CN113000585A - Composite catalytic oxidation degradation method and device for organochlorine pesticide contaminated soil - Google Patents
Composite catalytic oxidation degradation method and device for organochlorine pesticide contaminated soil Download PDFInfo
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- CN113000585A CN113000585A CN202110137156.4A CN202110137156A CN113000585A CN 113000585 A CN113000585 A CN 113000585A CN 202110137156 A CN202110137156 A CN 202110137156A CN 113000585 A CN113000585 A CN 113000585A
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- 239000002689 soil Substances 0.000 title claims abstract description 194
- 239000003993 organochlorine pesticide Substances 0.000 title claims abstract description 56
- 230000003647 oxidation Effects 0.000 title claims abstract description 55
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- 239000002351 wastewater Substances 0.000 claims abstract description 71
- 238000003795 desorption Methods 0.000 claims abstract description 64
- 238000005067 remediation Methods 0.000 claims abstract description 23
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 85
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000001514 detection method Methods 0.000 claims description 21
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 16
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/06—Reclamation of contaminated soil thermally
- B09C1/065—Reclamation of contaminated soil thermally by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
- B09C1/105—Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2101/00—Agricultural use
Abstract
The invention discloses a composite catalytic oxidation degradation method and a composite catalytic oxidation degradation device for organochlorine pesticide contaminated soil, which relate to the technical field of soil remediation and comprise the following steps of S1: soil pretreatment, S2: soil leaching, S3: wastewater treatment, S4: wet soil treatment, S5: according to the invention, most of organochlorine pesticides in soil are quickly removed by leaching, the organochlorine pesticide residue is quickly reduced, the residual organochlorine pesticide content in wet soil is removed by thermal desorption, the removal rate of the organochlorine pesticides residual in soil is high, the organochlorine pesticides in wastewater are quickly degraded by catalytic oxidation of the leached wastewater, and the wastewater is purified for recycling, so that the method is more environment-friendly and energy-saving.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a composite catalytic oxidation degradation method and a composite catalytic oxidation degradation device for organochlorine pesticide contaminated soil.
Background
With the 'two-in-three' of the city, after pesticide chemical enterprises in the urban area or suburb are closed and moved, a large number of pesticide chemical polluted sites to be repaired urgently are generated. Because the fields generally have the characteristics of long production history, complex pollution components, high soil viscosity and the like, and the characteristics of large quantity, wide range, dense peripheral sensitive receptors and the like, compared with other industrial pollution fields, the fields have larger dangers and higher risks, seriously threaten human living health and environmental safety, and become a great soil environment problem to be solved urgently at present. The development of rapid and high-flux pesticide pollution site high-efficiency treatment equipment is urgently needed, the development of the repair industry is promoted, the soil resources are protected, the ecological environment is improved, and the people can live at ease.
Because China is generally in the starting stage in the field of polluted site remediation, compared with the approximately 40-year history of polluted site remediation in developed countries such as America, Western Europe and the like, China is far behind European and American countries in the aspect of research and development of polluted site remediation technical equipment and is far from being adapted to urgent needs of the market in the field of polluted site remediation in China. Developed countries start early, the technology is mature, the equipment stability is high, but the equipment introduction cost is high; the research and development of domestic similar equipment are just started, the technical foundation is weak, the engineering application experience is lacked, the problems that the equipment performance cannot meet the requirements and the failure rate is high generally exist, so that the removal rate is low through a single technology and the ideal effect cannot be achieved, and therefore a safe and reliable method and a device for degrading the soil polluted by the organic chlorine pesticide are needed.
Disclosure of Invention
In order to solve the technical problem, the invention provides a composite catalytic oxidation degradation method of organochlorine pesticide polluted soil.
The technical scheme of the invention is as follows: a composite catalytic oxidation degradation method for organochlorine pesticide contaminated soil comprises the following steps:
s1: soil pretreatment: loosening and crushing polluted soil by using a land turner, and screening stones, plastics and branches in the soil;
s2: soil leaching: shoveling the soil into a leaching device by using a soil remediation vehicle, leaching the soil, and then performing solid-liquid separation to obtain wet soil and wastewater;
s3: wastewater treatment: transferring the obtained wastewater to a photocatalysis box, adjusting the pH value of the wastewater to 6.5-7.5, using a nickel net loaded with titanium dioxide as a photocatalyst, controlling the wavelength of ultraviolet light to be 240-256nm, controlling the photocatalytic reaction time of the wastewater to be 1.5-2h, carrying out electromagnetic stirring during the photocatalytic reaction, controlling the stirring speed to be 80r/min and the electromagnetic power to be 100W, introducing the wastewater into an ultrasonic oxidation box, controlling the sound intensity to be 80-100W/cm2The rated power is 3KW, the pH value of the wastewater is adjusted to 7-8 after the wastewater is subjected to oxidative degradation by ultrasonic waves, and organochlorine pesticides in the wastewater are sampled and detected, and the wastewater is recycled as leaching water after the detection is qualified;
s4: wet soil treatment: transferring the wet soil obtained in the step S2 to a thermal desorption device for thermal desorption treatment, wherein the heating mode adopts microwave heating, the heating temperature is 30 ℃, the heating time is 10min, collecting evaporated water vapor, then performing the step S2 of wastewater treatment, transferring the soil subjected to thermal desorption treatment to a bioremediation agent mixing device, spraying and stirring a bioremediation agent, and returning the soil subjected to mixed remediation agent to the field, wherein the mass ratio of the bioremediation agent to the soil is 1: 100;
s5: detection and evaluation: sampling detection is carried out on the soil after thermal desorption treatment, parameters of wastewater treatment and wet soil treatment are timely adjusted according to the content of the organochlorine pesticide in the organochlorine pesticide polluted soil, and the organochlorine pesticide content in the soil finally returned to the field is guaranteed to reach the standard.
