Preparation method and in-situ regeneration method of water body micromolecule purification module

Abstract

The invention discloses a preparation method and in-situ regeneration method of a water body micromolecule purification module, which comprises the following steps: firstly, carrying out physical-chemical modification curing by using an inorganic multi-purpose material and biomass charcoal as main raw materials to prepare a heterogeneous pore purification material, and then curing by using a hydrothermal technology to obtain the water body micromolecule purification module. A particle filler is prepared by combining a wet method and a rolling ball method; and thirdly, the particle filler is transferred into the purification module, the purification module is assembled with a net-shaped electrode device, sodium chloride and sodium hydroxide are utilized under the assistance of direct current, the regeneration speed can be increased, regeneration can be achieved without removing the filler, and the problem that independent activated carbon or biomass charcoal cannot be continuously used is solved.

Description

Technical Field

[0001] The invention belongs to the technical field of environmental protection and relates to a preparation method of a water body small molecule purification module and an in-situ regeneration method. Technical Background

[0002] The aqueous solution contains total nitrogen (nitrate), borate, chromate, vanadate and fluoride ions, as well as inorganic or organic small molecules such as dimethyl isoborneol and geosmin. These molecules or anions with a molecular weight of less than 300 Da affect the water quality and the final quality of the extracted chemicals. For example, the presence of organic small molecules such as dimethyl isoborneol, geosmin or inorganic salts such as borates, chromates, molybdates and vanadates in drinking water causes the water quality to exceed the national drinking water standard, and the presence of similar small molecules in industrial production process water leads to problems such as product quality degradation. Common purification and removal methods are ion exchange and adsorption. The ion exchange method uses ion exchange resins to selectively exchange and adsorb small molecules to achieve the purpose of removal. In many cases, ion exchange resins will fail due to organic small molecules, and the organic matter of the polymer resin will wear out to form similar microplastics and other pollutants, which are more harmful.

[0003] The main methods currently used are adsorption, chemical precipitation, biological denitrification, chemical denitrification, etc.

[0004] The attachment method is to adsorb the target object through materials with special adsorption properties, such as certain metal oxides. Some natural materials can also be used for adsorption after modification, such as modified biochar and activated carbon. However, the adsorption method cannot be regenerated and recycled in situ in many cases. Chemical precipitation, such as using calcium chloride as a precipitant, removes fluoride ions, vanadium, chromium, etc. by forming calcium salt precipitation. However, due to the effect of chemical equilibrium, the reactants and products of the reaction must maintain a certain ratio and the target pollutant must have a certain content. Among them, there is also a chemical reduction precipitation method, which uses a reducing agent (such as ferrous sulfate, etc.) to reduce the hexavalent chromium in the chromate to trivalent chromium. The trivalent chromium will form chromium hydroxide precipitation under alkaline conditions. It is difficult to adsorb or chemically precipitate nitrates, so the biological denitrification method is used, that is, denitrifying bacteria are used to reduce nitrates to nitrogen gas under anoxic conditions. This method has the characteristics of high efficiency and low consumption, and is considered to be the most promising method for deep denitrification of water quality. However, there are also disadvantages, mainly easy to cause secondary pollution (organic matter such as methanol needs to be added, and excessive organic matter needs to be treated later), which is not suitable for small-scale, decentralized treatment. There are also chemical denitrification methods, such as active metal denitrification and catalytic denitrification, which use certain reducing agents (such as active metal iron, aluminum or hydrogen as a reducing agent) to reduce nitrates in groundwater to nitrogen gas or ammonium ions. However, the selectivity and activity of chemical denitrification in the reaction process are greatly affected by mass transfer factors, which limits the practicality of this method.

[0005] In addition, there is also the microalgae treatment method. During the microalgae cultivation process, wastewater containing nitrate ions is introduced into the cultivation system to provide a nitrogen source for the microalgae. After the cultivation is completed, at least part of the microalgae culture solution needs to be separated from the solid and liquid, and the scope of application is limited. The membrane separation technology can be used to purify some small molecule pollutants, but pretreatment may be required before treatment to meet the requirements of membrane separation; and the equipment investment and operation and maintenance require a large investment, including nanofiltration and reverse osmosis membranes or electrodialysis technologies. The low water yield is also a major disadvantage. Therefore, the current existing technology is still insufficient in the deep purification of water bodies and aqueous solutions of inorganic anions and small organic molecules, as well as easy in-situ regeneration and high yield. Summary of the invention

[0006] The present invention provides a method for preparing a water body small molecule purification module and an in-situ regeneration method, which can accelerate the regeneration rate and achieve regeneration without removing the filler, thus overcoming the problem that a single activated carbon or biomass charcoal cannot be used continuously.

