight of organic modified sepiolite powder and MgCl with the mass concentration of 0.08mol/L 2 7 parts of solution, feCl with the mass concentration of 0.6mol/L 3 6 parts of a solution;
a third leacheate: the fermentation liquid comprises, by weight, 5 parts of aspergillus niger citric acid fermentation liquid with the mass fraction of 80%, 5% Trition X-100 parts, 3% TWEEN80 parts, 3 parts of rhamnolipid and 2 parts of saponin active agent.
The application of the eluent is applied to the eluent for repairing pesticide chemical polluted soil, and the application method comprises the following steps: the three leacheate are sequentially applied to the pesticide chemical polluted soil every m 3 The total amount of three leacheate applied in the soil was 850L, the first leacheate was 266L, the second leacheate was 318L, and the third leacheate was 266L.
Example 4
The present embodiment is different from embodiment 1 in that: the preparation parameters of the culture medium in the preparation of the aspergillus niger citric acid fermentation liquor are different.
S1-1, preparation of a culture medium: preparing a PDA culture medium and a shake flask culture medium, wherein the PDA culture medium comprises the following components in percentage by mass: 16% of starch, 2% of glucose, 2% of agar and the balance of deionized water, the components are mixed and boiled, the mixture is filtered and then placed in a high-temperature sterilization pot to be sterilized for 15min at the temperature of 125 ℃, and a PDA culture medium is obtained, wherein the shake flask culture medium comprises the following components in percentage by mass: 5% corn flour, 3% peptone, 0.15% sodium nitrate, 0.01% monopotassium phosphate, 0.005% magnesium sulfate, 0.4% yeast extract and the balance of deionized water, mixing the components, placing the mixture in a high-temperature sterilization pot, and sterilizing the mixture for 15min at 125 ℃ to obtain the shake flask culture medium.
Example 5
The present embodiment is different from embodiment 1 in that: the preparation parameters of the culture medium in the preparation of the aspergillus niger citric acid fermentation liquor are different.
S1-1, preparation of a culture medium: preparing a PDA culture medium and a shake flask culture medium, wherein the PDA culture medium comprises the following components in percentage by mass: mixing 18% of starch, 3% of glucose, 3% of agar and the balance of deionized water, boiling, filtering, placing in a high-temperature sterilization pot, and sterilizing at 130 ℃ for 20min to obtain a PDA culture medium, wherein the shake flask culture medium comprises the following components in percentage by mass: 6% of corn flour, 4% of peptone, 0.2% of sodium nitrate, 0.02% of monopotassium phosphate, 0.005% of magnesium sulfate, 0.6% of yeast extract and the balance of deionized water, and placing the mixed components in a high-temperature sterilization pot for sterilization at 130 ℃ for 20min to obtain the shake flask culture medium.
Example 6
The present embodiment is different from embodiment 1 in that: the preparation parameters of the aspergillus niger citric acid fermentation liquor are different.
S1-2, activating aspergillus niger: placing the 1-ring aspergillus niger strain in a PDA culture medium, and placing the PDA culture medium in a constant-temperature incubator at 32 ℃ for culturing for 5d to obtain activated aspergillus niger;
s1-3, preparing a suspension: taking out the culture medium, adding deionized water 30% of the culture medium, washing black spore, placing into shake flask, shaking at 200r/min for 30min, counting spores in shake flask with blood counting plate, and adjusting the number concentration of spores in shake flask to 3 × 10 6 Per ml, obtaining aspergillus niger spore suspension;
s1-4, inoculating aspergillus niger: transferring the aspergillus niger spore suspension into a shake flask culture medium, wherein the mass ratio of the aspergillus niger spore suspension to the shake flask culture medium is 1:10, putting the mixture into a constant-temperature shaking table at 32 ℃ for culturing for 30d to obtain aspergillus niger citric acid fermentation liquor.
Example 7
The present embodiment is different from embodiment 1 in that: the preparation parameters of the aspergillus niger citric acid fermentation liquor are different.
