CN111943439B - Groundwater chlorinated organic compound bioremediation device - Google Patents

Abstract

The invention relates to the field of groundwater treatment, in particular to a groundwater chlorinated organic compound bioremediation device which comprises a heat treatment remediation tank and a bioremediation tank which are connected from top to bottom; the heat treatment repair tank comprises an injection port, an extraction device, a heating device, a first stirring device and a first water tank; the bioremediation tank comprises a feed inlet, a second water tank, a second stirring device and a discharge outlet; the first water tank is connected with the second water tank through a water pumping pipeline, and a water pumping pump is arranged on the water pumping pipeline. The device for repairing the chlorinated organic-polluted underground water provided by the invention can eliminate the chlorinated organic matters to the greatest extent by using the device prepared by combining the two repairing technologies, namely the polluted underground water can reach the effect that the polluted underground water gradually changes from high concentration to medium and low concentration and finally can not be detected in the water body.

Description

Groundwater chlorinated organic compound bioremediation device

Technical Field

The invention relates to the field of groundwater treatment, in particular to a biological repair device for chlorinated organic compounds in groundwater.

Background

Chlorinated organics are high-efficiency cleaning chemicals which are widely applied to the fields of aircraft engines, metal parts, electronic elements, laundry industry and the like, and are common pollutants in groundwater environment because of groundwater environment pollution caused by disordered discharge and/or storage leakage, are not easy to degrade, have a 'three-cause' effect, and the pollution control of chlorinated organics in groundwater is widely paid attention.

Common repairing techniques for chlorinated organics include extraction treatment, heat treatment, in situ chemical oxidation/reduction, in situ bioremediation, and the like. The repair methods applicable to the chlorinated organic compounds of the groundwater with different concentrations are different, wherein the extraction treatment method and the heat treatment method are applicable to high-concentration pollution areas, and the in-situ chemical oxidation/reduction method and the in-situ bioremediation method are applicable to medium-low concentration areas. In addition, the chlorinated organic pollutants are difficult to completely remove by a single repair technology, and incomplete repair and rebound phenomenon easily occur by using a pumping treatment method and a heat treatment method; the reaction condition is higher by utilizing in-situ microorganism treatment, and the treatment period is long.

Disclosure of Invention

In view of the above problems, the present invention provides a groundwater chlorinated organic compound bioremediation device, comprising a heat treatment remediation tank and a bioremediation tank connected from top to bottom; the heat treatment repair tank comprises an injection port, an extraction device, a heating device, a first stirring device and a first water tank; the bioremediation tank comprises a feed inlet, a second water tank, a second stirring device and a discharge outlet; the first water tank is connected with the second water tank through a water pumping pipeline, and a water pumping pump is arranged on the water pumping pipeline; the feed inlet is used for throwing in the microbial preparation.

Preferably, the extraction device comprises an extraction pump and a gas storage tank; the gas storage tank is used for storing the gas pumped by the extraction pump.

Preferably, the heating device is also connected to the bioremediation tank; the heating device is also provided with a temperature sensor which can sense the temperature of the liquid in the heat treatment repair tank or the biological repair tank.

Preferably, a filter is provided on the injection port.

Preferably, a pH detector is also provided within the bioremediation tank.

Preferably, a sterilizer is arranged at the outlet; the sterilizer comprises a filter element and a sterilization material layer coated on the surface of the filter element.

Preferably, the filter element is prepared from modified polyethylene.

Preferably, the preparation method of the modified polyethylene comprises the following steps:

s1, weighing glutarimide, adding the glutarimide into DMF, and stirring until the glutarimide is dissolved to obtain a glutarimide solution; weighing 1, 2-propylene glycol and imidazole, adding the 1, 2-propylene glycol and the imidazole into DMF, and placing the DMF and the DMF in ice-water bath to stir the mixture until the mixture is uniform to obtain 1, 2-propylene glycol mixed liquor;

wherein, the mass ratio of the glutarimide to the DMF is 1:10; the mass ratio of the 1, 2-propylene glycol, the imidazole and the DMF is 10:0.1-0.2:3-5;

s2, dropwise adding the glutarimide solution into the 1, 2-propylene glycol mixed solution, maintaining the ice-water bath condition, stirring for 8-10 h, and then distilling under reduced pressure to remove the solvent to obtain an organism A; adding the organism A into an HCl solution with the concentration of 0.1mol/L, stirring to be uniform, extracting by using dichloromethane, taking an upper organic phase, and distilling under reduced pressure to remove the dichloromethane to obtain an organism B;

wherein the volume ratio of the glutarimide solution to the 1, 2-propanediol mixed solution is 1:1-2; the mass ratio of the organism A to the HCl solution is 1:8-10;

s3, adding the organism B into ethanol, stirring until the organism B is dissolved, adding o-butyl dithiocarbonate, stirring until the O-butyl dithiocarbonate is dissolved, reacting for 8-10 hours, firstly adding deionized water for washing, extracting by using dichloromethane, taking an organic phase, and distilling under reduced pressure to remove the dichloromethane to obtain an organism C;

wherein the mass ratio of the organism B, the o-butyl dithiocarbonate and the ethanol is 1:0.1-0.3:5-10;

s4, weighing the organism C, adding the organism C into N-methylpyrrolidone, adding azodiisobutyronitrile, stirring until the mixture is uniform, pouring the mixture into a reaction kettle, vacuumizing, introducing inert gas to normal pressure, introducing ethylene gas to the pressure of 100-300 MPa, heating to 40-50 ℃, reacting for 50-80 hours, precipitating by using acetone, and vacuum drying to obtain modified polyethylene;

wherein the mass ratio of the organism C, the azodiisobutyronitrile and the N-methylpyrrolidone is 1:0.05-0.2:6-8.

Preferably, the sterilization material layer is composed of the following components in parts by weight:

comprises 40 to 60 parts of modified phenolic resin, 20 to 40 parts of polypropylene resin and 10 to 15 parts of modified calcium carbonate.

