Method for removing phthalate ester in soil based on phenate-based system

Abstract

To provide a method for removing phthalate esters in soil.SOLUTION: Following the preparation of a phenate remediation agent from biochar, potassium ferrate, and a spray solution as raw materials, the phenate remediation agent is blended with a phthalate ester-contaminated soil in a specified proportion to remedy the phthalate ester-contaminated soil, thereby enabling the efficient and long-term removal of phthalate esters from the contaminated soil.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to the technical field of soil remediation, in particular to the application of phenate-based lids in soils. This invention relates to a method for removing esters of carboxylic acids. [Background technology]

[0002] Phthalic acid esters (PAEs), also known as phthalates, are esters formed from phthalic acid. It is a general term. It is considered to be a type of environmental hormone that is universally present in the living environment. Acid ester compounds are fat-soluble compounds, and are particularly prone to sticking to hot butter, animal fats, etc. in plastic bags. When packaging fatty foods, it increases the amount of fat that is ingested, which is bad for health. Environmental health hazards caused by chemical compounds have been widely reported in the fields of environmental science, public health, the media, and even the general public. It has also attracted widespread attention. Phthalate esters have been detected in agricultural soil in various regions, and some soil contamination is severe. This can be harmful to human health, and is currently the most common cause of phthalate contamination. Most of the methods for remediating contaminated soil are the Fenton process or the Fenton-like process. The method requires that the soil pH be kept relatively low to ensure that the reaction system is running. Although the Fenton-like process is expensive and highly destructive, the range of pH application has been expanded. However, hydrogen peroxide has the disadvantages of being easily decomposed and unstable, so Therefore, a method is needed to effectively remove phthalate esters from soil in order to prevent contamination of the soil. Summary of the Invention [Problem to be solved by the invention]

[0003] In order to solve the above technical problems, the present invention provides a method for the treatment of phthalic acid in soil based on phenate system. A method for removing esters is provided. [Means for solving the problem]