Further, the bioremediation agent in S4 is composed of the following components in parts by weight: 1-3 parts of chitosan, 80-200 parts of bentonite, 10-25 parts of green algae, 0.5-2 parts of citric acid, 2-9 parts of shell powder, 5-15 parts of flammulina velutipes mushroom bran, 40-80 parts of plant ash, 10-20 parts of rice bran, 5-15 parts of tea seed shells, 20-80 parts of cow dung, 25-60 parts of palm tree sawdust, 0.001-0.02 part of complex enzyme preparation and 0.005-0.048 part of complex microbial agent.
Further, the compound microbial agent in the bioremediation agent comprises the following components in parts by weight: 1-4 parts of alternate mucor fungus powder, 2-3 parts of bacillus megaterium powder, 4-5 parts of pseudomonas flexuralis powder, 2-5 parts of bacillus subtilis powder, 3-7 parts of sulfate reducing bacteria powder, 1-2 parts of corynebacterium couchrum powder, 3-4 parts of trichoderma powder, 1.5-3 parts of penicillium powder and 6-7 parts of lactic acid bacteria powder.
Further, the complex enzyme preparation in the bioremediation agent consists of aldehyde dehydrogenase, catalase and nitroreductase according to the mass ratio of 1:2: 2.
Further, a compound catalytic oxidation degradation device of organochlorine pesticide contaminated soil, including locomotive, couple one, couple two, turn over the quick-witted, drip washing device, photocatalysis case, ultrasonic oxidation case, thermal desorption device, bioremediation agent mixing arrangement, carriage, electromagnetic stirring device, pulp extractor, suction pump, turn over the quick-witted and pass through couple one with the rear swing joint of locomotive, the carriage is through couple two swing joint at the machine rear that turns over, the drip washing device is located the carriage head, the below at the drip washing device is fixed to the photocatalysis case, electromagnetic stirring device fixes in the photocatalysis case below, ultrasonic oxidation case fixed connection is on the right side of photocatalysis case, and the water inlet of ultrasonic oxidation case passes through pulp extractor and photocatalysis case communicate with each other, the delivery port of the water inlet of ultrasonic oxidation case passes through the suction pump with the drip washing device communicates with each other, the right side at the drip washing device is fixed to thermal desorption device, bioremediation agent mixing arrangement fixed connection is on thermal desorption device's right side, the drip washing device includes drench washing water tank, drip washing shower nozzle, conveyer belt one, drench washing case, drip washing case the place ahead is equipped with the shovel soil chain that transports soil to drip washing case, it sets up to drench washing water tank drench washing case's top conveyer belt one rotates to be connected in the drip washing case, and the surface of conveyer belt adopts the industry filter cloth, the inner wall at drip washing shower nozzle installation drip washing roof portion, and communicates with the drip washing water tank, carries out the normal position restoration through integrated device to polluting soil, reduces the transportation link, saves soil repair cost.
Furthermore, the soil turning machine comprises a vehicle body, a soil pushing device, a scattering device and a screen, wherein the soil pushing device is installed at the bottom in front of the vehicle body, the scattering device is rotatably installed above the soil pushing device, and the screen is installed behind the soil pushing device, so that sundries in soil can be effectively removed.
Furthermore, the photocatalysis case includes nickel net, ultraviolet lamp, the nickel net has two, and two nickel nets fixed mounting are inside the photocatalysis case, ultraviolet lamp has four, respectively fixed mounting is in four side inner walls of photocatalysis case department, degrades organic pesticide through photocatalysis.
Furthermore, the ultrasonic oxidation box comprises a partition plate and two ultrasonic generators, wherein the partition plate is transversely fixed inside the ultrasonic oxidation box, the two ultrasonic generators are respectively fixed on the inner walls of the upper side and the lower side of the ultrasonic oxidation box, and the organic pesticide is correspondingly and rapidly degraded through ultrasonic cavitation.
Further, the thermal desorption device comprises a second conveyor belt, a thermal desorption box and a microwave generator, wherein the microwave generator is fixed at the bottom of the thermal desorption box, the second conveyor belt is transversely installed in the middle of the thermal desorption box, and residual pesticides in the wet soil are removed through thermal desorption.
Further, bioremediation agent mixing arrangement includes that remediation agent adds device and mixing arrangement, remediation agent adds the top that the device was fixed at bioremediation agent mixing arrangement, mixing arrangement rotates and installs in remediation agent adds the device below, increases the self degradation ability of soil.
The invention has the beneficial effects that:
according to the invention, most of organochlorine pesticides in the soil are quickly removed by leaching, the organochlorine pesticide residue is quickly reduced, the residual organochlorine pesticide content in the wet soil is removed by thermal desorption, and the removal rate of the organochlorine pesticides residual in the soil is high.
According to the invention, the organic chlorine pesticide in the wastewater is rapidly degraded by carrying out catalytic oxidation on the leached wastewater, and the wastewater is purified for recycling, so that the method is more environment-friendly and energy-saving.