Preferably, the modified phenolic resin is obtained by modifying phenolic resin by quaternized melamine-aldehyde microspheres.

Preferably, the preparation method of the quaternized melamine-aldehyde microsphere comprises the following steps:

s1, weighing formaldehyde, adding the formaldehyde into deionized water, placing the deionized water under ice-water bath, stirring the mixture until the mixture is uniform, sequentially adding melamine and tween-80, heating the mixture to 40-50 ℃, and continuously stirring the mixture for reaction for 1-3 hours to obtain melamine-formaldehyde reaction liquid;

wherein the mass ratio of melamine, tween-80, formaldehyde to deionized water is 1:0.1-0.2:2-5:5-10;

s2, pouring the melamine-formaldehyde reaction liquid into a reaction kettle, sealing, heating to 110-150 ℃, reacting for 12-18 h, cooling, filtering to obtain a solid, washing with acetone for three times, washing with deionized water for three times, and drying under reduced pressure to obtain melamine-aldehyde microspheres;

s3, weighing the melamine-aldehyde microspheres, adding the melamine-aldehyde microspheres into N, N-dimethylformamide, stirring and dispersing the microspheres until the microspheres are uniform, adding alpha-naphthylacetic acid, continuously stirring and dispersing the microspheres until the microspheres are uniform, dripping sodium hydroxide solution until the pH value is 10.0-11.0, heating the microspheres to 60-70 ℃, and stirring and reacting the microspheres for 5-8 hours to obtain carboxylated microsphere mixed solution;

wherein the mass ratio of the melamine-aldehyde microsphere, the alpha-naphthylacetic acid and the N, N-dimethylformamide is 1:0.2-0.3:5-10;

s4, heating the carboxylated microsphere mixed solution to 80-90 ℃, adding trimethyl benzyl ammonium chloride and sodium iodide, stirring and reacting for 10-12 hours, filtering and taking solid matters, washing with deionized water until the washing solution is neutral, washing with acetone for three times, and drying under reduced pressure to obtain quaternized melamine-aldehyde microspheres;

wherein, the mass ratio of the trimethyl benzyl ammonium chloride to the sodium iodide to the carboxylated microsphere mixed solution is 1:0.1-0.2: 10 to 12.

Preferably, the preparation method of the modified calcium carbonate comprises the following steps:

s1, dropwise adding an ethanol water solution with the mass concentration of 50% to pH=10.0-11.0 by using 0.1mol/L sodium hydroxide, adding metformin, and stirring until the metformin is dissolved to obtain a metformin mixed solution;

wherein the mass ratio of the metformin to the ethanol aqueous solution is 1:6-10;

s2, weighing calcium carbonate powder, adding the calcium carbonate powder into the metformin mixed solution, stirring and dispersing the mixture until the mixture is uniform, heating the mixture to 70-90 ℃, refluxing and stirring the mixture for 0.5-1 h, dropwise adding a titanate coupling agent, continuously stirring the mixture for 3-5 h, naturally cooling the mixture to room temperature, standing the mixture for 8-10 h, filtering the mixture to obtain a solid, washing the solid with acetone for three times, and drying the solid in an oven at 90-100 ℃ to obtain modified calcium carbonate;

wherein the mass ratio of the calcium carbonate powder to the titanate coupling agent to the metformin mixed solution is 1:0.05-0.1:5-8.

The beneficial effects of the invention are as follows:

1. the device for repairing the chlorinated organic-polluted groundwater provided by the invention is characterized in that the polluted groundwater is firstly treated by a heat treatment method and then treated by an in-situ microorganism treatment method, and the chlorinated organic-polluted groundwater can be removed to the greatest extent by using the device prepared by combining the two repairing technologies, namely, the effect that the polluted groundwater gradually changes from high concentration to medium and low concentration and is almost undetected in water body finally can be achieved after the polluted groundwater passes through the device provided by the invention.

The repairing device prepared by the invention has better underground water repairing property, shortens the repairing time, reduces the repairing cost, has wide application range and realizes the complete removal of chlorinated organic pollutants in the underground water.

2. The filter core material of the sterilization device is a modified polyethylene material, and the polyethylene has good chemical stability and excellent corrosion resistance, is very suitable for being used as a sewage filter core material, and is also a short plate with poor environmental stress sensitivity and thermal aging resistance. The invention prepares the modified polyethylene by using a reversible deactivation free radical polymerization method, improves the mechanical strength and the thermal aging resistance of the polyethylene, and achieves better effect. The preparation method comprises the steps of reacting glutarimide, 1, 2-propylene glycol and imidazole, synthesizing under an acidic condition to obtain a broken chain transfer polymerization reagent, and controlling the polymerization reaction of polyethylene by using the chain transfer polymerization reagent to form a chain extender between molecular chains of the finally obtained modified polyethylene, so that the modified polyethylene has excellent heat aging resistance and mechanical properties.

3. The sterilization material layer is composed of modified phenolic resin, polypropylene resin and modified calcium carbonate, wherein the phenolic resin has the advantages of relatively excellent corrosion resistance and low toxicity, the polypropylene resin has the advantages of corrosion resistance, impact resistance and water resistance, and the advantages of the polypropylene resin and the polypropylene resin are mutually combined and complemented after being combined. Specifically, melamine-aldehyde microspheres are prepared firstly, then alpha-naphthylacetic acid is added for carboxylation treatment, and trimethyl benzyl ammonium chloride is added for quaternization treatment. The melamine-aldehyde microsphere is used as a carrier, and quaternary ammonium organic salt is grafted on the surface of the carrier uniformly, so that the microsphere carrier has sterilizing property, and after the carrier is combined with phenolic resin, the sterilizing microsphere can be uniformly distributed in the resin.