[0004] The technical solution of the present invention is as follows: A method for removing steal, comprising the steps of: Producing a phenate repair agent, comprising: Biochar heated to 80-100℃ and potassium ferrate at 20-30℃ were mixed in a ratio of 6-12:1. Mix in the appropriate ratio, add milling balls to it, and mix to mill. After stirring and milling for 10 to 15 minutes, the biochar and potassium ferrate were added to the mixture. Spray 4 to 8% of the spray liquid based on the total mass of the mixture of charcoal and potassium ferrate, and then leave for 30 minutes. n Mix and mill, The spray liquid is a sodium hydroxide solution as a base liquid, and 3% sodium chloride is added to the base liquid by mass. The base solution is made of sodium hydroxide and 1.5% hydroxymethylcellulose. The thorium solution is 1 mol / L, and the spray temperature of the spray liquid is 20-30°C. After that, it is left to stand for 3 minutes, then milled and stirred again until it is completely dry. Step S1 of obtaining an ethylenate restorative; Remediating the phthalate-contaminated soil, comprising: The phenate remediation agent was mixed with the phthalate ester-contaminated soil in a weight ratio of 0.1 to 0.2:1. and step S2 of remediating the phthalate-contaminated soil. According to one aspect of the present invention, the biochar is an activated biochar, In the activation treatment method, biochar is added to a mixture of zinc chloride and hydroxyethyl cellulose. Add the biochar and leave it to soak for 10-20 minutes, then take out the biochar and spread it evenly on the mesh. The mesh was placed in a tube furnace and heated with a high-temperature mixture of CO2 and nitrogen gas at a flow rate of 100 mL / min. After 3 hours of treatment, nitrogen gas was introduced at a flow rate of 20 mL / min to reduce the temperature in the tube furnace. The temperature was lowered to 25°C, and the biochar was then acid-washed and rinsed multiple times with deionized water to activate it. Obtaining treated biochar; In the high-temperature mixed gas containing CO2 and nitrogen gas, the volume ratio of CO2 to nitrogen gas is The ratio of the biochar, zinc chloride, hydrochloric acid, and the like is 3:7, and the temperature of the high-temperature mixed gas is 500°C. The mass ratio of hydroxyethyl cellulose added was 12:2:3. Description: Biochar is activated by soaking it in a mixed liquid or by using high-temperature CO2 gas. By integrating the activation of biochar through physical activation, the adsorption of biochar This significantly improves performance and subsequently improves the effectiveness of the use of the prepared phenate repair agent. According to one aspect of the present invention, the surface of the milling ball is covered with a heat insulating material, The insulation material is a thermal insulating ceramic, and the coating thickness is 2 mm. Description: By coating the milling balls with insulating ceramics, The heat absorption of the balls is what causes the biochar at 80-100℃ and potassium ferrate at 20-30℃ to melt. To avoid affecting the processing effect by stirring and milling. According to one aspect of the present invention, in-situ repair processing is used in step S2. In practice, the phenate amendment is spread evenly on the contaminated soil, then turned over and sprayed with water. Mist the contaminated soil to reduce its moisture content to 40%. Explanation: Removing phthalate esters from soil by in-situ remediation is a simple and easy remediation method. No need for operations such as transportation or excavation, so the amount of remediation work is small and phthalate ester-contaminated soil can be effectively treated. can be repaired. According to one aspect of the present invention, in the step S1, a phenate repair agent is prepared. The device used includes a tank, a cover, and a storage tank for storing biochar and potassium ferrate. The present invention includes a mixing unit for mixing the spray liquid with the spraying liquid, and a spray unit for controlling the spraying of the spray liquid. The stirring unit includes a stirring motor, a stirring shaft, a stirring blade, and a heating unit. The stirring motor is provided in a groove on the inner bottom surface of the tank, and one end of the stirring shaft is connected to the output shaft of the stirring motor. The impeller is fixedly connected to the agitator shaft and has a collar that is fitted to the agitator shaft and a side wall of the collar. The tank includes a plurality of semicircular stirring plates provided along the circumferential direction, and the inner bottom surface of the tank includes the semicircular stirring plates. A semicircular groove is provided to fit the circular stirring plate, and the heating portion corresponds one-to-one to the semicircular stirring plate. A plurality of heating plates are provided so as to be detachably connected to the semicircular stirring plate at the bottom of the heating section. An engagement groove is provided, The spray unit includes a threaded rod, a threaded ring, an airbag ring, and a liquid a control box, one end of the threaded rod being fixedly connected to a groove in the top surface of the cover. the other end of the threaded ring is rotatably connected to the other end of the agitator shaft, and the threaded ring is The airbag ring is fitted onto the threaded rod and into the groove on the top surface of the cover. The liquid control box is annular and is mounted on the top surface of the cover. The airbag ring is connected to the top surface of the liquid control box via a plurality of hoses. A check valve is provided in the liquid control box to allow gas to flow in one direction. The bottom surface of the box is provided with multiple nozzles that penetrate the cover, The heating section has an outer bottom surface provided with a plurality of countersunk holes, and a rotatable support is provided in the countersunk holes. A control tray is provided which is connected to the control unit and has a central post extending through a counterbore. A winding box and a transmission bar are provided on one side of the inner bottom surface of the heating section, One end of the transmission bar is connected to the winding box, and the other end of the transmission bar passes through the heating section and is screwed. The control tray is connected to the ring, and the inner bottom surface of the heating section is connected to the control tray by contacting the transmission bar with the central column. A stopper is provided for rotating the control tray. The counterbore and the control tray are provided with A through hole is provided for discharging biochar, and the threaded ring is connected to the biochar discharge hole via a plurality of telescopic rods. The connector is then permanently attached to the collar. Description: When using this device to produce a phenate repair agent, a threaded rod and a threaded ring are After mixing and milling for 10 to 15 minutes, the It is possible to automatically add the spray liquid, and this can be done without adding any electronic control elements. The device can effectively perform the manufacturing procedure of the phenate repair agent. This simplifies and enables efficient production of phenate repair agents. In addition, the movement of the threaded ring controls the heating section, converting the biochar into potassium ferrate. The temperature of the potassium ferrate rises and the temperature of the potassium ferrate increases due to the large amount of addition. The temperature of the ionochar is quickly lowered, and the biochar and potassium ferrate are mixed at a certain temperature difference. By using this device, the biochar and calcium ferrate can be easily mixed. The manufacturing effect of mixing with sodium due to the temperature difference has been further improved, resulting in a more excellent phenanthrene with better usability. A base repair agent is obtained. According to one aspect of the present invention, the transmission bar and the central column adopt a friction transmission method. Description: The friction transmission is used to transmit power between the transmission bar and the central column. To effectively control the rotation of the control tray while ensuring the sealing of the sliding connection with the heating section, and Low manufacturing costs. According to another aspect of the present invention, the transmission bar and the central column adopt a tooth transmission method, and the transmission The moving bar is provided with transmission teeth, and the central column is provided with tooth grooves that mesh with the transmission bar to transmit power. It will be established. Description: The transmission between the transmission bar and the central column is performed through tooth transmission, which makes the transmission efficiency higher. Compared with the friction transmission method, slippage occurs in friction transmission, which affects the rotation efficiency of the control tray. This effectively avoids the susceptibility to Effect of the Invention

