CN116274330B - Method for repairing organic pollutant polluted soil - Google Patents
Method for repairing organic pollutant polluted soil Download PDFInfo
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- CN116274330B CN116274330B CN202310279175.XA CN202310279175A CN116274330B CN 116274330 B CN116274330 B CN 116274330B CN 202310279175 A CN202310279175 A CN 202310279175A CN 116274330 B CN116274330 B CN 116274330B
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- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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Abstract
The invention relates to the technical field of soil remediation, in particular to a remediation method of organic pollutant contaminated soil, which is used for solving the problems of complicated remediation process, slow remediation, easy secondary pollution and poor remediation effect of the existing soil organic pollutant contaminated remediation process; according to the repairing method, after the pollution degradation agent is added into the organic pollutant polluted soil, the excellent photocatalytic performance of titanium dioxide can be utilized to absorb and degrade the organic pollutant, the carbon coating layer improves the absorption performance of the organic pollutant, micropores on the carbon coating layer facilitate migration of the organic pollutant in the soil, support the soil, facilitate migration of oxygen and moisture in the soil, provide oxygen and moisture for microorganisms and plants in the soil, enable iron elements to have good redox performance, degrade the organic matters, and enable the response spectrum of the titanium dioxide to be expanded towards visible light by doping iron, so that the photocatalytic efficiency of the titanium dioxide is improved.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a remediation method of organic pollutant contaminated soil.
Background
With the rapid development of industrialization in China, the soil environment is continuously endangered by various pollution, and meanwhile, the requirements for restoring and treating the polluted soil are increasingly greater. Organic pollutants are one of the main pollutants commonly existing in soil, and mainly comprise organic pesticides, phenols, synthetic detergents, harmful microorganisms caused by urban sewage, sludge and fertilization, and the like. Organic pollutants enter the soil system through various ways, the physicochemical properties of the soil are changed, the local ecological system is destroyed, indirect and direct toxic effects are generated on animals and plants in the area, and the using function of the soil is seriously affected, however, the existing soil organic pollution repairing process is complicated, the repairing is slow, and meanwhile, secondary pollution is easy to generate and the repairing effect is poor.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a method for repairing organic pollutant polluted soil, which comprises the following steps: adding titanium dioxide, polyvinyl chloride and absolute ethyl alcohol into an Anthree-mouth flask for ultrasonic dispersion, stirring for reaction, cooling a reaction product to room temperature after the reaction is finished, rotary evaporating, calcining an evaporation product, cooling along with a furnace to obtain carbon-coated particles, soaking the carbon-coated particles in a nitric acid solution, taking out and adding the carbon-coated particles into the three-mouth flask, adding absolute ethyl alcohol for stirring for reaction, simultaneously dropwise adding an iron nitrate solution and a sodium hydroxide solution while stirring, continuously stirring for reaction after the dropwise addition is finished, drying the reaction product after the reaction is finished, calcining, cooling along with the furnace to obtain degradation particles, adding degradation particles, a degradation particle dispersing agent, absolute ethyl alcohol and deionized water into the three-mouth flask for stirring for reaction, vacuum filtering the reaction product after the reaction is finished, washing and drying a filter cake to obtain a pollution degradation agent, uniformly spraying the pollution degradation agent into the surface of organic pollutant polluted soil, and deep ploughing and mixing.