Drawings
FIG. 1 is a schematic structural diagram of the composite catalytic oxidative degradation apparatus of the present invention.
FIG. 2 is a schematic view of the structure of the photocatalytic tank of the present invention.
FIG. 3 is a schematic view of the structure of the ultrasonic oxidation tank of the present invention.
Fig. 4 is a schematic structural view of the thermal desorption apparatus of the present invention.
FIG. 5 is a schematic view of the construction of the bioremediation agent mixing device of the present invention.
Wherein, 1-vehicle head, 2-first hook, 3-second hook, 4-ground turner, 5-leaching device, 6-photocatalysis box, 7-ultrasonic oxidation box, 8-thermal desorption device, 9-bioremediation agent mixing device, 10-vehicle, 11-electromagnetic stirring device, 12-pulp extractor, 13-water pump, 51-leaching water tank, 52-leaching spray head, 53-first conveyor belt, 54-leaching box, 55-shovel chain, 41-vehicle body, 42-bulldozer device, 43-scattering device, 44-screen, 61-nickel screen, 62-ultraviolet lamp, 71-clapboard, 72-ultrasonic generator, 81-second conveyor belt, 82-thermal desorption box, 83-microwave generator, 91-repair agent adding device, 92-mixing device.
Detailed Description
Example 1:
a composite catalytic oxidation degradation method for organochlorine pesticide contaminated soil comprises the following steps:
s1: soil pretreatment: loosening and crushing the polluted soil by using a land turner 4, and screening stones, plastics and branches in the soil;
s2: soil leaching: shoveling the soil into a leaching device 5 by using a soil remediation vehicle, leaching the soil, and then performing solid-liquid separation to obtain wet soil and wastewater;
S3：wastewater treatment: transferring the obtained wastewater to a photocatalytic box 6, adjusting the pH value of the wastewater to 6.5, using a nickel mesh 61 loaded with titanium dioxide as a photocatalyst, the wavelength of ultraviolet rays is 240nm, the photocatalytic reaction time of the wastewater is 1.5h, stirring the wastewater with electromagnetic stirring during photocatalysis at a stirring speed of 80r/min and an electromagnetic power of 100W, introducing the wastewater into an ultrasonic oxidation box 7, and adjusting the sound intensity to 80W/cm2The rated power is 3KW, the pH value of the wastewater is adjusted to 7 after the wastewater is subjected to oxidative degradation by ultrasonic waves, organochlorine pesticides in the wastewater are sampled and detected, and the wastewater is recycled as water for drip washing after the detection is confirmed to be qualified;
s4: wet soil treatment: transferring the wet soil obtained by S2 to a thermal desorption device 8 for thermal desorption treatment, wherein the heating mode adopts microwave heating, the heating temperature is 30 ℃, the heating time is 10min, the waste water treatment link of S2 is carried out after the evaporation water vapor is collected, the soil subjected to thermal desorption treatment is transferred to a bioremediation agent mixing device 9, a bioremediation agent is sprayed and stirred, and the bioremediation agent consists of the following components in parts by weight: 1 part of chitosan, 80 parts of bentonite, 10 parts of green algae, 0.5 part of citric acid, 2 parts of shell powder, 5 parts of flammulina velutipes fungus chaff, 40 parts of plant ash, 10 parts of rice bran, 5 parts of tea seed shells, 20 parts of cow dung, 25 parts of palm wood dust, 0.001 part of complex enzyme preparation and 0.005 part of complex microbial agent; the composite microbial agent in the bioremediation agent comprises the following components in parts by weight: 1 part of alternate mucor fungus powder, 2 parts of bacillus megaterium powder, 4 parts of pseudomonas flexuralensis powder, 2 parts of bacillus subtilis powder, 3 parts of sulfate reducing bacteria powder, 1 part of corynebacterium couchsii powder, 3 parts of trichoderma powder, 1.5 parts of penicillium powder and 6 parts of lactic acid bacteria powder; the composite enzyme preparation in the bioremediation agent consists of aldehyde dehydrogenase, catalase and nitroreductase according to the mass ratio of 1:2: 2; the mass ratio of the bioremediation agent to the soil is 1:100, and then the soil mixed with the bioremediation agent is returned to the field;
s5: detection and evaluation: sampling detection is carried out on the soil after thermal desorption treatment, parameters of wastewater treatment and wet soil treatment are timely adjusted according to the content of the organochlorine pesticide in the organochlorine pesticide polluted soil, and the organochlorine pesticide content in the soil finally returned to the field is guaranteed to reach the standard.