4. The invention also adds modified calcium carbonate into the sterilization material, and the calcium carbonate is used as a natural antibacterial agent, has low toxicity, is safe to use, is insoluble in water and is widely used as an antibacterial inorganic substance, but has higher requirement on the pH value of liquid, and has lower sterilization property per se, thus limiting the use of the inorganic substance. According to the invention, the metformin is used for grafting modification of calcium carbonate, so that the activity of the surface of the calcium carbonate is enhanced, the adsorptivity of the calcium carbonate to fungus in liquid is enhanced, and meanwhile, the sterilization performance of the calcium carbonate is greatly enhanced, so that the modified calcium carbonate can be more suitable for being used as a sterilization material of water bodies. The modified calcium carbonate has excellent fungus adsorptivity, sterilization property and sterilization durability in a sterilization material layer obtained by combining the modified phenolic resin and the polypropylene resin, and belongs to a nontoxic and safe sterilization material.

Drawings

The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.

FIG. 1 is a schematic diagram of a groundwater chlorinated organic bioremediation device of the invention;

reference numerals: the heat treatment repair tank 1, the bioremediation tank 2, the water pumping pipe 3, the injection port 11, the extraction device 12, the heating device 13, the first stirring device 14, the first water tank 15, the feed port 21, the second water tank 22, the second stirring device 23, the discharge port 24, the water pumping pump 31, the filter 111, the extraction pump 121, the gas storage tank 122, and the sterilizer 241.

Detailed Description

The invention will be further described with reference to the following examples.

Example 1

A biological repair device for chlorinated organic compounds in groundwater comprises a heat treatment repair tank 1 and a biological repair tank 2 which are connected from top to bottom; wherein the heat treatment repair tank 1 comprises an injection port 11, an extraction device 12, a heating device 13, a first stirring device 14 and a first water tank 15; the bioremediation tank 2 comprises a feed inlet 21, a second water tank 22, a second stirring device 23 and a discharge outlet 24; the first water tank 15 is connected with the second water tank 22 through a water pumping pipeline 3, and a water pump 31 is arranged on the water pumping pipeline 3; the feed inlet 21 is used for throwing in the microbial preparation.

The extraction device 12 includes an extraction pump 121 and a gas storage tank 122; the gas storage tank 122 is used for storing the gas pumped by the pump 121.

The microbial preparation is introduced into the second water tank 22 through the feed port 21.

The heating device 13 is also connected with the bioremediation tank 2; the heating device 13 is further provided with a temperature sensor (not shown) capable of sensing the temperature of the liquid in the heat treatment repair tank 1 or the bioremediation tank 2.

The inlet 11 is provided with a filter 111.

A pH detector (not shown) is also provided in the bioremediation tank 2.

A sterilizer 241 is arranged at the outlet 24; the sterilizer 241 includes a filter cartridge and a sterilization material layer coated on the surface of the filter cartridge.

The filter element is prepared from modified polyethylene.

The preparation method of the modified polyethylene comprises the following steps:

s1, weighing glutarimide, adding the glutarimide into DMF, and stirring until the glutarimide is dissolved to obtain a glutarimide solution; weighing 1, 2-propylene glycol and imidazole, adding the 1, 2-propylene glycol and the imidazole into DMF, and placing the DMF and the DMF in ice-water bath to stir the mixture until the mixture is uniform to obtain 1, 2-propylene glycol mixed liquor;

wherein, the mass ratio of the glutarimide to the DMF is 1:10; the mass ratio of the 1, 2-propylene glycol, the imidazole and the DMF is 10:0.15:4;

s2, dropwise adding the glutarimide solution into the 1, 2-propylene glycol mixed solution, maintaining the ice-water bath condition, stirring for 8-10 h, and then distilling under reduced pressure to remove the solvent to obtain an organism A; adding the organism A into an HCl solution with the concentration of 0.1mol/L, stirring to be uniform, extracting by using dichloromethane, taking an upper organic phase, and distilling under reduced pressure to remove the dichloromethane to obtain an organism B;

wherein the volume ratio of the glutarimide solution to the 1, 2-propanediol mixed solution is 1:1.5; the mass ratio of the organism A to the HCl solution is 1:9;

s3, adding the organism B into ethanol, stirring until the organism B is dissolved, adding o-butyl dithiocarbonate, stirring until the O-butyl dithiocarbonate is dissolved, reacting for 8-10 hours, firstly adding deionized water for washing, extracting by using dichloromethane, taking an organic phase, and distilling under reduced pressure to remove the dichloromethane to obtain an organism C;

wherein the mass ratio of the organism B, the o-butyl dithiocarbonate and the ethanol is 1:0.2:7;

s4, weighing the organism C, adding the organism C into N-methylpyrrolidone, adding azodiisobutyronitrile, stirring until the mixture is uniform, pouring the mixture into a reaction kettle, vacuumizing, introducing inert gas to normal pressure, introducing ethylene gas to the pressure of 100-300 MPa, heating to 40-50 ℃, reacting for 50-80 hours, precipitating by using acetone, and vacuum drying to obtain modified polyethylene;

wherein the mass ratio of the organism C, the azodiisobutyronitrile and the N-methylpyrrolidone is 1:0.1:7.

The sterilizing material layer consists of the following components in parts by weight:

comprises 50 parts of modified phenolic resin, 30 parts of polypropylene resin and 12 parts of modified calcium carbonate.

The modified phenolic resin is obtained by modifying phenolic resin by quaternized melamine-aldehyde microspheres.