The aim of the invention can be achieved by the following technical scheme:
a method for repairing organic pollutant polluted soil comprises the following steps:
step one: adding titanium dioxide, polyvinyl chloride and absolute ethyl alcohol into a three-neck flask with a stirrer and a thermometer, performing ultrasonic dispersion for 20-30 min under the condition of ultrasonic frequency of 40-50kHz, stirring at the temperature of 25-30 ℃ and stirring rate of 500-600 r/min for 2-3h, cooling a reaction product to room temperature after the reaction is finished, performing rotary evaporation to remove a solvent, placing the evaporation product into a tubular furnace, introducing nitrogen for protection, performing heat preservation for 1-1.5h under the condition of heating at the heating rate of 4-5 ℃ mi to 120-125 ℃, performing calcination for 3-4h under the condition of heating to 820-850 ℃, and performing furnace cooling to obtain carbon-coated particles;
step two: soaking carbon-coated particles in nitric acid solution for 20-30h, taking out and adding the carbon-coated particles into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, adding absolute ethyl alcohol, stirring and reacting for 20-30 min under the condition that the temperature is 25-30 ℃ and the stirring rate is 500-600 r/min, simultaneously dropwise adding ferric nitrate solution and sodium hydroxide solution while stirring, controlling the dropping rate to be 1-2 drops/s, continuing stirring and reacting for 2-3h after the dripping is finished, placing a reaction product in a vacuum drying box after the reaction is finished, drying for 2-3h under the condition that the temperature is 100-105 ℃, then placing the reaction product in a tubular furnace, introducing nitrogen for protection, then heating to 500-520 ℃ at the heating rate of 8-10 ℃ min, calcining for 2-3h, and cooling along with the furnace to obtain degradation particles;
step three: adding degradation particles, a degradation particle dispersing agent, absolute ethyl alcohol and deionized water into a three-neck flask provided with a stirrer, a thermometer, an air duct and a reflux condenser, introducing nitrogen for protection, stirring and reacting for 20-30 min under the conditions of 25-30 ℃ and stirring speed of 500-600 r/min, heating to reflux, continuing stirring and reacting for 3-5h, vacuum filtering a reaction product after the reaction is finished, washing a filter cake with distilled water for 3-5 times, and then placing the filter cake in a vacuum drying oven, and drying for 4-5h under the conditions of 75-80 ℃ to obtain a pollution degradation agent;
step four: and uniformly spraying the pollution degradation agent into the surface of the organic pollutant polluted soil, and then carrying out deep ploughing and mixing.
As a further scheme of the invention: the dosage ratio of the titanium dioxide to the polyvinyl chloride to the absolute ethyl alcohol in the first step is 10g:5-10g:150-180mL.
As a further scheme of the invention: the dosage ratio of the carbon-coated particles, the absolute ethyl alcohol, the ferric nitrate solution and the sodium hydroxide solution in the second step is 10g:120-150mL:10-15mL:10-15mL, wherein the mass fraction of the nitric acid solution is 20-25%, and the molar concentration of the ferric nitrate solution and the sodium hydroxide solution is 1mol/L.
As a further scheme of the invention: the dosage ratio of the degradation particles, the degradation particle dispersing agent, the absolute ethyl alcohol and the deionized water in the third step is 10g:2.5-7.5g:80-100mL:60-80mL.
As a further scheme of the invention: the degradable particle dispersing agent is prepared by the following steps:
step a1: adding 4-hydroxybenzonitrile, 2-bromothiophene, anhydrous potassium carbonate and butanone into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring at a temperature of 25-30 ℃ and a stirring rate of 500-600 r/min for reacting for 20-30 min, heating to reflux, continuing stirring for reacting for 20-30h, cooling the reaction product to room temperature after the reaction, vacuum filtering, rotationally evaporating the filtrate to remove the solvent, and recrystallizing with absolute ethyl alcohol to obtain an intermediate 1;
the reaction principle is as follows:
step a2: adding metal sodium and 2-methyl-2-butanol into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring at 105-110 ℃ and stirring speed of 500-600 r/min for 3-5h, adding an intermediate 1 for continuously stirring for 20-30 min, then dropwise adding diethyl succinate while stirring, controlling the dropping speed to be 1-2 drops/s, continuously stirring for 15-20h after the dripping is finished, cooling a reaction product to room temperature after the reaction is finished, adding into absolute methanol, precipitating, performing vacuum suction filtration, placing a filter cake into a vacuum drying oven, and drying at 75-80 ℃ for 2-3h to obtain an intermediate 2;
the reaction principle is as follows:
step a3: adding the intermediate 2, 4-bromo-2-thiophenecarboxaldehyde, potassium tert-butoxide and anhydrous tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and an air duct, introducing nitrogen for protection, stirring and reacting for 8-10h under the conditions of 25-30 ℃ and stirring speed of 500-600 r/min, pouring the reaction product into ice water after the reaction is finished, extracting with dichloromethane for 2-3 times, washing the extract with distilled water for 3-5 times, drying with anhydrous magnesium sulfate, vacuum filtering, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 3;
the reaction principle is as follows:
step a4: adding the intermediate 3, pyrrole and N, N-dimethylformamide into a four-neck flask provided with a stirrer, a thermometer, an air duct, a reflux condenser pipe and a constant pressure dropping funnel, introducing nitrogen for protection, adding trifluoroacetic acid dropwise while stirring under the conditions of the temperature of 25-30 ℃ and the stirring rate of 500-600 r/min, controlling the dropping rate to be 1-2 drops/s, continuing stirring and reacting for 5-6h under the conditions of heating to reflux after the dropping is finished, cooling the reaction product to room temperature after the reaction is finished, vacuum filtering, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 4;
the reaction principle is as follows:
step a5: adding the intermediate 4, 3-bromopropyl trimethoxysilane, anhydrous potassium carbonate and absolute ethyl alcohol into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring at the temperature of 25-30 ℃ and the stirring speed of 500-600 r/min for reacting for 20-30 min, heating to reflux, continuing stirring for reacting for 4-5h, cooling the reaction product to room temperature after the reaction, vacuum suction filtering, and rotationally evaporating the filtrate to remove the solvent to obtain the degraded particle dispersing agent.