S1-2, activating aspergillus niger: placing 2-ring aspergillus niger strains in a PDA culture medium, and placing the PDA culture medium in a constant-temperature incubator at 35 ℃ for culture for 7d to obtain activated aspergillus niger;
s1-3, preparing a suspension: taking out the culture medium, adding deionized water 35% of the culture medium, washing black spore, placing into shake flask, shaking at shaking table rotation speed of 240r/min for 30min, counting spores in shake flask with blood counting plate, and adjusting the number concentration of spores in shake flask to 4 × 10 6 Obtaining Aspergillus niger spore suspension liquid in each ml;
s1-4, inoculating aspergillus niger: transferring the aspergillus niger spore suspension into a shake flask culture medium, wherein the mass ratio of the aspergillus niger spore suspension to the shake flask culture medium is 1:10, placing the mixture into a constant-temperature shaking table at 35 ℃ for culturing for 30d to obtain aspergillus niger citric acid fermentation liquor.
Example 8
The present embodiment is different from embodiment 1 in that: the first leacheate was prepared with different parameters.
S2, preparing a first leacheate: taking aspergillus niger citric acid fermentation liquor, adding deionized water into the aspergillus niger citric acid fermentation liquor to adjust the mass fraction of the aspergillus niger citric acid fermentation liquor to 80%, then dropwise adding a NaCl solution into the aspergillus niger citric acid fermentation liquor and continuously stirring, wherein the dropwise adding speed of the NaCl solution is 2ml/s, the stirring speed is 100r/min, and the stirring time is 10min, so that the first leacheate is obtained.
Example 9
The present embodiment is different from embodiment 1 in that: the first leacheate was prepared with different parameters.
S2, preparing a first leacheate: taking aspergillus niger citric acid fermentation liquor, adding deionized water into the aspergillus niger citric acid fermentation liquor to adjust the mass fraction of the aspergillus niger citric acid fermentation liquor to 85%, then dropwise adding a NaCl solution into the aspergillus niger citric acid fermentation liquor and continuously stirring, wherein the dropwise adding speed of the NaCl solution is 3ml/s, the stirring speed is 100r/min, and the stirring time is 15min, so as to obtain first leacheate.
Example 10
The present embodiment is different from embodiment 1 in that: the second leacheate was prepared with different parameters.
S3, preparing a second leacheate: grinding pericarpium Citri Grandis to particle size of 50 μm, mixing with organic modified sepiolite powder to obtain mixed powder, heating at 78 deg.C for 1 hr, rapidly cooling with liquid nitrogen to obtain microspherical particles with microcrack on surface, and placing the microspherical particles in MgCl 2 FeCl is added dropwise into the solution while stirring continuously 3 Solutions, feCl 3 The dropping speed of the solution is 1ml/s, the stirring speed is 60r/min, and the stirring is continued for 30min after the dropping is finished.
Example 11
The present embodiment is different from embodiment 1 in that: the second leacheate was prepared with different parameters.
S3, preparing a second leacheate: grinding pericarpium Citri Grandis to particle diameter of 60 μm, mixing with organic modified sepiolite powder to obtain mixed powder, heating at 85 deg.C for 1h, rapidly cooling with liquid nitrogen to obtain microspherical particles with microcrack on surface, and placing the microspherical particles in MgCl 2 In the solution, feCl is added dropwise while stirring continuously 3 Solutions, feCl 3 The dropping speed of the solution is 2ml/s, the stirring speed is 70r/min, and the stirring is continued for 30min after the dropping is finished.
Example 12
The present embodiment is different from embodiment 1 in that: the preparation method parameters of the organic modified sepiolite powder are different.