Example 2:
a composite catalytic oxidation degradation method for organochlorine pesticide contaminated soil comprises the following steps:
s1: soil pretreatment: loosening and crushing the polluted soil by using a land turner 4, and screening stones, plastics and branches in the soil;
s2: soil leaching: shoveling the soil into a leaching device 5 by using a soil remediation vehicle, leaching the soil, and then performing solid-liquid separation to obtain wet soil and wastewater;
s3: wastewater treatment: transferring the obtained wastewater to a photocatalytic box 6, adjusting the pH value of the wastewater to 7, using a nickel mesh 61 loaded with titanium dioxide as a photocatalyst, controlling the wavelength of ultraviolet light to be 250nm, controlling the photocatalytic reaction time of the wastewater to be 1.8h, carrying out electromagnetic stirring during the photocatalytic reaction, controlling the stirring speed to be 80r/min and the electromagnetic power to be 100W, introducing the wastewater into an ultrasonic oxidation box 7, and controlling the sound intensity to be 90W/cm2The rated power is 3KW, the pH value of the wastewater is adjusted to 7.5 after the wastewater is subjected to oxidative degradation by ultrasonic waves, and organochlorine pesticides in the wastewater are sampled and detected, and the wastewater is recycled as leaching water after the detection is qualified;
s4: wet soil treatment: transferring the wet soil obtained by S2 to a thermal desorption device 8 for thermal desorption treatment, wherein the heating mode adopts microwave heating, the heating temperature is 30 ℃, the heating time is 10min, the waste water treatment link of S2 is carried out after the evaporation water vapor is collected, the soil subjected to thermal desorption treatment is transferred to a bioremediation agent mixing device 9, a bioremediation agent is sprayed and stirred, and the bioremediation agent consists of the following components in parts by weight: 2 parts of chitosan, 100 parts of bentonite, 15 parts of green algae, 1 part of citric acid, 5 parts of shell powder, 10 parts of needle mushroom bran, 50 parts of plant ash, 15 parts of rice bran, 10 parts of tea seed shells, 50 parts of cow dung, 50 parts of palm sawdust, 0.01 part of a complex enzyme preparation and 0.03 part of a complex microbial agent; the composite microbial agent in the bioremediation agent comprises the following components in parts by weight: 3 parts of alternate mucor fungus powder, 2.5 parts of bacillus megaterium powder, 4.5 parts of pseudomonas flexuosus powder, 3 parts of bacillus subtilis powder, 5 parts of sulfate reducing bacteria powder, 1.5 parts of corynebacterium parvum powder, 3.5 parts of trichoderma powder, 2 parts of penicillium powder and 6.5 parts of lactic acid bacteria powder; the composite enzyme preparation in the bioremediation agent consists of aldehyde dehydrogenase, catalase and nitroreductase according to the mass ratio of 1:2: 2; the mass ratio of the bioremediation agent to the soil is 1:100, and then the soil mixed with the bioremediation agent is returned to the field;
s5: detection and evaluation: sampling detection is carried out on the soil after thermal desorption treatment, parameters of wastewater treatment and wet soil treatment are timely adjusted according to the content of the organochlorine pesticide in the organochlorine pesticide polluted soil, and the organochlorine pesticide content in the soil finally returned to the field is guaranteed to reach the standard.
Example 3:
a composite catalytic oxidation degradation method for organochlorine pesticide contaminated soil comprises the following steps:
s1: soil pretreatment: loosening and crushing the polluted soil by using a land turner 4, and screening stones, plastics and branches in the soil;
s2: soil leaching: shoveling the soil into a leaching device 5 by using a soil remediation vehicle, leaching the soil, and then performing solid-liquid separation to obtain wet soil and wastewater;
s3: wastewater treatment: transferring the obtained wastewater to a photocatalytic box 6, adjusting the pH value of the wastewater to 7.5, using a titanium dioxide-loaded nickel mesh 61 as a photocatalyst, controlling the wavelength of ultraviolet light to be 256nm, controlling the photocatalytic reaction time of the wastewater to be 2h, carrying out electromagnetic stirring during the photocatalytic reaction, controlling the stirring speed to be 80r/min and the electromagnetic power to be 100W, introducing the wastewater into an ultrasonic oxidation box 7, and controlling the sound intensity to be 100W/cm2The rated power is 3KW, the pH value of the wastewater is adjusted to 8 after the wastewater is subjected to oxidative degradation by ultrasonic waves, organochlorine pesticides in the wastewater are sampled and detected, and the wastewater is recycled as water for drip washing after the detection is confirmed to be qualified;
s4: wet soil treatment: transferring the wet soil obtained by S2 to a thermal desorption device 8 for thermal desorption treatment, wherein the heating mode adopts microwave heating, the heating temperature is 30 ℃, the heating time is 10min, the waste water treatment link of S2 is carried out after the evaporation water vapor is collected, the soil subjected to thermal desorption treatment is transferred to a bioremediation agent mixing device 9, a bioremediation agent is sprayed and stirred, and the bioremediation agent consists of the following components in parts by weight: 3 parts of chitosan, 200 parts of bentonite, 25 parts of green algae, 2 parts of citric acid, 9 parts of shell powder, 15 parts of needle mushroom fungus chaff, 80 parts of plant ash, 20 parts of rice bran, 15 parts of tea seed shells, 80 parts of cow dung, 60 parts of palm wood dust, 0.02 part of a complex enzyme preparation and 0.048 part of a complex microbial agent; the composite microbial agent in the bioremediation agent comprises the following components in parts by weight: 4 parts of alternate mucor fungus powder, 3 parts of bacillus megaterium powder, 5 parts of pseudomonas flexuralis powder, 5 parts of bacillus subtilis powder, 7 parts of sulfate reducing bacteria powder, 2 parts of corynebacterium couchslensis powder, 4 parts of trichoderma powder, 3 parts of penicillium powder and 7 parts of lactic acid bacteria powder; the composite enzyme preparation in the bioremediation agent consists of aldehyde dehydrogenase, catalase and nitroreductase according to the mass ratio of 1:2: 2; the mass ratio of the bioremediation agent to the soil is 1:100, and then the soil mixed with the bioremediation agent is returned to the field;
s5: detection and evaluation: sampling detection is carried out on the soil after thermal desorption treatment, parameters of wastewater treatment and wet soil treatment are timely adjusted according to the content of the organochlorine pesticide in the organochlorine pesticide polluted soil, and the organochlorine pesticide content in the soil finally returned to the field is guaranteed to reach the standard.