[0007] The technical solution of the present invention includes two parts: one part is the preparation and solidification of heterogeneous porous purification materials into particle fillers, and the other part is the method of assembling and applying purification modules and in-situ regeneration. The two parts are optimized to construct a modular unit that is easy to use.

[0008] The main raw materials for preparing the heterogeneous porous purification material are porous composite oxides such as silicates and aluminates or inorganic substances such as oxides and biomass carbonized materials; the steps are as follows:

[0009] (1) After washing and drying the selected inorganic material such as bentonite or zeolite powder, a divalent metal cation magnesium or iron salt and a trivalent metal cation aluminum or iron in a molar ratio of 3:1 are added, the pH is adjusted to 10-12 and the aging is carried out for 1-12 hours, and the powder is obtained after filtering.

[0010] (2) The biomass carbon is made of corn cobs, peach gum or hazelnut shells, etc., which are washed, dried and crushed to a size of less than 200 mesh and then carbonized with microwaves at a microwave power of more than 300 W for 1-3 hours;

[0011] (3) The mechanical mixing is mainly performed by a planetary ball mill or a reamer crusher to form a heterogeneous porous structure, and the particle size of the powder is below 50 microns (under a 200 mesh sieve) to form a heterogeneous porous purification material.

[0012] The steps of curing the particle filler of the heterogeneous pore purification material are as follows:

[0013] (4) Adding sodium alginate as a binder to the obtained heterogeneous pore purification material and adding water to mix into a slurry, the slurry is then sprayed into a calcium chloride solution by a syringe pump for wet ball making, the particle size of the spheres is 2-50 mm, filtered and dried, and the spheres with a particle size of less than 20 mm are used as mother balls, and the spheres with a particle size of more than 20 mm are used as spare balls.

[0014] (5) Add part of the mother balls below 20 mm to the disc granulator, and then add part of the inorganic powder and biochar powder, as well as peach gum, starch, sodium silicate and other binders, and roll them to make balls, and screen out spheres with a diameter of 30-60 mm.

[0015] (6) Add the obtained 30-60 mm spheres to a hydrothermal kettle, perform hydrothermal curing under the promotion of sodium carbonate, add 2-10% starch, control the sodium carbonate concentration to about 5%, keep the temperature at 80-300°C, heat for 1-6 hours, and cool and dry to obtain solidified particles. The liquid part can be concentrated into a liquid with a COD equivalent of 300,000 and recovered as a carbon source.

[0016] The steps for assembling the purification module are:

[0017] (7) First, the upper and lower packages are made of meshes less than 10-15 mm, and a corrosion-resistant and stable material is used as a frame to construct a unit frame. The module is provided with a titanium mesh electrode of a size matching the frame as a regeneration electrode, and is also provided with an inlet and an outlet of the solution equipped with a distributor.

[0018] (8) A 20-30 cm quartz sand support layer is set at the bottom of the frame, leaving 0.3-3.5 meters for the adsorbent filling height. When the unit is in use, the adsorbent is loaded into 80% of the frame, leaving 20% ​​expansion space for process control such as steam-water backwashing and regeneration flushing.

[0019] The steps for using the module and the in-situ regeneration method are:

[0020] (9) The purification process is to let untreated water enter the purification unit, control the residence contact time, ensure that the effluent meets the requirements, and stop the water intake and start regeneration when the effluent does not meet the requirements.

[0021] (10) The in-situ regeneration does not require the removal of the adsorbent, but requires the addition of a mixed solution of sodium chloride and sodium hydroxide at 1-10% of the regeneration agent. To enhance the regeneration speed, a DC power supply can be connected, and the current can be controlled at 10-300A.