The reaction principle is as follows:
as a further scheme of the invention: the dosage ratio of the 4-hydroxybenzonitrile, the 2-bromothiophene, the anhydrous potassium carbonate and the butanone in the step a1 is 0.1mol:0.11-0.12mol:20-25g:100-120mL.
As a further scheme of the invention: the dosage ratio of the metallic sodium, the 2-methyl-2-butanol, the intermediate 1 and the diethyl succinate in the step a2 is 1.0-1.5g:120-150mL:20mmol:10mmol.
As a further scheme of the invention: the dosage ratio of the intermediate 2, 4-bromo-2-thiophenecarboxaldehyde, potassium tert-butoxide and anhydrous tetrahydrofuran in the step a3 is 10mmol:22-25mmol:2.0-2.5g:120-150mL.
As a further scheme of the invention: the ratio of the amount of intermediate 3, pyrrole, N-dimethylformamide and trifluoroacetic acid in step a4 is 10mmol:45-50mmol:150-180mL:5-7mmol.
As a further scheme of the invention: the dosage ratio of the intermediate 4, 3-bromopropyl trimethoxysilane, anhydrous potassium carbonate and anhydrous ethanol in the step a5 is 10mmol:40mmol:45-50mmol:150-200mL.
The invention has the beneficial effects that:
adding titanium dioxide, polyvinyl chloride and absolute ethyl alcohol into an Ansankou flask for ultrasonic dispersion, stirring for reaction, cooling a reaction product to room temperature after the reaction is finished, then rotationally evaporating, calcining an evaporation product, cooling with a furnace to obtain carbon-coated particles, soaking the carbon-coated particles in nitric acid solution, taking out and adding the carbon-coated particles into the three-port flask, adding absolute ethyl alcohol for stirring reaction, stirring and simultaneously dropwise adding ferric nitrate solution and sodium hydroxide solution, continuing stirring for reaction after the dropwise addition, drying the reaction product after the reaction is finished, calcining, cooling with the furnace to obtain degradation particles, adding the degradation particles, a degradation particle dispersing agent, absolute ethyl alcohol and deionized water into the three-port flask for stirring reaction, vacuum suction filtering the reaction product after the reaction is finished, washing and drying a filter cake to obtain a pollution degradation agent, uniformly spraying the pollution degradation agent into the surface of the organic pollutant polluted soil, and then deep ploughing and mixing; according to the repairing method, firstly, polyvinyl chloride is coated on the surface of titanium dioxide, then the coated polyvinyl chloride is carbonized to form a carbon coating layer, carbon coating particles are obtained, nitric acid solution is used for soaking the carbon coating particles, so that impurities on the surfaces of the carbon coating particles can be removed, meanwhile, the wetting property of the surfaces of the carbon coating layers can be improved, a certain hole expanding effect can be achieved, a large number of micropores are formed, the surface area utilization rate of the carbon coating layers is improved, then iron ions are doped into the carbon coating layers and are calcined, degradation particles containing iron elements are obtained, and then degradation particles are modified by using a degradation particle dispersing agent, so that a pollution degradation agent is obtained; after the pollution degradation agent is added into the organic pollutant polluted soil, the excellent photocatalytic performance of titanium dioxide can be utilized to carry out adsorption degradation on the organic pollutant, the carbon coating layer improves the adsorption performance on the organic pollutant, micropores on the carbon coating layer facilitate migration of the organic pollutant in the soil, support the soil, facilitate migration of oxygen and moisture in the soil, provide oxygen and moisture for microorganisms and plants in the soil, degrade the organic matters in the soil by cooperating with the microorganisms and the plants, enable the iron element to have good redox performance, degrade the organic matters, and the response spectrum of the titanium dioxide is expanded to visible light by doping iron, so that the photocatalytic efficiency of the titanium dioxide is improved;
