CN112007945A - Device and method for repairing organic matter-heavy metal combined contaminated soil - Google Patents
Device and method for repairing organic matter-heavy metal combined contaminated soil Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
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- 230000003647 oxidation Effects 0.000 claims abstract description 56
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 56
- 238000005243 fluidization Methods 0.000 claims abstract description 54
- 239000005416 organic matter Substances 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims description 165
- 239000003814 drug Substances 0.000 claims description 56
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- 238000005067 remediation Methods 0.000 claims description 26
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- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
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- 231100000759 toxicological effect Toxicity 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D47/00—Separating dispersed particles from gases, air or vapours by liquid as separating agent
- B01D47/02—Separating dispersed particles from gases, air or vapours by liquid as separating agent by passing the gas or air or vapour over or through a liquid bath
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/44—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Soil Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Mycology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Health & Medical Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Biotechnology (AREA)
- Botany (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a device for restoring organic matter-heavy metal combined contaminated soil, which comprises a crushing unit, a microwave unit, an oxidation unit, an activation unit, a flue gas treatment unit and a fluidization reaction unit, wherein the crushing unit, the microwave unit, the oxidation unit, the activation unit and the flue gas treatment unit are sequentially connected; the method using the device is simple to operate, has a good heavy metal solidification effect and a high organic matter removal rate, and can be used for repairing soil with high organic matter concentration.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to the technical field of remediation of organic matter and heavy metal combined contaminated soil, and particularly relates to a device and a method for remediation of organic matter-heavy metal combined contaminated soil.
Background
The combined pollution caused by the coexistence of inorganic and organic pollutants is the direction and the focus of the current combined pollution research. Research is currently focused on organic chelating agents, pesticides, petroleum hydrocarbons and the combined contamination of aromatic compounds with heavy metals. Heavy metals and polycyclic aromatic hydrocarbons are two important pollutants in the soil environment, and often enter the soil environment simultaneously or sequentially to form composite pollution, and for a long time, many researches are carried out on the microbial ecological toxicological effect and remediation measures of the single pollution of the heavy metals and the polycyclic aromatic hydrocarbons and the composite pollution among different heavy metals at home and abroad. Most of the existing remediation methods only aim at single type pollutants, and few remediation methods aiming at the composite polluted soil have been reported.
CN106623380A discloses a method for remediating organic pollutant-heavy metal combined contaminated soil, which is characterized in that persulfate is added into organic pollutant-heavy metal combined contaminated soil, on the basis of effective oxidative degradation of the organic pollutant, iron-based biochar is further applied to passivate heavy metals with activation effect, and effective remediation of the organic pollutant-heavy metal combined contaminated soil is achieved, but the method only fixes the heavy metals on the surface, does not effectively achieve removal and transfer of the pollutant, and cannot be applied to remediation of soil with high organic matter content.
CN111054741A discloses a method and a device for restoring heavy metal-organic matter combined contaminated soil by an electric-leaching combined technology, wherein the process adopts the electric-leaching restoring technology to treat the heavy metal-organic matter combined contaminated soil, and has a good treatment effect on heavy metals such as cadmium (Cd), copper (Cu), lead (Pb), zinc (Zn) and the like in the soil and organic pollutants such as pyrene, benzo (a) pyrene, benzo (g, h, i) perylene and the like, but the method only can be used for specific organic matters, is narrow in application range, and the electric technology is difficult to popularize on a large scale.
CN109127723A discloses a combined remediation method for composite contaminated soil by using straws, which comprises the following steps: crushing the plant straws by a crusher; mixing the crushed plant straws with a compound fertilizer, wherein the mixing ratio is set as 3: 1; loosening the contaminated soil by a scarifier, taking out a certain amount of contaminated soil sample, and measuring the pH value and the heavy metal content; uniformly scattering plant straws mixed with the fertilizer into the surface layer of the polluted soil, and selecting proper surface layer thickness according to the PH value and the content of heavy metals; plant straws and polluted soil are mixed through the scarifier, so that the straws are turned to the inner layer of the soil, and then the latticed grooves are dug out of the soil. However, the method has long repairing time and does not realize the transfer of heavy metals.