[0022] (11) Calculate the concentration of the target ions in the regeneration solution. When the amount of ions entering the solution is more than 95% of the adsorption amount, the power can be stopped. After backwashing and flushing, the pH can be reused after it reaches 6-8. The size of the purification unit can be determined according to the amount of water. It can be used as a single module or assembled into a large adsorption purification system with multiple units, and can be automatically controlled with the help of online devices.

[0023] The present invention is suitable for organic small molecules and water bodies and solutions containing oxygen anions. It proposes to use stable inorganic substances such as inorganic silicates and aluminates to mechanically mix and chemically modify solid carbon prepared from organic biomass. In addition to the inorganic pores and pores of the carbon material itself, the gap pores between inorganic and organic are mainly constructed to prepare asymmetric heterogeneous pores with partial hydrophilicity and partial hydrophobicity, which can well adsorb and screen organic small molecules and inorganic ions, and construct particles of a certain size, which are installed in modules of appropriate sizes. Considering the need for rapid regeneration, an electrode plate is set in the module, and enhanced in-situ regeneration can be performed when saturated. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a process flow chart of the present invention.

[0025] Figure 2 The structural infrared spectrum (FTIR) of the heterogeneous pore purification material of Example 1 is

[0026] Figure 3 The structural infrared spectrum (FTIR) of the heterogeneous pore purification material of Example 2

[0027] Figure 4 The structural infrared spectrum (FTIR) of the heterogeneous pore purification material of Example 3 is

[0028] Figure 5 The structural infrared spectrum (FTIR) of the heterogeneous pore purification material of Example 4 is DETAILED DESCRIPTION

[0029] The present invention is further described below in conjunction with implementation examples and drawings.

[0030] Example 1: Purification of dimethyl isoborneol and geosmin in water

[0031] Take the dried corn cobs and wash the impurities with water. Take 10% sodium hydroxide solution, soak the corn cobs for 2 hours, rinse the corn cobs with plenty of water to remove excess sodium hydroxide. Dry the corn cobs and place them in a microwave oven for pyrolysis to prepare biochar. Purge with carbon dioxide for 20 minutes before starting heating to remove oxygen in the reaction chamber. Heat in a 0.3kw microwave oven for 1 hour, cool to room temperature, take out, and crush to less than 200 mesh to obtain prefabricated carbon.

[0032] The molar ratio of magnesium oxide to aluminum oxide is 3:1, and a 10% solution of total salt concentration is prepared and added to the bentonite powder, with a liquid-solid ratio of 1:1. The pH value is 12 using a sodium hydroxide bar, and the mixture is stirred for 20 minutes and aged for 12 hours. The powder obtained is filtered to obtain an inorganic powder.

[0033] Take part of the inorganic powder and mix it with prefabricated carbon and 2% alginate aqueous solution in a mass ratio of 1:1:2. Mechanically ball mill for 40 minutes, filter the powder through a 200-mesh sieve, add water to prepare a solution with a solid content of less than 10%, and inject it into a 10% calcium chloride aqueous solution with a syringe pump after mixing to make mother balls. The mother balls are dried at room temperature for use. Using a disc granulator and mother balls, add inorganic powder, prefabricated carbon, peach gum, starch and humic acid in the above mass ratio. Inorganic powder: prefabricated carbon: peach gum: starch: humic acid

[0034] =1:1:0.2:0.02:0.5 for disc granulation. During the process, it is necessary to spray a proper amount of 2% sodium silicate aqueous solution or water to obtain spherical particles with a particle size of 30 cm to 60 cm.

[0035] Add spherical particles to a hydrothermal kettle, then add 0.2% sodium carbonate aqueous solution, hydrothermal temperature 180 ° C, time 24h, rinse the sample with deionized water to pH 6-8, electrically heated and air-dried to obtain particle filler for use. The liquid in the kettle is evaporated and concentrated to a COD of 420,000 units, and the carbon source is recovered.

[0036] To examine the structure of the heterogeneous pore purification material, Fourier transform infrared spectroscopy (FTIR) analysis was performed to examine its functional groups and chemical structure. Figure 2 FTIR, A is the mother ball, B is the expanded ball. It can be seen that the two are basically the same, mainly with inorganic functional groups and carbon-containing organic functional groups. The pore size measured by BET is mainly distributed between 1.8-2.5nm.