in the process of repairing organic pollutant polluted soil, a degradation particle dispersing agent is firstly prepared, hydroxyl on 4-hydroxybenzonitrile and bromine atoms on 2-bromothiophene are firstly utilized to carry out nucleophilic substitution reaction to generate an intermediate 1, then the intermediate 1 is reacted with diethyl succinate to generate an intermediate 2, then secondary amino on the intermediate 2 and bromine atoms on 4-bromo-2-thiophenecarboxaldehyde are subjected to nucleophilic substitution reaction to generate an intermediate 3, then the intermediate 3 is reacted with pyrrole by utilizing aldehyde groups to obtain an intermediate 4, and then secondary amino on the intermediate 4 and bromine atoms on 3-bromopropyl trimethoxysilane are subjected to nucleophilic substitution reaction to generate the degradation particle dispersing agent; the degradable particle dispersing agent is used for treating the degradable particles, siloxane on the degradable particle dispersing agent is hydrolyzed to form silanol, and the silanol is dehydrated and condensed with hydroxyl on the surface of the degradable particles, so that the degradable particles are coated on the surface of the degradable particles, the degradable particles can be protected, the capability of degrading organic pollutants caused by corrosion of the degradable particles in soil environment is avoided, the dispersibility of the degradable particles can be greatly improved after the degradable particles are coated by the degradable particle dispersing agent, the degradation capability is avoided to be reduced, the molecular structure of the degradable particle dispersing agent contains a large number of thiophene rings and pyrrole rings, the thiophene rings and the pyrrole rings have good photosensitivity, the response spectrum of titanium dioxide can be further promoted to expand to visible light, the photocatalytic efficiency of the titanium dioxide is greatly improved, the degradation capability of organic pollutants polluting the degradable agent is improved, and the restoration effect of the soil is improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the embodiment is a preparation method of a degradable particle dispersing agent, which comprises the following steps:
step a1: adding 0.1 mL of 4-hydroxybenzonitrile, 0.11 mol of 2-bromothiophene, 20g of anhydrous potassium carbonate and 100mL of butanone into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring at a temperature of 25 ℃ and a stirring rate of 500 r/min for reaction for 20 min, heating to reflux, continuing stirring for reaction for 20h, cooling the reaction product to room temperature after the reaction is finished, performing vacuum suction filtration, rotationally evaporating the filtrate to remove the solvent, and then performing recrystallization by using absolute ethyl alcohol to obtain an intermediate 1;
step a2: adding 1.0g of metallic sodium and 120mL of 2-methyl-2-butanol into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring at 105 ℃ and stirring speed of 500 r/min for 3h, adding 20mmo of intermediate 1 for continuous stirring for 20 min, adding 10mmo of diethyl succinate dropwise while stirring, controlling the dropping speed to be 1 drop/s, continuing stirring for 15h after the dropping, cooling the reaction product to room temperature after the reaction is finished, adding into absolute methanol, precipitating and filtering in vacuum, placing a filter cake into a vacuum drying oven, and drying at 75 ℃ for 2h to obtain intermediate 2;
step a3: adding 10mmo l of intermediate 2, 22mmo l of 4-bromo-2-thiophenecarboxaldehyde, 2.0g of potassium tert-butoxide and 120mL of anhydrous tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and an air duct, introducing nitrogen for protection, stirring at the temperature of 25 ℃ and the stirring rate of 500 r/min for reaction for 8 hours, pouring the reaction product into ice water after the reaction is finished, extracting with dichloromethane for 2 times, washing the extract with distilled water for 3 times, drying with anhydrous magnesium sulfate, vacuum filtering, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 3;
step a4: adding 10mmo l of intermediate 3, 45mmo l of pyrrole and 150mLN, N-dimethylformamide into a four-neck flask provided with a stirrer, a thermometer, an air duct, a reflux condenser and a constant pressure dropping funnel, introducing nitrogen for protection, adding 5mmo l of trifluoroacetic acid dropwise while stirring under the condition that the temperature is 25 ℃ and the stirring rate is 500 r/min, controlling the dropping rate to be 1 drop/s, continuing stirring and reacting for 5 hours under the condition that the temperature rises to reflux after the dropping is finished, cooling the reaction product to room temperature after the reaction is finished, then carrying out vacuum suction filtration, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 4;