[0005] The beneficial effects of the present invention are as follows: (1) In the present invention, a phenate-based remediation agent for phthalate ester-contaminated soil is By simply mixing the phenate remediation agent with the phthalate ester-contaminated soil and turning it over, This can effectively remove phthalate esters from contaminated soil. (2) In the present invention, the manufacturing method of the phenate repair agent is optimized to obtain phthalate ester. The effectiveness of the phenate remediation agent for terbium-contaminated soil was effectively improved, and the lid It can effectively and long-term remove esters of carboxylic acids. (3) In the present invention, an apparatus based on a method for producing a phenate repair agent is provided, and the apparatus is used This effectively simplifies the manufacturing procedure of the phenate repair agent, and can be efficiently manufactured, thereby saving production costs and shortening the production cycle. [Brief description of the drawings]

[0006] [Figure 1] FIG. 1 is an external view of an apparatus according to the present invention. [Diagram 2]FIG. 2 is a schematic diagram of the internal structure of the device of the present invention. [Diagram 3] FIG. 2 is a schematic diagram of the assembled structure of the stirring shaft and threaded rod of the present invention. [Figure 4] FIG. 6 is a schematic diagram of the internal structure of a heating unit according to a second embodiment of the present invention. [Diagram 5] FIG. 11 is a schematic diagram of a cross-sectional structure of a heating section according to a second embodiment of the present invention. [Figure 6] FIG. 11 is a schematic diagram of the bottom structure of the heating part according to the second embodiment of the present invention. [Figure 7] FIG. 11 is a structural schematic diagram of the control tray of the heating section according to the second embodiment of the present invention; [Figure 8] FIG. 11 is a schematic diagram of the internal structure of a heating unit according to a third embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] In order to more clearly illustrate the advantages of the present invention, the present invention will be described below by way of a specific embodiment. This will be explained in more detail below. Example 1 A phenate-based method for removing phthalate esters from soil, comprising the steps of: include. S1: Preparation of phenate repair agent Biochar heated to 95°C was mixed with potassium ferrate at 25°C in a weight ratio of 8:1, and then Add milling balls coated with 2mm thick insulating ceramic and stir. Milling, After stirring and milling for 12 min, the mixture of biochar and potassium ferrate was added with biochar and iron. Spray 6.5% of potassium hydroxide solution based on the total mass of the mixture and stir for another 30 min. Then, milling is performed. The spray liquid is a sodium hydroxide solution as the base liquid, and 3% sodium chloride is added to the base liquid by mass. 1.5% hydroxymethylcellulose was added to the base solution, and sodium hydroxide was added to the The concentration of the solution was 1 mol / L, and the spray temperature of the spray solution was 25°C. After that, it is left to stand for 3 minutes, then milled and stirred again until it is completely dry. A phenate repair agent is obtained. S4. Remediation of phthalate-contaminated soil The phenate remediation agent is evenly spread on the contaminated soil, then it is turned over and sprayed with water to remove the contaminant. The moisture content of dyed soil is set at 40%, and soil contaminated with phthalates is remediated. The phenate amendment and the contaminated soil were mixed at a ratio of 120 g of phenate amendment to 1 kg of contaminated soil. do. To verify the effectiveness of the above-mentioned phenate remediation agent on phthalate ester-contaminated soil To this end, an experiment is conducted and the following comparative examples are provided. 1) Comparative Example 1: Potassium ferrate 120g: 120g of potassium ferrate per kg of contaminated soil Weigh out as a repair agent, and sprinkle potassium ferrate evenly on the contaminated soil, then cut it and Then, a sodium sulfite solution was sprayed to bring the moisture content of the contaminated soil to 40%, and the phthalate esters were removed. The contaminated soil was remediated using a sodium sulfite solution with a concentration of 0.4 mol / L. do. 2) Comparative Example 2: The weight ratio of biochar to potassium ferrate was 8:1. 120g of ferric iron + biochar) : 106g of biochar and 14g of potassium ferrate per 1kg of contaminated soil g were weighed and mixed to form a remediation agent, and the mixture of biochar and potassium ferrate was evenly distributed on the contaminated soil. The soil was first sprayed with water, then turned over and sprayed with water until the moisture content of the contaminated soil reached 40%. 3) Comparative Example 3: 120 g of phenate remediation agent was added to 1 kg of contaminated soil. Weigh out 20g of the phenate amendment and spread it evenly on the contaminated soil, then turn it over. The soil was sprayed with sodium sulfite solution to bring the moisture content to 40%. The dye soil is repaired, where the concentration of sodium sulfite solution is 0.4 mol / L. The following describes the restoration methods in Example 1, Comparative Example 1, and Comparative Example 2 for the phthalic acid The ester-contaminated soil was remediated and the results of measurements are shown in Table 1 below. Table 1. Effect of various phenate systems on phthalate removal rate