In conclusion, the existing remediation method for the organic matter-heavy metal combined polluted soil has the problems of narrow application range and poor remediation.
Therefore, it is necessary to develop a new device and method for remediating organic matter-heavy metal complex contaminated soil, which provides a technology that is easy to implement and has good remediation effect.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a device and a method for repairing organic matter-heavy metal composite contaminated soil, wherein the device integrates the technologies of microwave, oxidation, activation, fluidization treatment and the like, can repair heavy metal and high-concentration organic matter composite contaminated soil, and has the advantages of good curing effect on heavy metal, high removal rate of organic matter and wide application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a device for repairing organic matter-heavy metal combined polluted soil, which comprises a crushing unit, a microwave unit, an oxidation unit, an activation unit and a flue gas treatment unit which are sequentially connected; the microwave unit comprises a microwave device; the microwave unit also comprises a first gas outlet arranged at the upper part of the microwave device and a first soil outlet arranged at the lower part of the microwave device; the first gas outlet is connected with the oxidation unit; the device also comprises a fluidization reaction unit connected with the first soil outlet; the fluidization reaction unit is connected with the flue gas treatment unit.
The device for restoring the organic matter-heavy metal combined polluted soil, provided by the invention, integrates the technologies of microwave catalytic degradation, oxidation, biological activation, fluidization treatment and the like, can restore the heavy metal and high-concentration organic matter combined polluted soil, has a good curing effect on the heavy metal, is high in removal rate of the organic matter, and has a wide application prospect, wherein the heavy metal is particularly polluted by arsenic which is difficult to treat, and the organic matter comprises polycyclic aromatic hydrocarbon, polychlorinated biphenyl, petroleum hydrocarbon, pesticide and the like combined polluted soil.
The microwave unit can be used for catalytically degrading organic matters in soil such as polycyclic aromatic hydrocarbon, polychlorinated biphenyl, petroleum hydrocarbon or pesticides and organic heavy metals such as organic arsenic into inorganic micromolecules and separating the inorganic micromolecules from the soil; forming gas after microwave and soil after microwave; after the microwave, the gas is further oxidized and degraded into small molecules by the oxidation unit, and carried heavy metals, dust and the like are washed off, and the main organic small molecular substances in the oxidized gas enter the activation unit for biodegradation and basically reach the emission standard; the soil after the microwave treatment still contains organic matters and soluble heavy metals, and is in full contact reaction with the medicament in the fluidization reaction unit, so that the further degradation of the organic matters and the solidification of the heavy metals can be well realized, a better soil remediation effect is achieved, the soil remediated by the device can be remediated by centipede fern organisms, and the separation of the heavy metals from the soil is realized.
Preferably, the microwave unit comprises a microwave hood and a microwave cavity arranged at one end of the microwave hood.
Preferably, a microwave generating device is connected to the upper part of the microwave cavity.
Preferably, the top of the microwave cavity is provided with a first gas outlet.
Preferably, an air exhaust device is arranged at the top of the microwave cavity.
Preferably, a waveguide tube is arranged at the lower part of the microwave cavity.
Preferably, the waveguides are provided in at least two.
Preferably, a transmission part is arranged in the microwave hood.
Preferably, the conveying means is a conveyor belt.
Preferably, a first medicament adder is arranged at the upper part of the conveying part in the microwave hood.
Preferably, the first medicament adder is a first medicament sprayer.
The first agent sprayer is preferably adopted, so that the uniform contact and timely supplement of the agent and the soil can be facilitated, and the catalytic degradation effect is remarkably improved.
Preferably, the oxidation unit comprises a counter current oxidizer.
Preferably, a first gas inlet is arranged at the bottom of the countercurrent oxidizer.
Preferably, a second gas outlet is provided at an end of the countercurrent oxidizer remote from the first gas inlet.
Preferably, a second medicament inlet is arranged at one end of the countercurrent oxidizer far away from the first gas inlet and on the side opposite to the second gas outlet.
Preferably, a second medicament outlet is arranged on one side of the countercurrent oxidizer close to the first gas inlet end.
Preferably, the second medicament outlet is connected to a third medicating device.