Compared with examples 1-3, the data parameters of example 3 are the highest for organochlorine pesticide removal in soil and the best for soil self-remediation.
Example 4:
a composite catalytic oxidation degradation method for organochlorine pesticide contaminated soil comprises the following steps:
s1: soil pretreatment: loosening and crushing the polluted soil by using a land turner 4, and screening stones, plastics and branches in the soil;
s2: soil leaching: shoveling the soil into a leaching device 5 by using a soil remediation vehicle, leaching the soil, and then performing solid-liquid separation to obtain wet soil and wastewater;
s3: wastewater treatment: transferring the obtained wastewater to a photocatalytic tank 6, adjusting the pH value of the wastewater to 7.5, and using the wastewater loaded with titanium dioxideThe nickel screen 61 is used as photocatalyst, the wavelength of ultraviolet is 256nm, the photocatalytic reaction time of the wastewater is 2h, the electromagnetic stirring is carried out during the photocatalytic reaction, the stirring speed is 80r/min, the electromagnetic power is 100W, then the wastewater is led into an ultrasonic oxidation box 7, the sound intensity is 100W/cm2The rated power is 3KW, the pH value of the wastewater is adjusted to 8 after the wastewater is subjected to oxidative degradation by ultrasonic waves, organochlorine pesticides in the wastewater are sampled and detected, and the wastewater is recycled as water for drip washing after the detection is confirmed to be qualified;
s4: wet soil treatment: transferring the wet soil obtained by S2 to a thermal desorption device 8 for thermal desorption treatment, wherein the heating mode adopts microwave heating, the heating temperature is 30 ℃, the heating time is 10min, the waste water treatment link of S2 is carried out after the evaporation water vapor is collected, the soil subjected to thermal desorption treatment is transferred to a bioremediation agent mixing device 9, a bioremediation agent is sprayed and stirred, and the bioremediation agent consists of the following components in parts by weight: 3 parts of chitosan, 200 parts of bentonite, 25 parts of green algae, 2 parts of citric acid, 9 parts of shell powder, 15 parts of needle mushroom fungus chaff, 80 parts of plant ash, 20 parts of rice bran, 15 parts of tea seed shells, 80 parts of cow dung, 60 parts of palm wood dust, 0.02 part of a complex enzyme preparation and 0.048 part of a complex microbial agent; the composite microbial agent in the bioremediation agent comprises the following components in parts by weight: 4 parts of alternate mucor fungus powder, 3 parts of bacillus megaterium powder, 5 parts of pseudomonas flexuralis powder, 5 parts of bacillus subtilis powder, 7 parts of sulfate reducing bacteria powder, 2 parts of corynebacterium couchslensis powder, 4 parts of trichoderma powder, 3 parts of penicillium powder and 7 parts of lactic acid bacteria powder; the composite enzyme preparation in the bioremediation agent consists of aldehyde dehydrogenase, catalase and nitroreductase according to the mass ratio of 1:2: 2; the mass ratio of the bioremediation agent to the soil is 1:100, and then the soil mixed with the bioremediation agent is returned to the field;
s5: detection and evaluation: sampling detection is carried out on the soil after thermal desorption treatment, parameters of wastewater treatment and wet soil treatment are timely adjusted according to the content of the organochlorine pesticide in the organochlorine pesticide polluted soil, and the organochlorine pesticide content in the soil finally returned to the field is guaranteed to reach the standard.
As shown in figure 1, the composite catalytic oxidation degradation device for organochlorine pesticide contaminated soil comprises a headstock 1, a first hook 2, a second hook 3, a ploughing machine 4, a leaching device 5, a photocatalytic box 6, an ultrasonic oxidation box 7, a thermal desorption device 8, a bioremediation agent mixing device 9, a carriage 10, an electromagnetic stirring device 11, a slurry pump 12 and a water pump 13, wherein the ploughing machine 4 is movably connected with the rear of the headstock 1 through the first hook 2, the carriage 10 is movably connected with the rear of the ploughing machine 4 through the second hook 3, the leaching device 5 is positioned at the head of the carriage 10, the photocatalytic box 6 is fixed below the leaching device 5, the electromagnetic stirring device 11 is fixed below the photocatalytic box 6, the ultrasonic oxidation box 7 is fixedly connected to the right side of the photocatalytic box 6, a water inlet of the ultrasonic oxidation box 7 is communicated with the photocatalytic box 6 through the slurry pump 12, a water outlet of a water inlet of the ultrasonic oxidation box 7 is communicated with the leaching device 5 through the water pump 13, the thermal desorption device 8 is fixed on the right side of the leaching device 5, the bioremediation agent mixing device 9 is fixedly connected on the right side of the thermal desorption device 8, the leaching device 5 comprises a leaching water tank 51, a leaching spray head 52, a first conveyor belt 53 and a leaching tank 54, a soil shoveling chain 55 for conveying soil to the leaching tank 54 is arranged in front of the leaching tank 54, the leaching water tank 51 is arranged at the top of the leaching tank 54, the first conveyor belt 53 is rotatably connected in the leaching tank 54, industrial filter cloth is adopted on the surface of the conveyor belt, the leaching spray head 52 is installed on the inner wall of the top of the leaching tank 54 and is communicated with the leaching water tank 51, in-situ remediation is carried out on the polluted soil through an integrated device, the transportation link is reduced, and the soil.