[0008] TIFF2025023773000002.tif28157

[0009] From the comparison in Table 1, the phenate repair agent prepared in Example 1 has a low nitrile content when used. There is no need to spray sodium sulfate solution, and the phthalate ester removal rate is higher than in Comparative Example 1. It was found that the rate was higher and the consumption of potassium ferrate was significantly reduced. The phenate repair agent produced by is more economical and more environmentally friendly. Compared to Example 1 From the comparison of Example 2, when biochar and potassium ferrate are mixed and used, the amount of phthalate ethylene is It was found that the sterilization rate was clearly decreased. When the moisture content of the contaminated soil was controlled using sodium phthalate solution, the removal rate of phthalates was Although there was an improvement, the degree of improvement was small, and in view of costs, secondary pollution, etc., Example 1 is more preferable. Example 2 This example describes the apparatus used to prepare the phenate remediation agent of Example 1. As shown in FIGS. 1 to 7, the device includes a tank 1, a cover 2, and a a mixing unit 3 for mixing the biochar and potassium ferrate, and a liquid spray control unit 4 for controlling the liquid spray. A spray unit 4, The stirring unit 3 includes a stirring motor 31, a stirring shaft 32, a stirring blade 33, a heating unit 34, and The agitator motor 31 is provided in a groove in the inner bottom surface of the tank 1, and one end of the agitator shaft 32 is The agitation blade 33 is fixedly connected to the output shaft of the motor 31, and is detachably attached to the agitation shaft 32. A collar 331 is fitted into the collar 331, and a plurality of semi-circular grooves are provided on the side wall of the collar 331 along the circumferential direction. The tank 1 includes a circular stirring plate 332, and a semicircular stirring plate 332 is fitted to the semicircular stirring plate 332 on the inner bottom surface of the tank 1. A plurality of heating parts 34 are provided so as to correspond one-to-one to the semicircular stirring plates 332. The bottom surface of the heating section 34 is provided with an engagement groove that is removably connected to a semicircular stirring plate 332. was established, The spray unit 4 comprises a threaded rod 41, a threaded ring 42, and an airbag ring 4. 3 and a liquid control box 44, one end of the threaded rod 41 is connected to the top surface of the cover 2. The other end of the agitator shaft 32 is rotatably connected to the other end of the agitator shaft 32 and is threaded. The ring 42 is threaded onto the threaded rod 41, and the airbag ring 43 is threaded onto the threaded rod. The liquid control box 44 is fitted into the door 41 and fixedly connected to the groove on the top surface of the cover 2. The airbag ring 43 is annular and is provided on the upper surface of the cover 2. The airbag ring 43 is connected to the cover 2 through a plurality of hoses. The hose is connected to the top of the liquid control box 44, and the gas is supplied to the liquid control box 44 through the hose. The bottom of the liquid control box 44 is provided with a check valve that allows the liquid to flow in one direction. A plurality of nozzles are provided, A plurality of countersunk holes 341 are provided on the outer bottom surface of the heating portion 34. A control tray 342 is provided which is rotatably connected to the control tray 342 and has a counterbore A central pillar 343 is provided penetrating the inner bottom surface of the heating section 34. One end of the transmission bar 344 is connected to the winding box. The other end of the transmission bar 344 passes through the heating portion 34 and is connected to the threaded ring 42. The inner bottom surface of the control tray 342 is provided with a transmission bar 344 in contact with the central column 343 to rotate the control tray 342. The counterbore 341 and the control tray 342 are provided with stoppers for adjusting the position of the counterbore 341 and the control tray 342. The threaded ring 42 is provided with a plurality of extendable rods. The transmission bar 344 and the central column 343 are fixedly connected to the collar 331 via a friction transmission. Formula is adopted. The method of operation of the above device is as follows. Open the cover 2, place the biochar in the heating section 34, and pour potassium ferrate into the tank 1. Next, the ceramic-coated milling ball is inserted while the spray liquid is controlled. The box 44 is filled, and then the stirring motor 31 is started. There are operating modes. Operation mode 1: The agitator motor 31 is driven by the threaded rod 41 and the threaded ring 42. The number of rotations is controlled, and after 12 minutes of rotation, the threaded ring 42 is attached to the airbag ring 43. When pressed, the airbag ring 43 sends gas to the top of the liquid control box 44. The spray liquid was injected into the tank 1 through a nozzle equipped with a pressure valve by the action of air pressure. As the threaded ring 42 rises, it pulls the transmission bar 344 The transmission bar 344 and the central column 343 perform friction transmission, so that the control tray 342 rotates. The holes were opened intermittently by rotating the plate to allow the biochar to fall intermittently onto the potassium ferrate. The