[0037] The test device is to prepare the filter module into a filter bed with an area of ​​40×40cm and a height of 1.8 meters. The inlet and outlet are arranged in the up and down direction, and the distributor and titanium mesh electrode are installed. The obtained spherical or quasi-spherical particle filler is loaded into the filter module. The filler is added by using 24-80cm quartz sand as a cushion layer at the bottom in advance, with a height of 0.2-0.3 meters. Use 50-60cm diameter small balls to fill 0.2 meters, and 30-40cm small balls to fill 0.3 meters for standby use.

[0038] A reservoir water contaminated with dimethyl isoborneol and geosmin was used as a test, and raw water was added using a peristaltic pump to ensure that the contact time was greater than 10 minutes. The regeneration process was carried out using a mixture of 5% sodium hydroxide and 5% sodium chloride, and the regeneration time was 30 minutes. The data of four cycles without power supply and with a current of 10A for 15 minutes are shown in Table 1.

[0039] Table 1: Results of purification and regeneration of dimethyl isoborneol and geosmin in water

[0040]

[0041]

[0042] It can be seen that the spherical particles prepared by the heterogeneous porous purification material can effectively purify dimethyl isoborneol (molecular weight 182) and geosmin (molecular weight 168), and the use of 5% sodium hydroxide can be regenerated without power supply, but the regeneration time can be shortened after the 10A current is passed, which has an efficiency advantage.

[0043] Example 2: Purification and recycling of nitrate and total nitrogen

[0044] Regarding the purification of nitrates and total nitrogen in water bodies, ammonia nitrogen and other substances will be oxidized to nitrates in the presence of oxygen, and the removal rate of total nitrogen is limited. In the process of nitrate purification, it is ensured that it is not reduced to ammonia nitrogen, and total nitrogen will also be effectively removed.

[0045] This method is basically the same as the process of Example 1. In addition to corn cobs, biomass can be selected as raw materials. The specific method is as follows: the activated sludge is dried at 60°C and then placed in a microwave oven for pyrolysis to prepare biochar. Before heating, carbon dioxide and nitrogen are swept for 15 minutes to remove oxygen in the reaction chamber. After heating for 1 hour in a 0.3kw microwave oven, it is cooled to room temperature and taken out, and crushed to 38.5 microns (under a 200 mesh sieve) to obtain prefabricated carbon.

[0046] The preparation of inorganic powder is the same as that in Example 1, and the specific raw material ratio can be adjusted. The molar ratio of magnesium oxide to aluminum oxide is 3:1, respectively, and a 20% solution of total salt concentration is added to the natural zeolite powder, and the liquid-solid ratio is 1:5. The pH value is 12 using sodium hydroxide, and the mixture is stirred for 20 minutes and aged for 1 hour. The powder obtained by filtering is the inorganic powder.

[0047] Take the inorganic powder and prefabricated carbon and 5% alginate aqueous solution in a mass ratio of 1:1:1, mechanically ball mill for 60 minutes, and then pass the powder through a 200-mesh sieve to take the sieve. Add water to prepare a slurry with a solid content of less than 20%, and after mixing, use a syringe pump to inject it into a 5% calcium chloride aqueous solution to make mother balls.

[0048] Disc granulation mechanism particle filler: add the above-mentioned mother ball into the disc granulator, turn on the disc granulator and control the speed below 100rpm. Add inorganic powder according to the following ratio: prefabricated carbon: peach gum: starch: humic acid = 1:1:0.02:0.1:0.2 to make disc granulation mechanism balls. During the process, it is necessary to spray 2% sodium silicate aqueous solution or water appropriately to control the spherical particles with a particle size of 20cm to 60cm.

[0049] The spherical particles were added to the hydrothermal reactor, and then 1% sodium carbonate aqueous solution was added. The hydrothermal temperature was 150°C for 12 hours. The sample was rinsed with deionized water until the pH was 6-8, and then electrically heated and dried with air to obtain the particle filler for use. In order to determine the surface functional groups of the heterogeneous pore purification material, the structural infrared spectroscopy (FTIR) was characterized, and the results are shown in Figure 3 .Install the filter module, and the test process is the same as Example 1; take the groundwater with ammonia nitrogen of 22 and total nitrogen of 23.3 mg / l for testing. In the regeneration solution of 3% sodium hydroxide and 10% sodium chloride, the current of power regeneration is controlled between 280-300A. The results and regeneration conditions are shown in Table 2.