The preparation method of the organic modified sepiolite powder comprises the following steps:
s3-1: grinding the raw sepiolite stone to the particle size of 70 mu m to obtain raw sepiolite stone powder;
s3-2: mixing sepiolite raw stone powder with deionized water, wherein the mass concentration of the sepiolite raw stone powder is 15g/L, then adding sodium hexametaphosphate, controlling the volume concentration of the sodium hexametaphosphate to be 0.5ml/L, stirring and reacting for 8 hours at 135 ℃, and standing for 3 hours to obtain a hydrothermal modified sepiolite suspension;
s3-3: centrifugally separating the hydrothermal modified sepiolite suspension, drying the precipitate at 70 ℃, and grinding the precipitate until the particle size is 20 mu m to obtain hydrothermal modified sepiolite powder;
s3-4: mixing hydrothermal modified sepiolite powder with deionized water, wherein the mass concentration of the hydrothermal modified sepiolite powder is 23g/L, dropwise adding cetyl trimethyl ammonium bromide into the mixture and continuously stirring the mixture, controlling the volume concentration of the cetyl trimethyl ammonium bromide to be 3.15ml/L, then continuously dropwise adding sodium dodecyl sulfate into the mixture and continuously stirring the mixture, controlling the volume concentration of the sodium dodecyl sulfate to be 2.75ml/L, centrifugally separating the mixture after the dropwise adding is finished, and drying the precipitate at the temperature of 60 ℃ to obtain the organic modified sepiolite.
Example 13
The present embodiment is different from embodiment 1 in that: the preparation method parameters of the organic modified sepiolite powder are different.
The preparation method of the organic modified sepiolite powder comprises the following steps:
s3-1: grinding the raw sepiolite stone to the particle size of 80 mu m to obtain raw sepiolite stone powder;
s3-2: mixing sepiolite raw stone powder with deionized water, controlling the mass concentration of the sepiolite raw stone powder to be 17g/L, then adding sodium hexametaphosphate, controlling the volume concentration of the sodium hexametaphosphate to be 0.9ml/L, stirring and reacting for 10 hours at the temperature of 140 ℃, and standing for 3 hours to obtain a hydrothermal modified sepiolite suspension;
s3-3: centrifugally separating the hydrothermal modified sepiolite suspension, drying the precipitate at 80 ℃, and grinding the precipitate until the particle size is 30 mu m to obtain hydrothermal modified sepiolite powder;
s3-4: mixing hydrothermal modified sepiolite powder with deionized water, wherein the mass concentration of the hydrothermal modified sepiolite powder is 26g/L, dropwise adding cetyl trimethyl ammonium bromide into the mixture and continuously stirring the mixture, controlling the volume concentration of the cetyl trimethyl ammonium bromide to be 3.3ml/L, then continuously dropwise adding sodium dodecyl sulfate into the mixture and continuously stirring the mixture, controlling the volume concentration of the sodium dodecyl sulfate to be 2.9ml/L, centrifugally separating the mixture after the dropwise adding is finished, and drying the precipitate at 70 ℃ to obtain the organic modified sepiolite.
Example 14
The present embodiment is different from embodiment 1 in that: the third leacheate was prepared with different parameters.
S4, preparing a third leacheate: taking Aspergillus niger citric acid fermentation broth, adding HNO 3 Adjusting the pH value of aspergillus niger citric acid fermentation liquor to 4 by using the solution, then adding deionized water to adjust the mass fraction of the aspergillus niger citric acid fermentation liquor to 75%, then adding a mixture of Trition X-100, TWEEN80, rhamnolipid and saponin active agent, and performing ultrasonic dispersion for 30min at the ultrasonic dispersion power of 300W and the frequency of 20kHz to obtain third leacheate.
Example 15
The present embodiment is different from embodiment 1 in that: the third leacheate was prepared with different parameters.
S4, preparing a third leacheate: taking Aspergillus niger citric acid fermentation broth, adding HNO 3 Adjusting the pH value of aspergillus niger citric acid fermentation liquor to 5 by using the solution, then adding deionized water to adjust the mass fraction of the aspergillus niger citric acid fermentation liquor to 80%, then adding a mixture of Trition X-100, TWEEN80, rhamnolipid and saponin active agent, and performing ultrasonic dispersion for 30min at the ultrasonic dispersion power of 350W and the frequency of 20kHz to obtain third leacheate.