temperature of the potassium ferrate increases when a large amount is added, and the temperature of the biochar decreases rapidly. , it is possible to avoid adversely affecting the effect of mixing with a temperature difference. Operation mode 2: The threaded ring 42 stirs the threaded rod 41 in two stages. The mixing area is divided into a stirring section and a pressing space, and the mixing is performed by the forward and reverse cycle of the stirring motor 31 due to the temperature difference. The entire process is controlled by the threaded ring 42 in the stirring space of the threaded rod 41. The agitator moves up and down in the water and continuously mixes potassium ferrate and biochar with the agitator blades 33. The mixture is stirred and mixed, during which biochar is intermittently released by the action of the heating section 34. After the min process, the rotation of the stirring motor 31 is adjusted so that the threaded ring 42 enters the pressing space. The screw ring 42 presses the air bag ring 43, and the spray liquid is sprayed into the pressure valve. The mixture is injected into the tank 1 through a nozzle, and then the stirring motor 31 rotates, and the threaded ring 42 In this way, the forward and reverse rotation cycle is repeated, and milling and mixing continue. will be done. Example 3 In this embodiment, compared with the second embodiment, as shown in FIG. 8, the transmission bar 344 and the central column 343 are The tooth transmission method is adopted, the transmission bar 344 is provided with transmission teeth, and the central column 343 is provided with The difference is that a tooth groove is provided for meshing with the transmission bar 344 to transmit power. The method of operation of the above device is as follows. Compared with the operating method of the second embodiment, the threaded ring 42 pulls the transmission bar 344 to the transmission bar 3 44 and the central column 343 are engaged to transmit power, so that the control tray 342 rotates. The difference is that the through holes are intermittently opened. Example 4 In this example, compared to Example 1, biochar heated to 80°C and potassium ferrate at 30°C were used. in a weight ratio of 8:1. Example 5 In this example, compared to Example 1, biochar heated to 100°C and potassium ferrate at 20°C were used. The difference is that the and are mixed in a weight ratio of 8:1. Example 6 In this example, compared to Example 1, biochar heated to 95°C and potassium ferrate at 25°C were used. The difference is that they are mixed in a weight ratio of 6:1. Example 7 In this example, compared to Example 1, biochar heated to 95°C and potassium ferrate at 25°C were used. The difference is that they are mixed in a weight ratio of 12:1. Example 8 In this example, compared to Example 1, after stirring and milling for 10 minutes, biochar and iron were A 6.5% solution of potassium ferrate was sprayed onto the mixture of biochar and potassium ferrate. However, there are differences in that the mixture is milled after stirring for 30 minutes and that the spray temperature is 20°C. do. Example 9 In this example, compared to Example 1, after stirring and milling for 15 minutes, biochar and iron were A 6.5% solution of potassium ferrate was sprayed onto the mixture of biochar and potassium ferrate. However, there are differences in that the mixture is milled after stirring for 30 minutes and that the spray temperature is 30°C. do. Example 10 In this example, compared to Example 1, after stirring and milling for 12 minutes, biochar and iron were A 4% spray solution based on the total mass of potassium ferrate was sprayed onto the mixture of biochar and potassium ferrate. The difference is that the mixture is mixed for 30 minutes and then milled. Example 11 In this example, compared to Example 1, after stirring and milling for 12 minutes, the biochar-oriented The mixture of potassium ferrate was sprayed with 8% spray solution based on the total mass of biochar and potassium ferrate. However, the difference is that the mixture is mixed for 30 minutes and then milled. Example 12 In this example, compared to Example 1, the phenate remediation agent and the contaminated soil were treated with 10% phenate remediation agent. The difference is that 0g: 1kg of contaminated soil is mixed. Example 13 In this example, compared to Example 1, the phenate remediation agent and the contaminated soil were treated with 20% phenate remediation agent. The difference is that 0g: 1kg of contaminated soil is mixed. In order to verify the remediation effect of the above-mentioned phenate remediation agent on phthalate ester-contaminated soil, To this end, an experiment is conducted and the following comparative examples are provided. 1) Comparative Example 4: The remaining parameters were the same except that the spray liquid was a 1 mol / L sodium hydroxide solution. All the data conditions were the same as in Example 1. 2) Comparative Example 5: Biochar at 25°C and potassium ferrate at 25°C are mixed in a weight ratio of 8:1. Other than that, the remaining parameter conditions are all the same as in the first embodiment. Using the repair methods in Examples 4 to 13 and Comparative Examples 4 and 5, a certain phthalate ester was The steril-contaminated soil was remediated and the results of measurements are shown in Table 2 below. Table 2. Effect of various phenate systems on phthalate removal rate