Example 4 the apparatus of example 4 is capable of removing organochlorine pesticides in soil with high efficiency compared to example 3.
Example 5:
a composite catalytic oxidation degradation method for organochlorine pesticide contaminated soil comprises the following steps:
s1: soil pretreatment: loosening and crushing the polluted soil by using a land turner 4, and screening stones, plastics and branches in the soil;
s2: soil leaching: shoveling the soil into a leaching device 5 by using a soil remediation vehicle, leaching the soil, and then performing solid-liquid separation to obtain wet soil and wastewater;
s3: wastewater treatment: transferring the obtained wastewater to photocatalysisA tank 6 for adjusting the pH value of the wastewater to 7.5, using a titanium dioxide-loaded nickel mesh 61 as a photocatalyst, the wavelength of ultraviolet light is 256nm, the photocatalytic reaction time of the wastewater is 2h, the stirring speed is 80r/min and the electromagnetic power is 100W during the photocatalytic reaction accompanied by electromagnetic stirring, and then introducing the wastewater into an ultrasonic oxidation tank 7 with the sound intensity of 100W/cm2The rated power is 3KW, the pH value of the wastewater is adjusted to 8 after the wastewater is subjected to oxidative degradation by ultrasonic waves, organochlorine pesticides in the wastewater are sampled and detected, and the wastewater is recycled as water for drip washing after the detection is confirmed to be qualified;
s4: wet soil treatment: transferring the wet soil obtained by S2 to a thermal desorption device 8 for thermal desorption treatment, wherein the heating mode adopts microwave heating, the heating temperature is 30 ℃, the heating time is 10min, the waste water treatment link of S2 is carried out after the evaporation water vapor is collected, the soil subjected to thermal desorption treatment is transferred to a bioremediation agent mixing device 9, a bioremediation agent is sprayed and stirred, and the bioremediation agent consists of the following components in parts by weight: 3 parts of chitosan, 200 parts of bentonite, 25 parts of green algae, 2 parts of citric acid, 9 parts of shell powder, 15 parts of needle mushroom fungus chaff, 80 parts of plant ash, 20 parts of rice bran, 15 parts of tea seed shells, 80 parts of cow dung, 60 parts of palm wood dust, 0.02 part of a complex enzyme preparation and 0.048 part of a complex microbial agent; the composite microbial agent in the bioremediation agent comprises the following components in parts by weight: 4 parts of alternate mucor fungus powder, 3 parts of bacillus megaterium powder, 5 parts of pseudomonas flexuralis powder, 5 parts of bacillus subtilis powder, 7 parts of sulfate reducing bacteria powder, 2 parts of corynebacterium couchslensis powder, 4 parts of trichoderma powder, 3 parts of penicillium powder and 7 parts of lactic acid bacteria powder; the composite enzyme preparation in the bioremediation agent consists of aldehyde dehydrogenase, catalase and nitroreductase according to the mass ratio of 1:2: 2; the mass ratio of the bioremediation agent to the soil is 1:100, and then the soil mixed with the bioremediation agent is returned to the field;
s5: detection and evaluation: sampling detection is carried out on the soil after thermal desorption treatment, parameters of wastewater treatment and wet soil treatment are timely adjusted according to the content of the organochlorine pesticide in the organochlorine pesticide polluted soil, and the organochlorine pesticide content in the soil finally returned to the field is guaranteed to reach the standard.
As shown in figure 1, the composite catalytic oxidation degradation device for organochlorine pesticide contaminated soil comprises a headstock 1, a first hook 2, a second hook 3, a ploughing machine 4, a leaching device 5, a photocatalytic box 6, an ultrasonic oxidation box 7, a thermal desorption device 8, a bioremediation agent mixing device 9, a carriage 10, an electromagnetic stirring device 11, a slurry pump 12 and a water pump 13, wherein the ploughing machine 4 is movably connected with the rear of the headstock 1 through the first hook 2, the carriage 10 is movably connected with the rear of the ploughing machine 4 through the second hook 3, the leaching device 5 is positioned at the head of the carriage 10, the photocatalytic box 6 is fixed below the leaching device 5, the electromagnetic stirring device 11 is fixed below the photocatalytic box 6, the ultrasonic oxidation box 7 is fixedly connected to the right side of the photocatalytic box 6, a water inlet of the ultrasonic oxidation box 7 is communicated with the photocatalytic box 6 through the slurry pump 12, a water outlet of a water inlet of the ultrasonic oxidation box 7 is communicated with the leaching device 5 through the water pump 13, the thermal desorption device 8 is fixed on the right side of the leaching device 5, the bioremediation agent mixing device 9 is fixedly connected on the right side of the thermal desorption device 8, the leaching device 5 comprises a leaching water tank 51, a leaching spray head 52, a first conveyor belt 53 and a leaching tank 54, a soil shoveling chain 55 for conveying soil to the leaching tank 54 is arranged in front of the leaching tank 54, the leaching water tank 51 is arranged at the top of the leaching tank 54, the first conveyor belt 53 is rotatably connected in the leaching tank 54, industrial filter cloth is adopted on the surface of the conveyor belt, the leaching spray head 52 is installed on the inner wall of the top of the leaching tank 54 and is communicated with the leaching water tank 51, in-situ remediation is carried out on the polluted soil through an integrated device, the transportation link is reduced, and the soil.