step a5: 10mmo l of intermediate 4, 40mmo l of 3-bromopropyl trimethoxysilane, 45mmo l of anhydrous potassium carbonate and 150mL of absolute ethyl alcohol are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, and are stirred at a temperature of 25 ℃ and a stirring rate of 500 r/min for reaction for 20 min, then the temperature is raised to reflux, the stirring reaction is continued for 4h, after the reaction is finished, the reaction product is cooled to room temperature, then vacuum suction filtration is carried out, and the solvent is removed by rotary evaporation of the filtrate, thus obtaining the degraded particle dispersing agent.
Example 2:
the embodiment is a preparation method of a degradable particle dispersing agent, which comprises the following steps:
step a1: adding 0.1 mL of 4-hydroxybenzonitrile, 0.12mol of 2-bromothiophene, 25g of anhydrous potassium carbonate and 120mL of butanone into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring at a temperature of 30 ℃ and a stirring rate of 600 r/min for reaction for 30 min, heating to reflux, continuing stirring for reaction for 30h, cooling the reaction product to room temperature after the reaction is finished, performing vacuum suction filtration, rotationally evaporating the filtrate to remove the solvent, and then performing recrystallization by using absolute ethyl alcohol to obtain an intermediate 1;
step a2: adding 1.5g of metallic sodium and 150mL of 2-methyl-2-butanol into a three-neck flask provided with a stirrer, a thermometer and a constant pressure dropping funnel, stirring and reacting for 5 hours under the condition that the temperature is 110 ℃ and the stirring rate is 600 r/min, adding 20mmo of intermediate 1, continuously stirring and reacting for 30 min, then dropwise adding 10mmo of diethyl succinate while stirring, controlling the dripping rate to be 2 drops/s, continuously stirring and reacting for 20 hours after the dripping is finished, cooling the reaction product to room temperature after the reaction is finished, adding into absolute methanol, precipitating and precipitating, vacuum filtering, placing a filter cake into a vacuum drying oven, and drying for 3 hours under the condition that the temperature is 80 ℃ to obtain intermediate 2;
step a3: adding 10mmo l of intermediate 2, 25mmo l of 4-bromo-2-thiophenecarboxaldehyde, 2.5g of potassium tert-butoxide and 150mL of anhydrous tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer and an air duct, introducing nitrogen for protection, stirring at the temperature of 30 ℃ and the stirring rate of 600 r/min for reaction for 10 hours, pouring the reaction product into ice water after the reaction is finished, extracting with dichloromethane for 3 times, washing the extract with distilled water for 5 times, drying with anhydrous magnesium sulfate, vacuum filtering, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 3;
step a4: adding 10mmol of intermediate 3, 50mmol of pyrrole and 180mLN, N-dimethylformamide into a four-neck flask provided with a stirrer, a thermometer, an air duct, a reflux condenser and a constant pressure dropping funnel, introducing nitrogen for protection, adding 7mmol of trifluoroacetic acid dropwise while stirring under the condition that the temperature is 30 ℃ and the stirring rate is 600 r/min, controlling the dropping rate to be 2 drops/s, continuing stirring and reacting for 6 hours under the condition that the temperature is raised to reflux after the dropping is finished, cooling the reaction product to room temperature after the reaction is finished, then carrying out vacuum suction filtration, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 4;
step a5: 10mmol of intermediate 4, 40mmol of 3-bromopropyl trimethoxy silane, 50mmol of anhydrous potassium carbonate and 200mL of absolute ethyl alcohol are added into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirred at a temperature of 30 ℃ and a stirring rate of 600 r/min for reaction for 30 min, then heated to reflux, stirred continuously for reaction for 5h, after the reaction is finished, the reaction product is cooled to room temperature, then vacuum suction filtration is carried out, and the solvent is removed by rotary evaporation of the filtrate, thus obtaining the degraded particle dispersing agent.