Experimental example 1
The eluents prepared by the preparation method in the embodiments 1 to 3 of the invention are applied to the pesticide chemical polluted soil, the main pollutant in the selected pesticide chemical polluted soil is heavy metal Pb, the application mode is that the three eluents are sequentially applied in sequence, and the application mode is compared with the conventional eluents, wherein the comparative example 1 is FeCl 3 The solution, comparative example 2, is an unfermented citric acid solution, and both of the two conventional eluents are commercially available eluents widely used, and the residue state and unstable too-content of the contaminants before and after the experiment were measured, and the experimental results are shown in table 1.
TABLE 1 EXAMPLES 1-3 AND COMPARATIVE EXAMPLES 1, 2 contaminant Pb content reduction
| Examples | The residue is in the state of% | Can be reduced to% |
| Example 1 | 63.4 | 77.9 |
| Example 2 | 62.8 | 76.4 |
| Example 3 | 61.9 | 78.3 |
| Comparative example 1 | 54.5 | 70.1 |
| Comparative example 2 | 58.2 | 68.4 |
The experimental data in table 1 show that the eluting agents prepared by the preparation methods in embodiments 1 to 3 of the present invention have significantly better removing effect on the heavy metal pollutants Pb in the contaminated soil than the two mature eluting agents in the prior art, which indicates that the eluting agents improved by the preparation method of the present invention can enhance the removing effect on the heavy metal pollutants in the soil;
continuing to compare examples 1-3, it can be seen that the Pb removal rate was the highest in the residue state in example 1, while the Pb removal rate was the highest in the reducible state in example 3, and in summary, the removal rate was not so high in examples 1-3, and the production parameters in example 1 were preferred.
Experimental example 2
For examples 4 and 5, the preparation parameters of the culture medium in the preparation of the aspergillus niger citric acid fermentation broth have little influence on the aspergillus niger citric acid fermentation broth, and the preparation effect can be well achieved by selecting the preparation parameters of the aspergillus niger citric acid fermentation broth culture medium provided by the invention.
Compared with the examples 6 and 7, the preparation parameters of the aspergillus niger citric acid fermentation liquor, particularly the amount of aspergillus niger strains are changed, the leaching effect of the eluent is influenced to a certain extent, the selected main pollutant of the polluted soil is Cd, the experimental method is the same as that of the experimental example 1, and the experimental results are shown in the table 2.
Table 2 examples 1, 6, 7 decrease in Cd content of contaminants
| Examples | The residue is in the state of% | Can be reduced to% |
| Example 1 | 63.4 | 77.9 |
| Example 6 | 57.2 | 76.8 |
| Example 7 | 64.5 | 79.0 |
It can be seen from the data in table 2 that, by changing the amount of aspergillus niger strains, the amount of spores in aspergillus niger citric acid fermentation broth has a small influence on the removal rate of reducible-state Cd pollutants in soil, the difference between the three groups of examples is small, and the residual-state Cd has a large influence, the amount of spores in aspergillus niger citric acid fermentation broth in example 6 is the smallest, so that the residual-state Cd removal rate is the lowest, which indicates that the amount of spores in aspergillus niger citric acid fermentation broth is in direct proportion to the removal rate of Cd pollutants in soil, and the difference between examples 1 and 7 is small, which indicates that to reach a saturation value, the continuous improvement of the amount of spores in aspergillus niger citric acid fermentation broth has a limited influence on the residual-state Cd removal rate, and the cost is increased, so that the preparation parameters in example 1 are selected to be the optimal.
Experimental example 3
The eluents prepared by the preparation methods of the embodiments 1, 12 and 13 of the present invention are applied to the pesticide chemical contaminated soil, the main pollutants in the selected pesticide chemical contaminated soil are organic pollutants o, p' -DDT, α -HCH and o-nitrochlorobenzene caused by pesticide residue, the application method is that the three eluents are sequentially applied, and simultaneously compared with the conventional eluents, wherein the comparative example 3 is hydroxypropyl β cyclodextrin eluents, which have been proved to have good application in the pesticide contaminated soil, the removal rates of the pollutants before and after the experiment are detected, and the experiment results are shown in table 3.