[0010] TIFF2025023773000003.tif53158

[0011] From the comparison in Table 2, the results of comparing Example 1 with Examples 4 and 5 show that the mixture with potassium ferrate In this case, the biochar temperature affected the remediation effect of the phenate remediator produced later. Among them, the parameters of Example 1 were found to be the most preferable. As a result of comparing with Example 6 and Example 7, the mixing mass ratio of biochar and potassium ferrate was The effect of the phenate repair agent on the repairing effect of the phenate repair agent is affected, and among them, the parameters of Example 1 It was found that the spray nozzle was relatively favorable. The temperature of the mist solution and the time of stirring and milling influence the repair effect of the phenate repair agent produced later. Among them, the parameters of Example 1 were found to be relatively favorable. As a result of comparing Example 1 with Examples 10 and 11, as the amount of the sprayed liquid increases, The rate at which the phthalate ester removal rate of the phenate repair agent produced increases tends to slow down. The removal rate was the highest in Example 11, but the difference with the removal rate in Example 1 was not that large. Therefore, from an economical point of view, it was found that the overall use effect of Example 1 was superior. As a result of comparing Example 1 with Examples 12 and 13, it was found that the increase in the amount of phenate repair agent The effectiveness of the phenate amendment in removing phthalate esters from contaminated soil was also examined. It was found that there was a tendency for the amount of the saturation to decrease. The difference in removal rate between the two is small, and from an economical point of view, the overall use effect of Example 1 is superior. It was found that this was the case. In addition, as a result of comparing Comparative Example 4 and Comparative Example 5, the spray liquid was changed and the mixture of biochar and potassium ferrate was used. The effectiveness of the produced phenate repair agent decreased due to changes in the mixing conditions. I found out. Example 14 In this example, compared to Example 1, the biochar is an activated biochar. In the chemical treatment method, biochar is added to a mixture of zinc chloride and hydroxyethyl cellulose. The biochar was then soaked in water for 16 minutes, and then taken out and spread evenly on the mesh. The tube was placed in a furnace and a high-temperature mixture of CO2 and nitrogen gas was introduced at a flow rate of 100 mL / min. After 3 hours of treatment, nitrogen gas was introduced at a flow rate of 20 mL / min to raise the temperature inside the tube furnace to 25°C. The biochar was then acid-washed and rinsed multiple times with deionized water to give an activated biochar. Obtaining biochar, In a high-temperature mixed gas containing CO2 and nitrogen gas, the volume ratio of CO2 to nitrogen gas is 3: 7, the temperature of the high-temperature mixed gas is 500°C, and biochar, zinc chloride, hydroxyethyl The difference is that the mass ratio of added cellulose is 12:2:3. Example 15 In this example, compared to Example 1, the zinc chloride and hydroxyethyl cellulose mixture was used. The difference is that ion charcoal is added and soaked for 10 minutes. Example 16 In this example, compared to Example 1, the zinc chloride and hydroxyethyl cellulose mixture was used. The difference is that ionized charcoal is added and soaked for 20 minutes. In order to verify the remediation effect of the above-mentioned phenate remediation agent on phthalate ester-contaminated soil, To this end, an experiment is conducted and the following comparative examples are provided. Comparative Example 6: Biochar was placed in a zinc chloride solution and soaked for 16 minutes. Except for the addition mass ratio of 12:2, the remaining parameters were all the same as in Example 1. I did. Using the remediation methods of Examples 14 to 16 and Comparative Example 6, a phthalate ester-contaminated soil in our city was The results of the restoration and measurement are shown in Table 3 below. Table 3. Effect of various phenate systems on phthalate removal rate