The preparation method of the quaternized melamine-aldehyde microsphere comprises the following steps:

s1, weighing formaldehyde, adding the formaldehyde into deionized water, placing the deionized water under ice-water bath, stirring the mixture until the mixture is uniform, sequentially adding melamine and tween-80, heating the mixture to 40-50 ℃, and continuously stirring the mixture for reaction for 1-3 hours to obtain melamine-formaldehyde reaction liquid;

wherein the mass ratio of melamine, tween-80, formaldehyde to deionized water is 1:0.1-0.2:2-5:5-10;

s2, pouring the melamine-formaldehyde reaction liquid into a reaction kettle, sealing, heating to 110-150 ℃, reacting for 12-18 h, cooling, filtering to obtain a solid, washing with acetone for three times, washing with deionized water for three times, and drying under reduced pressure to obtain melamine-aldehyde microspheres;

s3, weighing the melamine-aldehyde microspheres, adding the melamine-aldehyde microspheres into N, N-dimethylformamide, stirring and dispersing the microspheres until the microspheres are uniform, adding alpha-naphthylacetic acid, continuously stirring and dispersing the microspheres until the microspheres are uniform, dripping sodium hydroxide solution until the pH value is 10.0-11.0, heating the microspheres to 60-70 ℃, and stirring and reacting the microspheres for 5-8 hours to obtain carboxylated microsphere mixed solution;

wherein the mass ratio of the melamine-aldehyde microsphere, the alpha-naphthylacetic acid and the N, N-dimethylformamide is 1:0.2-0.3:5-10;

s4, heating the carboxylated microsphere mixed solution to 80-90 ℃, adding trimethyl benzyl ammonium chloride and sodium iodide, stirring and reacting for 10-12 hours, filtering and taking solid matters, washing with deionized water until the washing solution is neutral, washing with acetone for three times, and drying under reduced pressure to obtain quaternized melamine-aldehyde microspheres;

wherein, the mass ratio of the trimethyl benzyl ammonium chloride to the sodium iodide to the carboxylated microsphere mixed solution is 1:0.1-0.2: 10 to 12.

The preparation method of the modified calcium carbonate comprises the following steps:

s1, dropwise adding an ethanol water solution with the mass concentration of 50% to pH=10.0-11.0 by using 0.1mol/L sodium hydroxide, adding metformin, and stirring until the metformin is dissolved to obtain a metformin mixed solution;

wherein the mass ratio of the metformin to the ethanol aqueous solution is 1:6-10;

s2, weighing calcium carbonate powder, adding the calcium carbonate powder into the metformin mixed solution, stirring and dispersing the mixture until the mixture is uniform, heating the mixture to 70-90 ℃, refluxing and stirring the mixture for 0.5-1 h, dropwise adding a titanate coupling agent, continuously stirring the mixture for 3-5 h, naturally cooling the mixture to room temperature, standing the mixture for 8-10 h, filtering the mixture to obtain a solid, washing the solid with acetone for three times, and drying the solid in an oven at 90-100 ℃ to obtain modified calcium carbonate;

wherein the mass ratio of the calcium carbonate powder to the titanate coupling agent to the metformin mixed solution is 1:0.05-0.1:5-8.

When the repairing device is used, groundwater polluted by chlorinated organic matters is firstly introduced from the injection port 11 and enters the first water tank 15 of the heat treatment repairing tank 1, the first stirring device 14 is firstly opened, then the extraction pump 121 is opened to extract for 0.5-1 h under normal pressure, and then the heating device 13 is opened to slowly heat up to 20-50 ℃ so that chlorinated organic matters with lower boiling points in the water body can be basically extracted; and then closing the extraction pump 121, cooling the water body to room temperature, transferring the cooled water body into the second water tank 22 of the bioremediation tank 2 through the water pumping pipeline 3, then throwing a microbial preparation capable of decomposing chlorinated organic compounds into the feed inlet 21, adjusting the pH and the temperature of the water body, and starting the second stirring device 23 to carry out microbial remediation on the water body. After the microorganism is repaired, the water body is discharged through the outlet 24, and when the water body passes through the outlet 24, the sterilization treatment is performed through a sterilizer 241 arranged on the outlet 24, so that the groundwater which almost contains no chlorinated organic matters is finally obtained.

Example 2

A biological repair device for chlorinated organic compounds in groundwater comprises a heat treatment repair tank 1 and a biological repair tank 2 which are connected from top to bottom; wherein the heat treatment repair tank 1 comprises an injection port 11, an extraction device 12, a heating device 13, a first stirring device 14 and a first water tank 15; the bioremediation tank 2 comprises a feed inlet 21, a second water tank 22, a second stirring device 23 and a discharge outlet 24; the first water tank 15 is connected with the second water tank 22 through a water pumping pipeline 3, and a water pump 31 is arranged on the water pumping pipeline 3; the feed inlet 21 is used for throwing in the microbial preparation.

The extraction device 12 includes an extraction pump 121 and a gas storage tank 122; the gas storage tank 122 is used for storing the gas pumped by the pump 121.

The microbial preparation is introduced into the second water tank 22 through the feed port 21.

The heating device 13 is also connected with the bioremediation tank 2; the heating device 13 is further provided with a temperature sensor (not shown) capable of sensing the temperature of the liquid in the heat treatment repair tank 1 or the bioremediation tank 2.

The inlet 11 is provided with a filter 111.

A pH detector (not shown) is also provided in the bioremediation tank 2.

A sterilizer 241 is arranged at the outlet 24; the sterilizer 241 includes a filter cartridge and a sterilization material layer coated on the surface of the filter cartridge.

The filter element is prepared from modified polyethylene.