[0050] Table 2: Results of purification and regeneration of nitrate and total nitrogen in water

[0051]

[0052]

[0053] Example 3: Purification and recycling of chromate and vanadate ions

[0054] For the purification process of sewage containing chromate and vanadate ions, the main process is basically the same as that in Example 1; the raw material is hazelnut shell as the biomass raw material,

[0055] The specific method is as follows: dried hazelnut shells are placed in a microwave oven for pyrolysis to prepare biochar. Before heating, nitrogen is purged for 15 minutes to remove oxygen from the reaction chamber. After heating in a 0.3kw microwave oven for 0.5 hours, the shells are cooled to room temperature and taken out, crushed to 38.5 microns (under a 200 mesh sieve), and prefabricated carbon is obtained.

[0056] The preparation of inorganic powder is the same as that in Example 1, and the specific raw material ratio can be adjusted. The molar ratio of magnesium oxide and aluminum oxide is 3:1 respectively. A 2% solution of total salt concentration is added to natural zeolite powder and bentonite (1:1), and the liquid-solid ratio is 1:2. The pH value is 10 using sodium hydroxide bar, and the mixture is stirred for 30 minutes and aged for 6 hours. The powder obtained by filtering is the inorganic powder.

[0057] Take the inorganic powder and prefabricated carbon and 1% alginate aqueous solution in a mass ratio of 1:1:1, mechanically ball mill for 120 minutes, pass the powder through a 200-mesh sieve, and take the sieve. Add water to prepare a slurry with a solid content of less than 15%, and after mixing, use a syringe pump to inject it into a 5% calcium chloride aqueous solution to make mother balls.

[0058] Disc granulation mechanism particle filler: add the above-mentioned mother ball into the disc granulator, turn on the disc granulator and control the speed below 100rpm. Add inorganic powder according to the following ratio: prefabricated carbon: peach gum: starch: humic acid = 1:1:0.1:0.1:0.3 to make disc granulation mechanism balls. During the process, it is necessary to spray 5% sodium silicate aqueous solution or water appropriately to control the spherical particles with a particle size of 20cm to 60cm.

[0059] The spherical particles were added to a hydrothermal reactor, and then a 5% sodium carbonate aqueous solution was added. The hydrothermal temperature was 200°C for 8 hours. The sample was rinsed with deionized water until the pH was 6-7, and then dried by electric heating. In order to determine the surface functional groups of the heterogeneous pore purification material, the structural infrared spectroscopy (FTIR) was characterized. The results are shown in Figure 4 .

[0060] The filter module was installed and the test process was the same as in Example 1. Wastewater from a certain place was tested with a chromate content of 11.5 mg / L and a vanadate content of 12.2 mg / L. The current for power-on regeneration was controlled between 100-120A. The results and regeneration conditions are shown in Table 3.

[0061] Table 3: Results of purification and regeneration of nitrate and total nitrogen in water

[0062] project chromate Vanadate Turbidity pH Remark Water Intake 22mg / l 23.3mg / l 3.1 6 Regeneration 20min Water 0.1mg / l 0.2mg / l 1.2 6.4 Regeneration 20min 1 regeneration cycle 0.1mg / l 0.2mg / l 1.3 6.4 Regeneration 20min 2 regeneration cycles 0.2mg / l 0.1mg / l 1.2 6.4 Regeneration 30min 3 regeneration cycles 0.1mg / l 0.2mg / l 1.2 6.4 Regeneration 30min 4 regeneration cycles 0.2mg / l 0.2mg / l 1.2 7.0 Regeneration 30min Power on regeneration 1 0.1mg / l 0.2mg / l 1.2 6.7 Regeneration 15min Power on Regeneration 2 0.1mg / l 0.2mg / l 1.2 6.8 Regeneration 15min Power on regeneration 3 0.2mg / l 0.1mg / l 1.2 6.9 Regeneration 15min Power on regeneration 4 0.1mg / l 0.2mg / l 1.2 7.1 Regeneration 15min

[0063] Example 4: Purification and recycling of fluoride ions and

[0064] For the purification process of groundwater and sewage containing fluoride ions, the main process is basically the same as Example 1; the raw material is peach gum as the biomass raw material, and the peach gum exuded from the trunk of the peach tree is taken as the raw material. Dilute hydrochloric acid and phosphoric acid are added during the cleaning process for enhanced cleaning.