[0012] TIFF2025023773000004.tif27158

[0013] From the comparison of Table 3, the results of comparing Example 1 and Example 14 show that the activation treatment of biochar Therefore, the phenate remediation agent produced using this biochar can effectively reduce the amount of phthalate ethylene oxide in contaminated soil. It was found that the removal rate of steers was increased. The comparison showed that the phenate remediation agent produced reduced the amount of flocculation in the contaminated soil over time. It was found that the taric acid ester removal rate effect tends to decrease. As a result of comparing the results of Examples 1 and 14, the difference in the removal rate effect is small, and from an economical point of view, Example 1 is It was found that the overall effect of use of 4 was better. If the amount of the phenate repair agent is changed, the effectiveness of the agent will decrease to a certain extent. The phenate restorer made with the soaking composition of Example 14 was found to be comparatively superior. [Explanation of symbols] 1 - tank, 2 - cover, 3 - stirring unit, 31 - stirring motor, 32 - stirring shaft, 33 - Agitator blade, 331-collar, 332-semicircular agitator plate, 34-heating part, 341-counterbore hole, 342-control tray, 343-center column, 344-transmission bar, 345-stopper, 4-spray Fog unit, 41 - threaded rod, 42 - threaded ring, 43 - airbag ring, 44-Fluid Control Box

Claims

1. A phenate-based method for removing phthalate esters from soil, comprising the steps of: Producing a phenate repair agent, comprising: Biochar heated to 80-100°C and potassium ferrate at 20-30°C were mixed in a ratio of 6-12:

1. Mix in the appropriate ratio, add milling balls to it, and mix to mill. After mixing for 10 to 15 minutes and milling, the mixture of biochar and potassium ferrate was added to the biomass. A 4 to 8% spray solution was sprayed on the total mass of the mixture of charcoal and potassium ferrate, and then the mixture was sprayed for 30 min. n Stirring and milling, The spray liquid is a sodium hydroxide solution as a base liquid, and 3% sodium chloride is added to the base liquid by mass. The base solution is made of sodium hydroxide and 1.5% hydroxymethylcellulose. The thorium solution is 1 mol / L, and the spray temperature of the spray liquid is 20-30°C. After that, it is left to stand for 3 minutes, then milled and stirred again until it is completely dry. Step S1: obtaining an ethylenate repair agent; Remediating the phthalate-contaminated soil, comprising: The phenate remediation agent and the phthalate ester-contaminated soil were mixed in a weight ratio of 0.1 to 0.2:

1. and step S2 of remediating the phthalate-contaminated soil. 。

2. The biochar is an activated biochar; In the activation treatment method, biochar is added to a mixture of zinc chloride and hydroxyethyl cellulose. The biochar is then taken out and spread evenly on the mesh. The mesh was placed in a tube furnace and heated with a high-temperature mixture of CO2 and nitrogen gas at a flow rate of 100 mL / min. After 3 hours of treatment, nitrogen gas was introduced at a flow rate of 20 mL / min, and the temperature in the tubular furnace was The temperature was reduced to 25°C, and the biochar was then pickled, rinsed multiple times with deionized water, and activated. We obtained biochar that had been In the high-temperature mixed gas containing CO2 and nitrogen gas, the volume ratio of CO2 to nitrogen gas is The ratio of the biochar, zinc chloride, hydrochloric acid, and the like is 3:7, and the temperature of the high-temperature mixed gas is 500°C.