The grader 4 includes a vehicle body 41, a dozing device 42, a scattering device 43, and a screen 44, wherein the dozing device 42 is mounted at the front bottom of the vehicle body 41, the scattering device 43 is rotatably mounted above the dozing device 42, and the screen 44 is mounted at the rear of the dozing device 42, thereby effectively removing impurities in soil.
As shown in fig. 2, the photocatalytic box 6 includes two nickel nets 61 and two ultraviolet lamps 62, the two nickel nets 61 are fixedly installed inside the photocatalytic box 6, and the four ultraviolet lamps 62 are respectively fixedly installed on the inner walls of the four sides of the photocatalytic box 6, so as to degrade the organic pesticide through photocatalysis.
As shown in fig. 3, the ultrasonic oxidation box 7 comprises a partition plate 71 and two ultrasonic generators 72, wherein the partition plate 71 is transversely fixed inside the ultrasonic oxidation box 7, the two ultrasonic generators 72 are respectively fixed on the inner walls of the upper side and the lower side of the ultrasonic oxidation box 7, and the organic pesticide is correspondingly and rapidly degraded through ultrasonic cavitation.
As shown in fig. 4, the thermal desorption device 8 includes a second conveyor belt 81, a thermal desorption box 82 and a microwave generator 83, the microwave generator 83 is fixed at the bottom of the thermal desorption box 82, the second conveyor belt 81 is transversely installed in the middle of the thermal desorption box 82, and residual pesticides in the wet soil are removed through thermal desorption.
As shown in fig. 5, the bioremediation agent mixing device 9 includes a remediation agent adding device 91 and a mixing device 92, the remediation agent adding device 91 is fixed above the bioremediation agent mixing device 9, and the mixing device 92 is rotatably installed below the remediation agent adding device 91 to increase the self-degradation capability of the soil.
The slurry pump 12, the water pump 13, the ultraviolet lamp 62, the ultrasonic generator 72, and the microwave generator 83 used in examples 4 to 5 are commercially available products as long as the functions of the present invention can be achieved, and those skilled in the art can select and use the products according to the conventional general knowledge, and are not limited thereto.
Example 5 compared with example 4, in example 5, the structure of the photocatalytic tank 6, the ultrasonic oxidation tank 7, the thermal desorption device 8 and the bioremediation agent mixing device 9 can efficiently remove organochlorine pesticides in soil without generating new pollution, and the total removal effect of pollutants in example 5 is shown in table 1:
TABLE 1 Total removal of contaminants
Remarking: the weighted value is the sum of the pollutant content mg/kg in each component multiplied by the mass percentage of the component in the feed soil.
The processing capacity of example 5 reached 20 to 25m3And d, screening and grading to remove the target pollutants in the soil by more than 85 percent, wherein the removal rates of the pollutants in the coarse material and the gravel are respectively 90 percent and 85 percentThe above. The environment quality of the repaired soil meets the standard of the corresponding land type soil or meets the requirement of a safe recycling function, and the treated waste liquid meets the requirement of safe discharge.
Claims (10)
1. A composite catalytic oxidation degradation method for organochlorine pesticide contaminated soil is characterized by comprising the following steps:
s1: soil pretreatment: loosening and crushing the polluted soil by adopting a land turning machine (4), and screening stones, plastics and branches in the soil;
s2: soil leaching: shoveling the soil into a leaching device (5) by using a soil remediation vehicle, leaching the soil, and then performing solid-liquid separation to obtain wet soil and wastewater;
s3: wastewater treatment: transferring the obtained wastewater to a photocatalytic box (6), adjusting the pH value of the wastewater to 6.5-7.5, using a nickel net (61) loaded with titanium dioxide as a photocatalyst, setting the wavelength of ultraviolet light at 240-256nm, setting the photocatalytic reaction time of the wastewater to 1.5-2h, carrying out electromagnetic stirring during the photocatalytic reaction at a stirring speed of 80r/min and an electromagnetic power of 100W, introducing the wastewater into an ultrasonic oxidation box (7) with a sound intensity of 80-100W/cm2The rated power is 3KW, the pH value of the wastewater is adjusted to 7-8 after the wastewater is subjected to oxidative degradation by ultrasonic waves, and organochlorine pesticides in the wastewater are sampled and detected, and the wastewater is recycled as leaching water after the detection is qualified;
s4: wet soil treatment: transferring the wet soil obtained in the step S2 to a thermal desorption device (8) for thermal desorption treatment, wherein the heating mode adopts microwave heating, the heating temperature is 30 ℃, the heating time is 10min, the step S2 is carried out after the evaporated water vapor is collected, the soil subjected to thermal desorption treatment is transferred to a bioremediation agent mixing device (9), a bioremediation agent is sprayed and stirred, the mass ratio of the bioremediation agent to the soil is 1:100, and then the soil mixed with the bioremediation agent is returned to the field;
s5: detection and evaluation: sampling detection is carried out on the soil after thermal desorption treatment, parameters of wastewater treatment and wet soil treatment are timely adjusted according to the content of the organochlorine pesticide in the organochlorine pesticide polluted soil, and the organochlorine pesticide content in the soil finally returned to the field is guaranteed to reach the standard.