Example 3:
the embodiment is a method for repairing organic pollutant contaminated soil, comprising the following steps:
step one: adding 10g of titanium dioxide, 5g of polyvinyl chloride and 150mL of absolute ethyl alcohol into a three-neck flask with a stirrer and a thermometer, performing ultrasonic dispersion for 20 min under the condition of ultrasonic frequency of 40kHz, stirring and reacting for 2h under the condition of temperature of 25 ℃ and stirring rate of 500 r/min, cooling a reaction product to room temperature after the reaction is finished, removing a solvent by rotary evaporation, placing the evaporation product into a tubular furnace, introducing nitrogen for protection, then performing heat preservation for 1h under the condition of temperature rising rate of 4 ℃ min to 120 ℃, then performing calcination for 3h under the condition of temperature rising to 820 ℃, and cooling along with the furnace to obtain carbon-coated particles;
step two: soaking 10g of carbon-coated particles in a nitric acid solution with the mass fraction of 20% for 20 hours, taking out and adding the carbon-coated particles into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, adding 120mL of absolute ethyl alcohol, stirring and reacting for 20 min under the condition that the temperature is 25 ℃ and the stirring rate is 500 r/min, adding 10mL of ferric nitrate solution with the molar concentration of 1mol/L and 10mL of sodium hydroxide solution with the molar concentration of 1mol/L dropwise while stirring, controlling the dripping rate to be 1 mol/s, continuing to stir and react for 2 hours after the dripping is finished, placing the reaction product in a vacuum drying box after the reaction is finished, drying for 2 hours at the temperature of 100 ℃, then placing the reaction product in a tubular furnace, introducing nitrogen for protection, calcining for 2 hours under the condition that the temperature is raised to 500 ℃ at the heating rate of 8 ℃ mi, and cooling along with the furnace to obtain degradation particles;
step three: adding 10g of degradation particles, 2.5g of degradation particle dispersing agent, 80mL of absolute ethyl alcohol and 60mL of deionized water into a three-neck flask provided with a stirrer, a thermometer, an air duct and a reflux condenser, introducing nitrogen for protection, stirring and reacting for 20 min under the condition that the temperature is 25 ℃ and the stirring rate is 500 r/min, heating to reflux, continuing stirring and reacting for 3h, vacuum filtering the reaction product after the reaction is finished, washing a filter cake with distilled water for 3 times, and then placing in a vacuum drying oven, and drying for 4h under the condition that the temperature is 75 ℃ to obtain a pollution degradation agent;
step four: uniformly spraying the pollution degradation agent into the surface of the organic pollutant polluted soil, and then deep ploughing and mixing, wherein the adding amount of the pollution degradation agent is 5% of the mass of the organic pollutant polluted soil.