According to the invention, the second medicament outlet is preferably connected with the third medicament adding device, so that on one hand, the second medicament is in countercurrent contact with the gas, and then the dust and heavy metal carried in the gas are washed off, and the second medicament is inconvenient to directly enter a wastewater treatment system; on the other hand, after the reaction, the effective components of the second medicament are not completely reacted, and the second medicament can be added into a third medicament adding device for further utilization, so that the enrichment of heavy metals carried in gas is realized, the use amount of the medicament can be reduced, and the industrial application value is high.
Preferably, the activation unit comprises an activation device, and the bottom of the activation device is provided with a second gas inlet and a third gas inlet.
Preferably, an aeration device is arranged in the bottom of the activation device.
Preferably, the second gas inlet and the third gas inlet are both connected to an aeration device.
Preferably, the aeration device comprises an aeration pipe.
Preferably, the number of the aeration pipes is at least two, for example, 2, 3, 5, 8, 10, 12, 13, 15, 18 or 20, preferably 8 to 12.
Preferably, the bottom of the activation device is also provided with an activated sludge discharge port.
Preferably, an activation tank is arranged in the activation device.
Preferably, an activated sludge inlet is arranged on one side of the upper part of the activation device.
Preferably, a third gas outlet is further arranged on one side of the upper part of the activation device.
Preferably, the third gas outlet is connected to the flue gas treatment unit.
Preferably, the fluidized reaction unit comprises a circulating fluidized bed.
Preferably, a third medicament dosing device is arranged on a pipeline between the circulating fluidized bed and the microwave unit.
Preferably, the circulating fluidized bed comprises a circulating fluidized bed.
Preferably, a soil remediation discharge outlet is arranged at the bottom of the circulating fluidized bed body.
Preferably, one side of the bottom of the circulating fluidized bed body is provided with an air inlet.
Preferably, a gas distribution device communicated with the gas inlet is arranged in the bottom of the circulating fluidized bed body.
Preferably, a separating device is further arranged on one side of the upper part of the bed body of the circulating fluidized bed.
Preferably, an exhaust gas purification device is arranged at the upper part of the separation device.
Preferably, the upper part of the tail gas purification device is connected with a flue gas treatment unit.
Preferably, the flue gas treatment unit comprises a fan and a flue gas treatment tower which are connected in sequence.
Preferably, a gas buffering device is arranged between the flue gas treatment unit and the activation unit.
Preferably, the gas buffer device is a gas buffer tank.
Preferably, a valve is arranged on one side of the gas buffering device, which is close to the flue gas treatment unit.
In a second aspect, the invention provides a method for remedying organic matter-heavy metal combined contaminated soil, which comprises the following steps:
(1) the soil to be repaired enters a crushing unit, is crushed and then enters a microwave unit for microwave treatment;
(2) gas generated by the microwave treatment sequentially enters the oxidation unit from the first gas outlet, is subjected to oxidation treatment, is sent into the activation unit, is subjected to activation treatment, and is sent into the flue gas treatment unit for flue gas treatment;
(3) the soil after the microwave treatment is sent to a fluidization reaction unit through a first soil outlet to carry out fluidization reaction, and the restored soil is obtained; and the gas generated by the fluidization reaction unit is sent to a flue gas treatment unit for flue gas treatment.
The soil remediation method provided by the invention can better realize the removal of organic matters in soil and the solidification of heavy metals, is simple and convenient to operate, and has no secondary pollution.
Preferably, the method is carried out by using the device for remediating the organic matter-heavy metal combined contaminated soil according to the first aspect of the invention.
The content of organic substances in the high-concentration organic substance-contaminated soil is not less than 2000mg/kg, and may be, for example, 2000mg/kg, 2200mg/kg, 2300mg/kg, 2500mg/kg, 2800mg/kg, 3000mg/kg, or the like.
Preferably, the particle size of the soil after crushing in step (1) is 10mm or less, and may be, for example, 10mm, 9mm, 8mm, 7mm, 6mm, 5mm, 4mm, 3mm, 2mm, 1mm, 0.5mm, 0.2mm, 0.1mm, 0.02mm, 0.01mm, 0.001mm or the like.