2. The composition according to claim 1, characterized in that the weight ratio of hydroxyethyl cellulose added is 12:2:

3. The method described.

3. The surface of the milling ball is coated with a heat insulating material, and the heat insulating material is a heat insulating ceramic.

2. The method according to claim 1, characterized in that the coating is 2 mm thick.

4. In step S2, an in-situ repair process is used, specifically, a phenate repair agent Spray evenly on the contaminated soil, then turn it over and spray with water to determine the moisture content of the contaminated soil. 40%. The method of claim 1, wherein the .alpha.-methyl-2-propanediol is 40%.

5. In the step S1, the equipment used to produce the phenate repair agent is a tank ( 1), a cover (2), and a tank (1) for storing biochar and potassium ferrate. A mixing unit (3) for mixing, and a spray unit (4) for controlling the spray of the spray liquid. Including, The stirring unit (3) includes a stirring motor (31), a stirring shaft (32), and a stirring blade (33). ) and a heating unit (34), and the stirring motor (31) is One end of the stirring shaft (32) is fixedly connected to the output shaft of the stirring motor (31). The stirring blade (33) has a collar (331) fitted to the stirring shaft (32) and a front A plurality of semicircular stirring plates (332) are provided along the circumferential direction on the side wall of the collar (331), , and the inner bottom surface of the tank (1) is provided with a semicircular groove that fits with the semicircular stirring plate (332). The heating portion (34) is provided with a plurality of semicircular stirring plates (332) so as to correspond one-to-one to the semicircular stirring plates (332). A number of semicircular stirring plates (332) are provided on the bottom surface of the heating section (34) so ​​as to be detachably connected to the semicircular stirring plate (332). An engagement groove is provided, The spray unit (4) comprises a threaded rod (41), a threaded ring (42) and an air a bag ring (43) and a liquid control box (44), said threaded rod One end of (41) is fixedly connected to the groove on the top surface of the cover (2), and the other end is connected to the agitator shaft (32). The other end of the threaded ring (42) is rotatably connected to the threaded rod (41). The airbag ring (43) is fitted onto the threaded rod (41) and the cover The liquid control box (44) is fixedly connected to the groove on the top surface of the liquid control box (42), and the liquid control box (44) has an annular shape. The airbag ring (43) is provided on the upper surface of the cover (2) and is connected to the airbag ring (43) via a number of hoses. The hose is connected to the top of the liquid control box (44), and gas is supplied to the liquid control box (44). 4) is provided with a one-way check valve, and the bottom of the liquid control box (44) is provided with A plurality of nozzles are provided through the cover (2), A plurality of countersunk holes (341) are provided on the outer bottom surface of the heating portion (34). A control tray (342) is provided within and rotatably connected to said control tray (341). The control tray (342) is provided with a central pillar (343) that passes through the countersunk hole (341), A winding box and a transmission bar (344) are provided on one side of the inner bottom surface of the heating section (34). One end of the transmission bar (344) is connected to a winding box, and the other end of the transmission bar (344) is connected to a winding box. The end passes through the heating section (34) and is connected to a threaded ring (42) and the inside of the heating section (34) At the bottom, the control tray (342) is attached by connecting the transmission bar (344) to the central pillar (343). A stopper is provided for rotating the tray, and the counterbore (341) and the control tray (342) are The threaded ring (42) is provided with a through hole for discharging biochar in accordance with the above. ) is fixedly connected to the collar (331) via a number of telescopic rods. The method according to claim 1 .

6. The transmission bar (344) and the central column (343) adopt a tooth transmission method. (344) is provided with transmission teeth, and the central pillar (343) is meshed with the transmission bar (344).

6. The method according to claim 5, characterized in that intermeshing tooth spaces are provided for power transmission.

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