The preparation method of the modified polyethylene comprises the following steps:

s1, weighing glutarimide, adding the glutarimide into DMF, and stirring until the glutarimide is dissolved to obtain a glutarimide solution; weighing 1, 2-propylene glycol and imidazole, adding the 1, 2-propylene glycol and the imidazole into DMF, and placing the DMF and the DMF in ice-water bath to stir the mixture until the mixture is uniform to obtain 1, 2-propylene glycol mixed liquor;

wherein, the mass ratio of the glutarimide to the DMF is 1:10; the mass ratio of the 1, 2-propylene glycol, the imidazole and the DMF is 10:0.1:3;

s2, dropwise adding the glutarimide solution into the 1, 2-propylene glycol mixed solution, maintaining the ice-water bath condition, stirring for 8-10 h, and then distilling under reduced pressure to remove the solvent to obtain an organism A; adding the organism A into an HCl solution with the concentration of 0.1mol/L, stirring to be uniform, extracting by using dichloromethane, taking an upper organic phase, and distilling under reduced pressure to remove the dichloromethane to obtain an organism B;

wherein the volume ratio of the glutarimide solution to the 1, 2-propanediol mixed solution is 1:1; the mass ratio of the organism A to the HCl solution is 1:8;

s3, adding the organism B into ethanol, stirring until the organism B is dissolved, adding o-butyl dithiocarbonate, stirring until the O-butyl dithiocarbonate is dissolved, reacting for 8-10 hours, firstly adding deionized water for washing, extracting by using dichloromethane, taking an organic phase, and distilling under reduced pressure to remove the dichloromethane to obtain an organism C;

wherein the mass ratio of the organism B, the o-butyl dithiocarbonate and the ethanol is 1:0.1:5;

s4, weighing the organism C, adding the organism C into N-methylpyrrolidone, adding azodiisobutyronitrile, stirring until the mixture is uniform, pouring the mixture into a reaction kettle, vacuumizing, introducing inert gas to normal pressure, introducing ethylene gas to the pressure of 100-300 MPa, heating to 40-50 ℃, reacting for 50-80 hours, precipitating by using acetone, and vacuum drying to obtain modified polyethylene;

wherein the mass ratio of the organism C, the azodiisobutyronitrile and the N-methylpyrrolidone is 1:0.05:6.

The sterilizing material layer consists of the following components in parts by weight:

comprises 40 parts of modified phenolic resin, 20 parts of polypropylene resin and 10 parts of modified calcium carbonate.

The modified phenolic resin is obtained by modifying phenolic resin by quaternized melamine-aldehyde microspheres.

The preparation method of the quaternized melamine-aldehyde microsphere comprises the following steps:

s1, weighing formaldehyde, adding the formaldehyde into deionized water, placing the deionized water under ice-water bath, stirring the mixture until the mixture is uniform, sequentially adding melamine and tween-80, heating the mixture to 40-50 ℃, and continuously stirring the mixture for reaction for 1-3 hours to obtain melamine-formaldehyde reaction liquid;

wherein the mass ratio of melamine, tween-80, formaldehyde to deionized water is 1:0.1-0.2:2-5:5-10;

s2, pouring the melamine-formaldehyde reaction liquid into a reaction kettle, sealing, heating to 110-150 ℃, reacting for 12-18 h, cooling, filtering to obtain a solid, washing with acetone for three times, washing with deionized water for three times, and drying under reduced pressure to obtain melamine-aldehyde microspheres;

s3, weighing the melamine-aldehyde microspheres, adding the melamine-aldehyde microspheres into N, N-dimethylformamide, stirring and dispersing the microspheres until the microspheres are uniform, adding alpha-naphthylacetic acid, continuously stirring and dispersing the microspheres until the microspheres are uniform, dripping sodium hydroxide solution until the pH value is 10.0-11.0, heating the microspheres to 60-70 ℃, and stirring and reacting the microspheres for 5-8 hours to obtain carboxylated microsphere mixed solution;

wherein the mass ratio of the melamine-aldehyde microsphere, the alpha-naphthylacetic acid and the N, N-dimethylformamide is 1:0.2-0.3:5-10;

s4, heating the carboxylated microsphere mixed solution to 80-90 ℃, adding trimethyl benzyl ammonium chloride and sodium iodide, stirring and reacting for 10-12 hours, filtering and taking solid matters, washing with deionized water until the washing solution is neutral, washing with acetone for three times, and drying under reduced pressure to obtain quaternized melamine-aldehyde microspheres;

wherein, the mass ratio of the trimethyl benzyl ammonium chloride to the sodium iodide to the carboxylated microsphere mixed solution is 1:0.1-0.2: 10 to 12.

The preparation method of the modified calcium carbonate comprises the following steps:

s1, dropwise adding an ethanol water solution with the mass concentration of 50% to pH=10.0-11.0 by using 0.1mol/L sodium hydroxide, adding metformin, and stirring until the metformin is dissolved to obtain a metformin mixed solution;

wherein the mass ratio of the metformin to the ethanol aqueous solution is 1:6-10;

s2, weighing calcium carbonate powder, adding the calcium carbonate powder into the metformin mixed solution, stirring and dispersing the mixture until the mixture is uniform, heating the mixture to 70-90 ℃, refluxing and stirring the mixture for 0.5-1 h, dropwise adding a titanate coupling agent, continuously stirring the mixture for 3-5 h, naturally cooling the mixture to room temperature, standing the mixture for 8-10 h, filtering the mixture to obtain a solid, washing the solid with acetone for three times, and drying the solid in an oven at 90-100 ℃ to obtain modified calcium carbonate;

wherein the mass ratio of the calcium carbonate powder to the titanate coupling agent to the metformin mixed solution is 1:0.05-0.1:5-8.

When the repairing device is used, groundwater polluted by chlorinated organic matters is firstly introduced from the injection port 11 and enters the first water tank 15 of the heat treatment repairing tank 1, the first stirring device 14 is firstly opened, then the extraction pump 121 is opened to extract for 0.5-1 h under normal pressure, and then the heating device 13 is opened to slowly heat up to 20-50 ℃ so that chlorinated organic matters with lower boiling points in the water body can be basically extracted; and then closing the extraction pump 121, cooling the water body to room temperature, transferring the cooled water body into the second water tank 22 of the bioremediation tank 2 through the water pumping pipeline 3, then throwing a microbial preparation capable of decomposing chlorinated organic compounds into the feed inlet 21, adjusting the pH and the temperature of the water body, and starting the second stirring device 23 to carry out microbial remediation on the water body. After the microorganism is repaired, the water body is discharged through the outlet 24, and when the water body passes through the outlet 24, the sterilization treatment is performed through a sterilizer 241 arranged on the outlet 24, so that the groundwater which almost contains no chlorinated organic matters is finally obtained.