Table 3 removal rates of organic contaminants in examples 1, 12 and 13 and comparative example 3
| Examples | Removal rate% |
| Example 1 | 84.5 |
| Example 12 | 83.6 |
| Example 13 | 81.9 |
| Comparative example 3 | 63.4 |
As can be seen from the experimental data in table 3, the eluting agents prepared by the preparation methods in embodiments 1, 12 and 13 of the present invention have significantly better removal effects on organic pollutants in pesticide-contaminated soil than the more mature hydroxypropyl β cyclodextrin eluting agents in the prior art, which indicates that the eluting agents improved by the preparation method of the organically modified sepiolite powder of the present invention can enhance the removal effects on organic pollutants in soil;
continuing to compare examples 1, 12 and 13, it can be seen that the removal rate of organic pollutants is the highest in example 1, and the preparation parameters of the organic modified sepiolite powder in example 1 are preferred.
The parameters of the preparation methods of examples 8 to 11 and 14 to 15 are adjusted conventionally within the adjustable range of the parameters of the preparation method provided by the invention, the final remediation effect of the contaminated soil is not greatly different, and the optimal parameter of any one of the methods can achieve a good remediation effect.
Claims (7)
1. The utility model provides an eluent for restoreing pesticide chemical industry contaminated soil which characterized in that, includes 3 mutually independent eluents of group, and 3 groups of eluents are according to adding the order sequencing in proper order:
first rinse solution: the fermentation broth comprises, by weight, 10-12 parts of aspergillus niger citric acid fermentation broth with the mass fraction of 80-85% and 6-8 parts of NaCl solution with the mass concentration of 0.2-0.3 mol/L;
a second leacheate: comprises 8 to 11 portions of shaddock peel powder, 7 to 9 portions of organic modified sepiolite powder and MgCl with the mass concentration of 0.05 to 0.08mol/L 2 3-7 parts of solution, feCl with mass concentration of 0.4-0.6mol/L 3 5-6 parts of a solution;
a third leacheate: the fermentation broth comprises, by weight, 3-5 parts of aspergillus niger citric acid fermentation broth with the mass fraction of 75-80%, 5-6 parts of Trition X-100 with the mass fraction of 5%, 4-5 parts of TWEEN with the mass fraction of 3%, 2-3 parts of rhamnolipid and 1-2 parts of saponin active agent;
the preparation process of the eluting agent comprises the following steps:
s1, preparing aspergillus niger citric acid fermentation liquor:
s1-1, preparation of a culture medium: preparing a PDA culture medium and a shake flask culture medium;
s1-2, activating aspergillus niger: placing 1-2 ring Aspergillus niger strains in a PDA culture medium, and culturing in a constant temperature incubator at 32-35 deg.C for 5-7 days to obtain activated Aspergillus niger;
s1-3, preparing a suspension: taking out the culture medium, adding deionized water 30-35% of the culture medium, washing out black spores, placing into shake flask, shaking for 30min, counting spores in shake flask with blood counting plate, and adjusting the number concentration of spores in shake flask to 3-4 × 10 6 Obtaining Aspergillus niger spore suspension liquid in each ml;
s1-4, inoculating aspergillus niger: transferring the aspergillus niger spore suspension into a shake flask culture medium, wherein the mass ratio of the aspergillus niger spore suspension to the shake flask culture medium is 1:10, putting the mixture into a constant-temperature shaking table at the temperature of 32-35 ℃ for culturing for 30d to obtain aspergillus niger citric acid fermentation liquor;
s2, preparing a first leacheate: according to the weight parts, taking aspergillus niger citric acid fermentation liquor, adding deionized water into the aspergillus niger citric acid fermentation liquor to adjust the mass fraction of the aspergillus niger citric acid fermentation liquor to 80-85%, and then dropwise adding a NaCl solution into the aspergillus niger citric acid fermentation liquor and continuously stirring to obtain a first leacheate;