2. The method for the composite catalytic oxidative degradation of organochlorine pesticide-contaminated soil according to claim 1, wherein the bioremediation agent in S4 is composed of the following components in parts by weight: 1-3 parts of chitosan, 80-200 parts of bentonite, 10-25 parts of green algae, 0.5-2 parts of citric acid, 2-9 parts of shell powder, 5-15 parts of flammulina velutipes mushroom bran, 40-80 parts of plant ash, 10-20 parts of rice bran, 5-15 parts of tea seed shells, 20-80 parts of cow dung, 25-60 parts of palm tree sawdust, 0.001-0.02 part of complex enzyme preparation and 0.005-0.048 part of complex microbial agent.
3. The method for the composite catalytic oxidative degradation of organochlorine pesticide-contaminated soil according to claim 2, wherein the composite microbial agent in the bioremediation agent comprises the following components in parts by weight: 1-4 parts of alternate mucor fungus powder, 2-3 parts of bacillus megaterium powder, 4-5 parts of pseudomonas flexuralis powder, 2-5 parts of bacillus subtilis powder, 3-7 parts of sulfate reducing bacteria powder, 1-2 parts of corynebacterium couchrum powder, 3-4 parts of trichoderma powder, 1.5-3 parts of penicillium powder and 6-7 parts of lactic acid bacteria powder.
4. The method for the composite catalytic oxidative degradation of organochlorine pesticide-contaminated soil according to claim 2, wherein the composite enzyme preparation in the bioremediation agent is composed of aldehyde dehydrogenase, catalase and nitroreductase in a mass ratio of 1:2: 2.
5. The composite catalytic oxidation degradation device for organochlorine pesticide contaminated soil, according to claim 1, is characterized by comprising a vehicle head (1), a first hook (2), a second hook (3), a plowing machine (4), a leaching device (5), a photocatalytic box (6), an ultrasonic oxidation box (7), a thermal desorption device (8), a bioremediation agent mixing device (9), a carriage (10), an electromagnetic stirring device (11), a slurry pumping machine (12) and a water suction pump (13), wherein the plowing machine (4) is movably connected with the rear of the vehicle head (1) through the first hook (2), the carriage (10) is movably connected with the rear of the plowing machine (4) through the second hook (3), the leaching device (5) is located at the head of the carriage (10), the photocatalytic box (6) is fixed below the leaching device (5), the electromagnetic stirring device (11) is fixed below the photocatalytic box (6), ultrasonic oxidation case (7) fixed connection is on the right side of photocatalysis case (6), and the water inlet of ultrasonic oxidation case (7) passes through pulp extractor (12) communicates with each other with photocatalysis case (6), and the delivery port of the water inlet of ultrasonic oxidation case (7) passes through suction pump (13) with drip washing device (5) communicates with each other, thermal desorption apparatus (8) are fixed on the right side of drip washing device (5), bioremediation agent mixing arrangement (9) fixed connection is on the right side of thermal desorption apparatus (8), drip washing device (5) are including drip washing water tank (51), drip washing shower nozzle (52), conveyer belt one (53), drip washing case (54) the place ahead is equipped with scraper chain (55) that transports soil to drip washing case (54), drip washing water tank (51) sets up the top of drip washing case (54), conveyer belt one (53) rotate and connect in drip washing case (54), the surface of the conveyor belt adopts industrial filter cloth, and the leaching spray head (52) is arranged on the inner wall of the top of the leaching tank (54) and is communicated with the leaching water tank (51).
6. The method for the combined catalytic oxidative degradation of organochlorine pesticide-contaminated soil according to claim 5, wherein the plowing machine (4) comprises a vehicle body (41), a soil shifting device (42), a scattering device (43) and a screen (44), the soil shifting device (42) is installed at the front bottom of the vehicle body (41), the scattering device (43) is rotatably installed above the soil shifting device (42), and the screen (44) is installed behind the soil shifting device (42).
7. The method for the combined catalytic oxidative degradation of organochlorine pesticide-contaminated soil according to claim 5, wherein the photocatalytic box (6) comprises two nickel screens (61) and four ultraviolet lamps (62), wherein two nickel screens (61) are fixedly installed inside the photocatalytic box (6), and four ultraviolet lamps (62) are respectively fixedly installed on the inner walls of the four sides of the photocatalytic box (6).
8. The method for the composite catalytic oxidative degradation of organochlorine pesticide-contaminated soil according to claim 5, wherein the ultrasonic oxidation box (7) comprises a partition plate (71) and two ultrasonic generators (72), wherein the partition plate (71) is transversely fixed inside the ultrasonic oxidation box (7), and the two ultrasonic generators (72) are respectively fixed on the upper and lower inner walls of the ultrasonic oxidation box (7).
9. The method for the composite catalytic oxidative degradation of the organochlorine pesticide-contaminated soil according to claim 5, wherein the thermal desorption device (8) comprises a second conveyor belt (81), a thermal desorption box (82) and a microwave generator (83), the microwave generator (83) is fixed at the bottom of the thermal desorption box (82), and the second conveyor belt (81) is transversely installed in the middle of the thermal desorption box (82).
10. The method for the composite catalytic oxidative degradation of the organochlorine pesticide-contaminated soil according to claim 5, wherein the thermal desorption device (8) comprises a second conveyor belt (81), a thermal desorption box (82) and a microwave generator (83), the microwave generator (83) is fixedly installed at the bottom of the thermal desorption box (82), and the second conveyor belt (81) is transversely installed inside the thermal desorption box (82).
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| JP7061245B1 (en) | 2022-04-28 |
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