Example 3

A biological repair device for chlorinated organic compounds in groundwater comprises a heat treatment repair tank 1 and a biological repair tank 2 which are connected from top to bottom; wherein the heat treatment repair tank 1 comprises an injection port 11, an extraction device 12, a heating device 13, a first stirring device 14 and a first water tank 15; the bioremediation tank 2 comprises a feed inlet 21, a second water tank 22, a second stirring device 23 and a discharge outlet 24; the first water tank 15 is connected with the second water tank 22 through a water pumping pipeline 3, and a water pump 31 is arranged on the water pumping pipeline 3; the feed inlet 21 is used for throwing in the microbial preparation.

The extraction device 12 includes an extraction pump 121 and a gas storage tank 122; the gas storage tank 122 is used for storing the gas pumped by the pump 121.

The microbial preparation is introduced into the second water tank 22 through the feed port 21.

The heating device 13 is also connected with the bioremediation tank 2; the heating device 13 is further provided with a temperature sensor (not shown) capable of sensing the temperature of the liquid in the heat treatment repair tank 1 or the bioremediation tank 2.

The inlet 11 is provided with a filter 111.

A pH detector (not shown) is also provided in the bioremediation tank 2.

A sterilizer 241 is arranged at the outlet 24; the sterilizer 241 includes a filter cartridge and a sterilization material layer coated on the surface of the filter cartridge.

The filter element is prepared from modified polyethylene.

The preparation method of the modified polyethylene comprises the following steps:

s1, weighing glutarimide, adding the glutarimide into DMF, and stirring until the glutarimide is dissolved to obtain a glutarimide solution; weighing 1, 2-propylene glycol and imidazole, adding the 1, 2-propylene glycol and the imidazole into DMF, and placing the DMF and the DMF in ice-water bath to stir the mixture until the mixture is uniform to obtain 1, 2-propylene glycol mixed liquor;

wherein, the mass ratio of the glutarimide to the DMF is 1:10; the mass ratio of the 1, 2-propylene glycol, the imidazole and the DMF is 10:0.2:5;

s2, dropwise adding the glutarimide solution into the 1, 2-propylene glycol mixed solution, maintaining the ice-water bath condition, stirring for 8-10 h, and then distilling under reduced pressure to remove the solvent to obtain an organism A; adding the organism A into an HCl solution with the concentration of 0.1mol/L, stirring to be uniform, extracting by using dichloromethane, taking an upper organic phase, and distilling under reduced pressure to remove the dichloromethane to obtain an organism B;

wherein the volume ratio of the glutarimide solution to the 1, 2-propanediol mixed solution is 1:2; the mass ratio of the organism A to the HCl solution is 1:10;

s3, adding the organism B into ethanol, stirring until the organism B is dissolved, adding o-butyl dithiocarbonate, stirring until the O-butyl dithiocarbonate is dissolved, reacting for 8-10 hours, firstly adding deionized water for washing, extracting by using dichloromethane, taking an organic phase, and distilling under reduced pressure to remove the dichloromethane to obtain an organism C;

wherein the mass ratio of the organism B, the o-butyl dithiocarbonate and the ethanol is 1:0.3:10;

s4, weighing the organism C, adding the organism C into N-methylpyrrolidone, adding azodiisobutyronitrile, stirring until the mixture is uniform, pouring the mixture into a reaction kettle, vacuumizing, introducing inert gas to normal pressure, introducing ethylene gas to the pressure of 100-300 MPa, heating to 40-50 ℃, reacting for 50-80 hours, precipitating by using acetone, and vacuum drying to obtain modified polyethylene;

wherein the mass ratio of the organism C, the azodiisobutyronitrile and the N-methylpyrrolidone is 1:0.2:8.

The sterilizing material layer consists of the following components in parts by weight:

comprises 60 parts of modified phenolic resin, 40 parts of polypropylene resin and 15 parts of modified calcium carbonate.

The modified phenolic resin is obtained by modifying phenolic resin by quaternized melamine-aldehyde microspheres.

The preparation method of the quaternized melamine-aldehyde microsphere comprises the following steps:

s1, weighing formaldehyde, adding the formaldehyde into deionized water, placing the deionized water under ice-water bath, stirring the mixture until the mixture is uniform, sequentially adding melamine and tween-80, heating the mixture to 40-50 ℃, and continuously stirring the mixture for reaction for 1-3 hours to obtain melamine-formaldehyde reaction liquid;

wherein the mass ratio of melamine, tween-80, formaldehyde to deionized water is 1:0.1-0.2:2-5:5-10;

s2, pouring the melamine-formaldehyde reaction liquid into a reaction kettle, sealing, heating to 110-150 ℃, reacting for 12-18 h, cooling, filtering to obtain a solid, washing with acetone for three times, washing with deionized water for three times, and drying under reduced pressure to obtain melamine-aldehyde microspheres;

s3, weighing the melamine-aldehyde microspheres, adding the melamine-aldehyde microspheres into N, N-dimethylformamide, stirring and dispersing the microspheres until the microspheres are uniform, adding alpha-naphthylacetic acid, continuously stirring and dispersing the microspheres until the microspheres are uniform, dripping sodium hydroxide solution until the pH value is 10.0-11.0, heating the microspheres to 60-70 ℃, and stirring and reacting the microspheres for 5-8 hours to obtain carboxylated microsphere mixed solution;

wherein the mass ratio of the melamine-aldehyde microsphere, the alpha-naphthylacetic acid and the N, N-dimethylformamide is 1:0.2-0.3:5-10;

s4, heating the carboxylated microsphere mixed solution to 80-90 ℃, adding trimethyl benzyl ammonium chloride and sodium iodide, stirring and reacting for 10-12 hours, filtering and taking solid matters, washing with deionized water until the washing solution is neutral, washing with acetone for three times, and drying under reduced pressure to obtain quaternized melamine-aldehyde microspheres;

wherein, the mass ratio of the trimethyl benzyl ammonium chloride to the sodium iodide to the carboxylated microsphere mixed solution is 1:0.1-0.2: 10 to 12.