Preferably, the temperature of the microwave treatment is 200 to 400 ℃, for example, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 250 ℃, 280 ℃, 300 ℃, 320 ℃, 350 ℃, 380 ℃ or 400 ℃ and the like.
Preferably, the residence time of the microwave treatment is 20-60 min, for example, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60 min.
Preferably, a first agent is added to the microwave treatment.
Preferably, the first medicament is added by spraying.
Preferably, the first agent comprises an organic matter degradation catalyst, preferably ferrite.
According to the invention, the organic matter degradation catalyst is preferably ferrite, and compared with other catalysts, the organic matter degradation catalyst has the advantages of harmlessness and catalytic efficiency.
Preferably, the weight percentage of the ferrite in the first agent is 2-25 wt%, for example, 2 wt%, 4 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 20 wt%, 22 wt% or 25 wt%.
Preferably, the liquid-solid ratio of the first chemical to the crushed soil is 0.1 to 0.25mL:1g, and may be, for example, 0.1mL:1g, 0.12mL:1g, 0.15mL:1g, 0.16mL:1g, 0.18mL:1g, 0.2mL:1g, 0.22mL:1g, or 0.25mL:1 g.
Preferably, the oxidation treatment in the step (2) includes: and the gas generated by the microwave treatment is in countercurrent contact with a second medicament for oxidation treatment.
Preferably, the second agent comprises fenton's reagent.
Preferably, H in the second agent2O2The concentration is 10 g/L-100 g/L; FeSO4The concentration is 20g/L to 200g/L, wherein H2O2The concentration may be, for example, 10g/L, 12g/L, 15g/L, 20g/L, 22g/L, 25g/L, 28g/L, 30g/Lg/L, 35g/L, 40g/L, 45g/L, 50g/L, 55g/L, 60g/L, 65g/L, 70g/L, 75g/L, 80g/L, 85g/L, 90g/L, 95g/L, or 100g/L, etc.; FeSO4The concentration may be, for example, 20g/L, 25g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L, 80g/L, 90g/L, 100g/L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L, 160g/L, 170g/L, 180g/L, 190g/L, or 200g/L, etc.
Preferably, the ratio of the Fenton reagent to the gas generated by the microwave treatment in the oxidation treatment is 0.5-2L: 1m3For example, it may be 0.5L:1m3、0.6L:1m3、0.8L:1m3、0.9L:1m3、1.0L:1m3、1.2L:1m3、1.3L:1m3、1.4L:1m3、1.5L:1m3、1.8L:1m3Or 2.0L:1m3And the like.
Preferably, the temperature of the oxidation treatment is 50 to 90 ℃, and may be, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃.
Preferably, the residence time of the oxidation treatment is 1 to 10min, and may be, for example, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min, 5min, 5.5min, 6min, 6.5min, 7min, 7.5min, 8min, 8.5min, 9min, 9.5min, 10min, or the like.
Preferably, air is introduced during the activation treatment.
Preferably, the activated sludge is discharged from an activated sludge discharge port.
Preferably, in the step (2), before the flue gas treatment, the activated gas enters a gas buffering device for storage.
Preferably, the soil after the microwave treatment in the step (3) is mixed with a third agent and then enters a fluidization reaction unit for fluidization reaction.
Preferably, the third agent is a fenton's reagent.
Preferably, H in the third agent2O2The concentration is 50 g/L-300 g/L; FeSO4The concentration is 40g/L to 450g/L, wherein H2O2The concentration may be, for example, 50g/L, 55g/L, 60g/L, 100g/L, 120g/L, 150g/L, 180g/L(ii) each of,/L, 200g/L, 220g/L, 230g/L, 250g/L, 280g/L, or 300 g/L; FeSO4The concentration may be, for example, 40g/L, 50g/L, 80g/L, 100g/L, 120g/L, 150g/L, 180g/L, 200g/L, 220g/L, 250g/L, 300g/L, 350g/L, 400g/L, or 450g/L, etc.