Example 4:
the embodiment is a method for repairing organic pollutant contaminated soil, comprising the following steps:
step one: adding 10g of titanium dioxide, 10g of polyvinyl chloride and 180mL of absolute ethyl alcohol into a three-neck flask with a stirrer and a thermometer, performing ultrasonic dispersion for 30 min under the condition of ultrasonic frequency of 50kHz, stirring for 3h under the condition of temperature of 30 ℃ and stirring rate of 600 r/min, cooling the reaction product to room temperature after the reaction is finished, removing the solvent by rotary evaporation, placing the evaporation product into a tubular furnace, introducing nitrogen for protection, then performing heat preservation for 1.5h under the condition of temperature rising rate of 5 min to 125 ℃, performing calcination for 4h under the condition of temperature rising to 850 ℃, and performing furnace cooling to obtain carbon-coated particles;
step two: soaking 10g of carbon-coated particles in a nitric acid solution with the mass fraction of 25% for 30 hours, taking out and adding the carbon-coated particles into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, adding 150mL of absolute ethyl alcohol, stirring and reacting for 30 min under the condition that the temperature is 30 ℃ and the stirring rate is 600 r/min, adding 15mL of ferric nitrate solution with the molar concentration of 1mol/L and 15mL of sodium hydroxide solution with the molar concentration of 1mol/L dropwise while stirring, controlling the dripping rate to be 2 drops/s, continuing to stir and react for 3 hours after the dripping is finished, placing the reaction product in a vacuum drying box after the reaction is finished, drying for 3 hours at the temperature of 105 ℃, then placing the reaction product in a tubular furnace, introducing nitrogen for protection, calcining for 3 hours under the condition that the temperature is raised to 520 ℃ at the heating rate of 10 ℃ mi, and cooling along with the furnace to obtain degradation particles;
step three: adding 10g of degradation particles, 7.5g of degradation particle dispersing agent, 100mL of absolute ethyl alcohol and 80mL of deionized water into a three-neck flask provided with a stirrer, a thermometer, an air duct and a reflux condenser, introducing nitrogen for protection, stirring and reacting for 30 min under the condition that the temperature is 30 ℃ and the stirring rate is 600 r/min, heating to reflux, continuing stirring and reacting for 5h, vacuum filtering the reaction product after the reaction is finished, washing a filter cake with distilled water for 5 times, and then placing in a vacuum drying oven, and drying for 5h under the condition that the temperature is 80 ℃ to obtain a pollution degradation agent;
step four: uniformly spraying the pollution degradation agent into the surface of the organic pollutant polluted soil, and then deep ploughing and mixing, wherein the adding amount of the pollution degradation agent is 10% of the mass of the organic pollutant polluted soil.
Comparative example 1:
comparative example 1 differs from example 4 in that no contaminating degrading agent was added.
Comparative example 2:
comparative example 2 differs from example 4 in that titanium dioxide was used instead of the contaminating degradation agent.
Comparative example 3:
comparative example 3 differs from example 4 in that instead of contaminating degrading agents, degrading particles are used.
And determining the degradation rate change of the organic pollutants in the organic pollutant polluted soil restoration process, wherein the main pollutants of the organic pollutant polluted soil are petroleum hydrocarbon, polychlorinated biphenyl and benzene, and the detection results are shown in the following table:
referring to the above table data, it can be seen from the comparison of examples 3 to 4 and comparative examples 1 to 3 that when the organic pollutant contaminated soil to which no substance was added was degraded and volatilized slowly, a large amount of organic pollutant remained therein after 30d, and titanium dioxide, degradation particles and a contaminant degradation agent were added to the organic pollutant contaminated soil to rapidly degrade the organic pollutant therein, improving the soil environment, and that when the added substance was the contaminant degradation agent, the best soil restoration effect was shown.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (10)
1. The method for repairing the organic pollutant polluted soil is characterized by comprising the following steps of:
step one: adding titanium dioxide, polyvinyl chloride and absolute ethyl alcohol into an Anthree-neck flask for ultrasonic dispersion, stirring for reaction, cooling a reaction product to room temperature after the reaction is finished, performing rotary evaporation, calcining an evaporation product, and cooling with a furnace to obtain carbon-coated particles;
step two: soaking carbon-coated particles in nitric acid solution, taking out and adding the carbon-coated particles into a three-neck flask, adding absolute ethyl alcohol, stirring and reacting, simultaneously dropwise adding ferric nitrate solution and sodium hydroxide solution while stirring, continuing stirring and reacting after the dropwise adding is finished, drying a reaction product after the reaction is finished, calcining, and cooling along with a furnace to obtain degradation particles;
step three: adding degradation particles, a degradation particle dispersing agent, absolute ethyl alcohol and deionized water into a three-neck flask, stirring for reaction, vacuum filtering a reaction product after the reaction is finished, and washing and drying a filter cake to obtain a pollution degradation agent;
step four: and uniformly spraying the pollution degradation agent into the surface of the organic pollutant polluted soil, and then carrying out deep ploughing and mixing.