The preparation method of the modified calcium carbonate comprises the following steps:

s1, dropwise adding an ethanol water solution with the mass concentration of 50% to pH=10.0-11.0 by using 0.1mol/L sodium hydroxide, adding metformin, and stirring until the metformin is dissolved to obtain a metformin mixed solution;

wherein the mass ratio of the metformin to the ethanol aqueous solution is 1:6-10;

s2, weighing calcium carbonate powder, adding the calcium carbonate powder into the metformin mixed solution, stirring and dispersing the mixture until the mixture is uniform, heating the mixture to 70-90 ℃, refluxing and stirring the mixture for 0.5-1 h, dropwise adding a titanate coupling agent, continuously stirring the mixture for 3-5 h, naturally cooling the mixture to room temperature, standing the mixture for 8-10 h, filtering the mixture to obtain a solid, washing the solid with acetone for three times, and drying the solid in an oven at 90-100 ℃ to obtain modified calcium carbonate;

wherein the mass ratio of the calcium carbonate powder to the titanate coupling agent to the metformin mixed solution is 1:0.05-0.1:5-8.

When the repairing device is used, groundwater polluted by chlorinated organic matters is firstly introduced from the injection port 11 and enters the first water tank 15 of the heat treatment repairing tank 1, the first stirring device 14 is firstly opened, then the extraction pump 121 is opened to extract for 0.5-1 h under normal pressure, and then the heating device 13 is opened to slowly heat up to 20-50 ℃ so that chlorinated organic matters with lower boiling points in the water body can be basically extracted; and then closing the extraction pump 121, cooling the water body to room temperature, transferring the cooled water body into the second water tank 22 of the bioremediation tank 2 through the water pumping pipeline 3, then throwing a microbial preparation capable of decomposing chlorinated organic compounds into the feed inlet 21, adjusting the pH and the temperature of the water body, and starting the second stirring device 23 to carry out microbial remediation on the water body. After the microorganism is repaired, the water body is discharged through the outlet 24, and when the water body passes through the outlet 24, the sterilization treatment is performed through a sterilizer 241 arranged on the outlet 24, so that the groundwater which almost contains no chlorinated organic matters is finally obtained.

Comparative example

A biological repair device for chlorinated organic compounds in groundwater comprises a biological repair tank; wherein, the bioremediation tank is provided with a feed inlet and an outlet;

a sterilizer is arranged at the outlet; the sterilizer comprises a filter element and a sterilization material layer coated on the surface of the filter element.

The filter element is made of polyethylene materials.

The sterilizing material layer consists of the following components in parts by weight:

comprises 40 to 60 parts of phenolic resin, 20 to 40 parts of polypropylene resin and 10 to 15 parts of calcium carbonate.

For a clearer explanation of the present invention, the filter cartridges and the sterilization material layers prepared in examples 1 to 3 and comparative examples of the present invention were subjected to performance test, and the results are shown in tables 1 and 2:

wherein, the aging conditions are as follows: heat treated in an oven at 150 ℃ for one week (7 days).

Table 1 performance test of filter elements

	Example 1	Example 2	Example 3	Comparative example
					Tensile Strength/MPa	18.9	18.5	18.7	8.3
Elongation at break/%	412	406	411	112
					Tensile Strength Change Rate/%	+12.3	+12.5	+12.1	+21.6
Elongation at break change after aging/％	-10.3	-10.8	-10.7	-37.3

As can be seen from Table 1, the filter elements prepared in examples 1 to 3 of the present invention are far greater in tensile strength and elongation at break than those of the comparative examples, and the change rates of tensile strength and elongation at break after aging are also far smaller than those of the comparative examples, which indicates that the filter elements prepared in examples 1 to 3 of the present invention have relatively excellent mechanical properties and thermal aging resistance.

TABLE 2 Performance test of sterilizing Material layers

As can be seen from Table 2, the sterilization rates of the sterilization material layers prepared in the embodiments 1 to 3 of the present invention on Escherichia coli and Staphylococcus aureus can reach 97% and 98% respectively when the sterilization material layers are used for the first time, and the sterilization rate can still reach more than 85% after the sterilization material layers are used repeatedly for 100 times, which indicates that the sterilization material layers prepared in the embodiments 1 to 3 of the present invention have excellent sterilization effects and long-term usability.

Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (6)

1. The device for biologically repairing the chlorinated organic compounds in the groundwater is characterized by comprising a heat treatment repairing tank and a biological repairing tank which are connected from top to bottom; the heat treatment repair tank comprises an injection port, an extraction device, a heating device, a first stirring device and a first water tank; the bioremediation tank comprises a feed inlet, a second water tank, a second stirring device and a discharge outlet; the first water tank is connected with the second water tank through a water pumping pipeline, and a water pumping pump is arranged on the water pumping pipeline; the feed inlet is used for feeding a microbial preparation;

a sterilizer is arranged at the outlet; the sterilizer comprises a filter element and a sterilization material layer coated on the surface of the filter element;

the filter element is prepared from modified polyethylene; the preparation method of the modified polyethylene comprises the following steps:

s1, weighing glutarimide, adding the glutarimide into DMF, and stirring until the glutarimide is dissolved to obtain a glutarimide solution; weighing 1, 2-propylene glycol and imidazole, adding the 1, 2-propylene glycol and the imidazole into DMF, and placing the DMF and the DMF in ice-water bath to stir the mixture until the mixture is uniform to obtain 1, 2-propylene glycol mixed liquor;

wherein, the mass ratio of the glutarimide to the DMF is 1:10; the mass ratio of the 1, 2-propylene glycol, the imidazole and the DMF is 10:0.1-0.2:3-5;