[0065] The specific method is as follows: peach gum exuded from the trunk of peach tree is used as raw material, and dilute hydrochloric acid and phosphoric acid are added during the cleaning process for enhanced cleaning. After drying, it is placed in a microwave oven for pyrolysis to prepare biochar. Before starting heating, nitrogen is purged for 15 minutes to remove oxygen in the reaction chamber. After heating in a 0.3kw microwave oven for 1 hour, it is cooled to room temperature, taken out, and crushed under a 200-mesh sieve to obtain prefabricated carbon.

[0066] The preparation of inorganic powder is the same as that in Example 1, and the specific raw material ratio can be adjusted. The molar ratio of magnesium oxide and aluminum oxide is 3:1 respectively. A 5% solution of total salt concentration is added to natural zeolite powder and diatomaceous earth (1:1), and the liquid-solid ratio is 2:1. The pH is 11 using sodium hydroxide bars, and the mixture is stirred for 30 minutes and aged for 8 hours. The powder obtained by filtering is an inorganic powder.

[0067] Take the inorganic powder and prefabricated carbon and 3% alginate aqueous solution in a mass ratio of 2:1:1, mechanically ball mill for 120 minutes, and then pass the powder through a 200-mesh sieve to take the sieve. Add water to prepare a slurry with a solid content of 8%, and after mixing, use a syringe pump to inject it into a 6% calcium chloride aqueous solution to make mother balls.

[0068] Disc granulation mechanism particle filler: add the above-mentioned mother ball into the disc granulator, turn on the disc granulator and control the speed below 100rpm. Add inorganic powder according to the following ratio: prefabricated carbon: peach gum: starch: humic acid = 1:1:0.2:0.4:0.5 to make disc granulation mechanism balls. During the process, it is necessary to spray 3% sodium silicate aqueous solution or water appropriately to control the spherical particles with a particle size of 20cm to 60cm.

[0069] Hydrothermal curing: add spherical particles into a hydrothermal kettle, then add a mixed solution of 6% sodium carbonate and 2% starch, hydrothermal temperature 200℃, time 8h, rinse the sample with deionized water to pH 6-7, electrically heat and blow dry the particle filler for use. Concentrate the liquid to a COD of 300,000 units, and recover the carbon source.

[0070] In order to determine the surface functional groups of the heterogeneous pore purification material, the structural infrared spectroscopy (FTIR) characterization was carried out, and the results are shown in Figure 5 .

[0071] Table 4: Results of purification and regeneration of nitrate and total nitrogen in water

[0072] project Fluoride ion Turbidity pH Remark Water Intake 8.7mg / l 1.1 8.1 Regeneration 20min Water 0.6mg / l 0.3 8.4 Regeneration 20min 1 regeneration cycle 0.8mg / l 1.3 7.1 Regeneration 20min 2 regeneration cycles 0.7mg / l 1.3 6.9 Regeneration 30min 3 regeneration cycles 0.5mg / l 1.3 7.4 Regeneration 30min Power on regeneration 1 0.6mg / l 1.3 7.4 Regeneration 15min Power on Regeneration 2 0.1mg / l 1.3 7.4 Regeneration 15min Power on regeneration 3 0.2mg / l 1.3 7.4 Regeneration 15min

[0073] Example 5: Purification and recycling of borate ions

[0074] The particle filler and test module of Example 4 were tested by the same method using reservoir water containing 2.8 mg / L of borate, and the results are shown in Table 5.