2. The method for restoring organic pollutant contaminated soil according to claim 1, wherein the amount of the titanium dioxide, the polyvinyl chloride and the absolute ethyl alcohol in the first step is 10g:5-10g:150-180mL.
3. The method for restoring organic pollutant contaminated soil according to claim 1, wherein the dosage ratio of the carbon-coated particles, the absolute ethyl alcohol, the ferric nitrate solution and the sodium hydroxide solution in the second step is 10g:120-150mL:10-15mL:10-15mL, wherein the mass fraction of the nitric acid solution is 20-25%, and the molar concentration of the ferric nitrate solution and the sodium hydroxide solution is 1mol/L.
4. The method for restoring organic pollutant contaminated soil according to claim 1, wherein the dosage ratio of the degradation particles, the degradation particle dispersant, the absolute ethyl alcohol and the deionized water in the third step is 10g:2.5-7.5g:80-100mL:60-80mL.
5. The method for restoring organic pollutant contaminated soil according to claim 1, wherein the degradation particle dispersing agent is prepared by the following steps:
step a1: adding 4-hydroxybenzonitrile, 2-bromothiophene, anhydrous potassium carbonate and butanone into a three-neck flask, stirring for reaction, cooling a reaction product to room temperature after the reaction is finished, performing vacuum filtration, rotationally evaporating filtrate, and recrystallizing to obtain an intermediate 1;
step a2: adding metal sodium and 2-methyl-2-butanol into a three-neck flask, stirring for reaction, adding an intermediate 1 and diethyl succinate, continuously stirring for reaction, cooling a reaction product to room temperature after the reaction is finished, adding the reaction product into anhydrous methanol to precipitate, performing vacuum filtration, and drying a filter cake to obtain an intermediate 2;
step a3: adding the intermediate 2, 4-bromo-2-thiophenecarboxaldehyde, potassium tert-butoxide and anhydrous tetrahydrofuran into a three-neck flask, stirring for reaction, pouring a reaction product into ice water after the reaction is finished, extracting, washing and drying an extract, vacuum filtering, and rotationally evaporating filtrate to obtain an intermediate 3;
step a4: adding the intermediate 3, pyrrole and N, N-dimethylformamide into a four-necked flask, dropwise adding trifluoroacetic acid while stirring, continuing stirring for reaction after the dropwise adding, cooling a reaction product to room temperature after the reaction is finished, vacuum filtering, and rotationally evaporating filtrate to obtain an intermediate 4;
step a5: adding the intermediate 4, 3-bromopropyl trimethoxy silane, anhydrous potassium carbonate and absolute ethyl alcohol into a three-neck flask, stirring for reaction, cooling the reaction product to room temperature after the reaction is finished, vacuum filtering, and rotationally evaporating the filtrate to obtain the degradation particle dispersing agent.
6. The method for restoring soil contaminated by organic pollutants according to claim 5, wherein the dosage ratio of 4-hydroxybenzonitrile, 2-bromothiophene, anhydrous potassium carbonate and butanone in step a1 is 0.1mol:0.11-0.12mol:20-25g:100-120mL.
7. The method for restoring soil contaminated by organic pollutants according to claim 5, wherein the dosage ratio of the metallic sodium, 2-methyl-2-butanol, intermediate 1 and diethyl succinate in step a2 is 1.0-1.5g:120-150mL:20mmol:10mmol.
8. The method for restoring soil contaminated by organic pollutants according to claim 5, wherein the dosage ratio of the intermediate 2, 4-bromo-2-thiophenecarboxaldehyde, potassium tert-butoxide and anhydrous tetrahydrofuran in step a3 is 10mmol:22-25mmol:2.0-2.5g:120-150mL.
9. The method for restoring soil contaminated with organic contaminants according to claim 5, wherein the intermediate 3, pyrrole, N-dimethylformamide and trifluoroacetic acid in step a4 are used in a ratio of 10mmol:45-50mmol:150-180mL:5-7mmol.
10. The method for restoring soil contaminated by organic pollutants according to claim 5, wherein the intermediate 4, 3-bromopropyl trimethoxysilane, anhydrous potassium carbonate and absolute ethanol in step a5 are used in an amount ratio of 10mmol:40mmol:45-50mmol:150-200mL.
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