s2, dropwise adding the glutarimide solution into the 1, 2-propylene glycol mixed solution, maintaining the ice-water bath condition, stirring for 8-10 hours, and then distilling under reduced pressure to remove the solvent to obtain an organism A; adding the organism A into an HCl solution with the concentration of 0.1mol/L, stirring to be uniform, extracting by using dichloromethane, taking an upper organic phase, and distilling under reduced pressure to remove the dichloromethane to obtain an organism B;

wherein the volume ratio of the glutarimide solution to the 1, 2-propanediol mixed solution is 1:1-2; the mass ratio of the organism A to the HCl solution is 1:8-10;

s3, adding the organism B into ethanol, stirring until the organism B is dissolved, adding o-butyl dithiocarbonate, stirring until the O-butyl dithiocarbonate is dissolved, reacting for 8-10 hours, firstly adding deionized water for washing, extracting by using dichloromethane, taking an organic phase, and distilling under reduced pressure to remove the dichloromethane to obtain an organism C;

wherein the mass ratio of the organism B, the o-butyl dithiocarbonate and the ethanol is 1:0.1-0.3:5-10;

s4, weighing the organism C, adding the organism C into N-methylpyrrolidone, adding azodiisobutyronitrile, stirring until the mixture is uniform, pouring the mixture into a reaction kettle, vacuumizing, introducing inert gas to normal pressure, introducing ethylene gas to the pressure of 100-300 MPa, heating to 40-50 ℃, reacting for 50-80 hours, precipitating by using acetone, and vacuum drying to obtain modified polyethylene;

wherein the mass ratio of the organism C, the azodiisobutyronitrile and the N-methylpyrrolidone is 1:0.05-0.2:6-8;

the sterilizing material layer consists of the following components in parts by weight:

the modified phenolic resin comprises 40-60 parts of modified phenolic resin, 20-40 parts of polypropylene resin and 10-15 parts of modified calcium carbonate;

the modified phenolic resin is obtained by modifying phenolic resin by quaternized melamine-aldehyde microspheres;

the preparation method of the quaternized melamine-aldehyde microsphere comprises the following steps:

s1, weighing formaldehyde, adding the formaldehyde into deionized water, placing the deionized water under ice-water bath, stirring the mixture until the mixture is uniform, sequentially adding melamine and tween-80, heating the mixture to 40-50 ℃, and continuously stirring the mixture for reaction for 1-3 hours to obtain melamine-formaldehyde reaction liquid;

wherein the mass ratio of melamine, tween-80, formaldehyde to deionized water is 1:0.1-0.2:2-5:5-10;

s2, pouring the melamine-formaldehyde reaction liquid into a reaction kettle, sealing, heating to 110-150 ℃, reacting for 12-18 h, cooling, filtering to obtain a solid, washing with acetone for three times, washing with deionized water for three times, and drying under reduced pressure to obtain melamine-aldehyde microspheres;

s3, weighing the melamine-aldehyde microspheres, adding the melamine-aldehyde microspheres into N, N-dimethylformamide, stirring and dispersing the microspheres until the microspheres are uniform, adding alpha-naphthylacetic acid, continuously stirring and dispersing the microspheres until the microspheres are uniform, dropwise adding a sodium hydroxide solution until the pH value is 10.0-11.0, heating the microspheres to 60-70 ℃, and stirring and reacting the microspheres for 5-8 hours to obtain carboxylated microsphere mixed solution;

wherein the mass ratio of the melamine-aldehyde microsphere, the alpha-naphthylacetic acid and the N, N-dimethylformamide is 1:0.2-0.3:5-10;

s4, heating the carboxylated microsphere mixed solution to 80-90 ℃, adding trimethyl benzyl ammonium chloride and sodium iodide, stirring and reacting for 10-12 hours, filtering and taking solid matters, washing with deionized water until the washing solution is neutral, washing with acetone for three times, and drying under reduced pressure to obtain quaternized melamine-aldehyde microspheres;

wherein, the mass ratio of the trimethyl benzyl ammonium chloride to the sodium iodide to the carboxylated microsphere mixed solution is 1:0.1-0.2: 10-12.

2. The groundwater chlorinated organic bioremediation device of claim 1, wherein the extraction device comprises an extraction pump and a gas storage tank; the gas storage tank is used for storing the gas pumped by the extraction pump.

3. A groundwater chlorinated organic bioremediation device in accordance with claim 1, wherein the heating device is further coupled to the bioremediation tank; the heating device is also provided with a temperature sensor which can sense the temperature of the liquid in the heat treatment repair tank or the biological repair tank.

4. The groundwater chlorinated organic bioremediation device of claim 1, wherein a filter is disposed on the injection port.

5. The groundwater chlorinated organic biological repair device of claim 1, wherein a pH detector is further disposed in the biological repair tank.

6. The groundwater chlorinated organic compound bioremediation device according to claim 1, wherein the preparation method of the modified calcium carbonate is as follows:

s1, dropwise adding an ethanol water solution with the mass concentration of 50% to pH=10.0-11.0 by using 0.1mol/L sodium hydroxide, adding metformin, and stirring until the metformin is dissolved to obtain a metformin mixed solution;

wherein the mass ratio of the metformin to the ethanol aqueous solution is 1:6-10;

s2, weighing calcium carbonate powder, adding the calcium carbonate powder into the metformin mixed solution, stirring and dispersing the calcium carbonate powder to be uniform, heating the mixture to 70-90 ℃, refluxing and stirring the mixture for 0.5-1 h, dropwise adding a titanate coupling agent, continuously stirring the mixture for 3-5 h, naturally cooling the mixture to room temperature, standing the mixture for 8-10 h, filtering the mixture to obtain a solid, washing the solid with acetone for three times, and drying the solid in an oven at 90-100 ℃ to obtain modified calcium carbonate;

wherein the mass ratio of the calcium carbonate powder to the titanate coupling agent to the metformin mixed solution is 1:0.05-0.1:5-8.

Images