[0075] Table 2: Results of borate purification and regeneration in water

[0076] project Borate Turbidity pH Remark Water Intake 2.8mg / l 2.1 7.5 Regeneration 20min Water 0.6mg / l 0.3 8.0 Regeneration 20min 1 regeneration cycle 0.8mg / l 1.3 8.0 Regeneration 20min 2 regeneration cycles 0.7mg / l 1.3 8.0 Regeneration 30min Power on regeneration 1 0.6mg / l 0.3 8.0 Regeneration 15min Power on Regeneration 2 0.8mg / l 1.3 8.0 Regeneration 15min

Claims

1. A method for preparing a water body small molecule purification module and an in-situ regeneration method, characterized in that: It includes two parts: one part is the preparation and solidification of heterogeneous porous purification materials into particle fillers, and the other part is the assembly and application of purification modules and the method of in-situ regeneration; The main raw materials for preparing the heterogeneous porous purification material are porous composite oxides such as silicates and aluminates or inorganic substances such as oxides and biomass carbonized materials; the steps are as follows: (1) washing and drying the selected inorganic material such as bentonite or zeolite powder, adding a divalent metal cation magnesium or iron salt and a trivalent metal cation aluminum or iron in a molar ratio of 3:1, adjusting the pH to 10-12 and aging for 1-12 hours, filtering to obtain a powder; (2) The biomass carbon is made of corn cobs, peach gum or hazelnut shells, etc., which are washed, dried and crushed to a size of less than 200 mesh and then carbonized with microwaves at a microwave power of more than 300 W for 1-3 hours; (3) Mechanically mixing to form a heterogeneous porous structure, wherein the particle size of the powder is less than 50 microns and the heterogeneous porous purification material; The steps of curing the particle filler of the heterogeneous pore purification material are as follows: (4) Adding a binder of sodium alginate to the obtained heterogeneous pore purification material and adding water to mix into a slurry, and using a syringe pump to spray into a calcium chloride solution for wet balling, the ball size is 2-50 mm particles, filtered and dried, and divided into 20 mm or less as mother balls and 20 mm or more; (5) adding part of the mother balls less than 20 mm to the disc granulator, and then adding part of the inorganic powder and biochar powder, as well as peach gum, starch, sodium silicate and other binders, rolling and balling, and screening out spheres with a diameter of 30-60 mm; (6) adding the obtained 30-60 mm spheres into a hydrothermal kettle, performing hydrothermal curing under the promotion of sodium carbonate, adding 2-10% starch, controlling the sodium carbonate concentration to about 5%, the temperature to 80-300° C., curing for 1-6 hours, cooling and drying to obtain cured particles; The steps for assembling the purification module are: (7) First, the upper and lower packaging is performed by using a mesh of less than 10-15 mm, and a corrosion-resistant and stable material is used as a frame to construct a unit frame; the module is provided with a titanium mesh electrode of a size matching the frame as a regeneration electrode, and is also provided with an inlet and an outlet of the solution equipped with a distributor; (8) A 20-30 cm quartz sand support layer is set at the bottom of the frame, leaving 0.3-3.5 meters for the adsorbent filling height. When the unit is in use, the adsorbent is loaded into 80% of the frame, leaving 20% ​​expansion space for process control such as steam-water backwashing and regeneration flushing; The steps of module use and in-situ regeneration method are: (9) The purification process is to let untreated water enter the purification unit, control the residence contact time, ensure that the effluent meets the requirements, and stop the water intake and start regeneration when the effluent does not meet the requirements; (10) The in-situ regeneration described above does not require the removal of the adsorbent, but requires the addition of a mixed solution of sodium chloride and sodium hydroxide at 1-10% of the regeneration agent; (11) Calculate the concentration of the target ions in the regeneration solution. When the amount of ions entering the solution is more than 95% of the adsorption amount, stop the power supply, perform backwashing and flushing, and reuse after the pH reaches 6-8.

2. The method for preparing a water body small molecule purification module and an in-situ regeneration method according to claim 1, characterized in that: In step (3), the mechanical mixing mainly utilizes a planetary ball mill or a reamer crusher.

3. The method for preparing a water body small molecule purification module and an in-situ regeneration method according to claim 1, characterized in that: In step (6), the liquid portion can be concentrated into a liquid with a COD equivalent of 300,000 and recovered as a carbon source.

4. The method for preparing a water body small molecule purification module and an in-situ regeneration method according to claim 1, characterized in that: In step (10), a DC power supply can be connected to enhance the in-situ regeneration speed, and the current is controlled at 10-300A.

5. The method for preparing a water body small molecule purification module and an in-situ regeneration method according to claim 1, characterized in that: In step (11), the size of the purification unit is determined according to the amount of water, and it can be used as a single module, or multiple units can be assembled and stacked to form a large adsorption purification system, and automatically controlled with the help of an online device.

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