s3, preparing a second leacheate: grinding the shaddock peel to the particle size of 50-60 mu m according to the weight parts, mixing the ground shaddock peel with organic modified sepiolite powder to obtain mixed powder, heating the mixed powder for 1h at the temperature of 78-85 ℃, then rapidly cooling the mixed powder by using liquid nitrogen to obtain microspherical particles with microcracks on the surfaces, and then placing the microspherical particles into MgCl 2 In the solution, feCl is added dropwise while stirring continuously 3 Continuously stirring the solution for 30min after the dropwise addition is finished;
the preparation method of the organic modified sepiolite powder in the step S3 comprises the following steps:
s3-1: grinding the raw sepiolite stone to the particle size of 70-80 μm to obtain raw sepiolite stone powder;
s3-2: mixing sepiolite raw stone powder with deionized water, controlling the mass concentration of the sepiolite raw stone powder to be 15-17g/L, then adding sodium hexametaphosphate, controlling the volume concentration of the sodium hexametaphosphate to be 0.5-0.9ml/L, stirring and reacting for 8-10h at 135-140 ℃, and standing for 3h to obtain a hydrothermal modified sepiolite suspension;
s3-3: centrifugally separating the hydrothermal modified sepiolite suspension, drying the precipitate at 70-80 ℃, and grinding the precipitate until the particle size is 20-30 mu m to obtain hydrothermal modified sepiolite powder;
s3-4: mixing hydrothermal modified sepiolite powder with deionized water, wherein the mass concentration of the hydrothermal modified sepiolite powder is 23-26g/L, dropwise adding cetyl trimethyl ammonium bromide into the mixture and continuously stirring the mixture, controlling the volume concentration of the cetyl trimethyl ammonium bromide to be 3.15-3.3ml/L, then continuously dropwise adding sodium dodecyl sulfate into the mixture and continuously stirring the mixture, controlling the volume concentration of the sodium dodecyl sulfate to be 2.75-2.9ml/L, centrifugally separating the mixture after dropwise adding is finished, and drying the precipitate at the temperature of 60-70 ℃ to obtain the organic modified sepiolite;
s4, preparing a third leacheate: taking aspergillus niger citric acid fermentation liquor according to the weight parts, and adding HNO into the aspergillus niger citric acid fermentation liquor 3 The pH value of the aspergillus niger citric acid fermentation liquor is adjusted to 4-5 by the solution, then deionized water is added to adjust the mass fraction of the aspergillus niger citric acid fermentation liquor to 75-80%, and Trition X-100, TWEEN80, rhamnolipid and saponin active agent are addedAnd ultrasonically dispersing the mixture for 30min to obtain a third leacheate.
2. The eluent for remediating agrichemical-chemical contaminated soil as set forth in claim 1, wherein the PDA medium in step S1-1 comprises the following components in percentage by mass: mixing the above materials, boiling, filtering, sterilizing at 125-130 deg.C for 15-20min in a high temperature sterilizing pot to obtain PDA culture medium.
3. The eluent for remediating agrochemical contaminated soil according to claim 1, characterised in that the shake flask culture medium in step S1-1 comprises the following components in mass percent: 5-6% of corn flour, 3-4% of peptone, 0.15-0.2% of sodium nitrate, 0.01-0.02% of monopotassium phosphate, 0.005% of magnesium sulfate, 0.4-0.6% of yeast extract and the balance of deionized water, mixing the components, placing the mixture in a high-temperature sterilization pot, and sterilizing the mixture for 15-20min at 125-130 ℃ to obtain the shake flask culture medium.
4. The eluent for remediating agrichemical-chemical contaminated soil as set forth in claim 1, wherein the shaking table rotation speed in step S1-4 is 200-240r/min.
5. The eluent for remediating agrichemical-chemical contaminated soil as set forth in claim 1, wherein the NaCl solution is added dropwise at a rate of 2-3ml/S, the stirring rate is 100r/min, and the stirring time is 10-15min in step S2.
6. The eluent for remediating agrochemical contaminated soil as set forth in claim 1, wherein FeCl is adopted in step S3 3 The dropping speed of the solution is 1-2ml/s, and the stirring speed is 60-70r/min.
7. The eluent for remediating agrichemical-chemical contaminated soil as set forth in claim 1, wherein the power of ultrasonic dispersion in step S4 is 300-350W, and the frequency is 20kHz.
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