Preferably, the ratio of the third agent to the soil after microwave treatment is 2.5 to 12mL:1g, and may be, for example, 2.5mL:1g, 3mL:1g, 3.2mL:1g, 3.5mL:1g, 4.0mL:1g, 4.2mL:1g, 4.5mL:1g, 4.8mL:1g, 5.0mL:1g, 5.5mL:1g, 5.8mL:1g, 6.0mL:1g, 6.2mL:1g, 6.5mL:1g, 6.8mL:1g, 7.0mL:1g, 7.2mL:1g, 7.5mL:1g, 7.8mL:1g, 8mL:1g, 8.5mL:1g, 9.0mL:1g, 9.5mL:1g, 10.5mL:1g, 11.5mL:1g, or 1g, and preferably 1g, 2.5mL:1g, 11.5mL, or 2 mL.
Preferably, ozone is introduced into the fluidized reaction.
Preferably, the ratio of ozone to soil after microwave treatment in the fluidization reaction is 20 to 100mL:1g, and may be, for example, 20mL:1g, 25mL:1g, 30mL:1g, 35mL:1g, 40mL:1g, 45mL:1g, 50mL:1g, 55mL:1g, 60mL:1g, 65mL:1g, 70mL:1g, 75mL:1g, 80mL:1g, 85mL:1g, 90mL:1g, 95mL:1g, or 100mL:1 g.
According to the invention, the ratio of ozone to soil treated by microwave in the fluidization reaction is preferably controlled to be 20-100 mL:1g, so that the soil remediation effect can be better improved while the using amount of ozone is balanced.
When the ozone is not introduced enough to fluidize the soil, the invention can assist in introducing oxygen and/or air, and the flow rate of the total gas is not specially limited as long as the operation of the fluidized bed can be realized.
Preferably, the temperature of the fluidization reaction is 80-200 ℃, for example, 80 ℃, 85 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃.
Preferably, the soil after remediation is subjected to bioremediation and heavy metal transfer.
Preferably, the bioremediation comprises: performing bioremediation by using centipede fern and transferring heavy metal.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) the method comprises the steps that soil to be repaired enters a crushing unit and is crushed until the particle size is smaller than or equal to 10mm, then enters a microwave unit, microwave treatment is carried out for 20-60 min at 200-400 ℃, a first medicament is sprayed in the microwave treatment, the first medicament is ferrite, the mass percentage of ferrite in the first medicament is 2-25 wt%, and the liquid-solid ratio of the first medicament to the crushed soil is 0.1-0.25 mL:1 g;
(2) gas generated by the microwave treatment enters the oxidation unit from the first gas outlet to be in countercurrent contact with the Fenton reagent, and oxidation treatment is carried out for 1-10 min at 50-90 ℃; h in the Fenton reagent2O2The concentration is 10 g/L-100 g/L; FeSO4The concentration is 20 g/L-200 g/L; the proportion of Fenton reagent to gas generated by microwave treatment in the oxidation treatment is 0.5-2L: 1m3；
The gas after oxidation treatment is sent to an activation unit for activation treatment, air is introduced in the activation treatment process, and the gas after activation treatment enters a gas buffer device for storage and buffering and is sent to a flue gas treatment unit for flue gas treatment;
(3) discharging the soil subjected to microwave treatment through a first soil outlet, mixing the soil with a third agent, and feeding the mixture into a fluidization reaction unit for fluidization reaction to obtain restored soil; the gas generated by the fluidization reaction unit is sent to a flue gas treatment unit for flue gas treatment;
the third agent is a fenton reagent; h in the third agent2O2The concentration is 50 g/L-300 g/L; FeSO4The concentration is 40 g/L-450 g/L; the ratio of the third agent to the soil after microwave treatment is 2.5-12 mL:1 g; introducing ozone into the fluidized reaction; the ratio of ozone to the soil after microwave treatment in the fluidization reaction is 20-100 mL:1 g; the temperature of the fluidization reaction is 80-200 ℃;
performing bioremediation on the repaired soil by using centipede fern, and transferring heavy metal.
The step of performing bioremediation by using centipede fern is not particularly limited, and a method well known to those skilled in the art can be adopted.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the device for restoring the organic matter-heavy metal compound contaminated soil integrates microwave, oxidation, activation and fluidization treatment technologies, can restore the heavy metal and high-concentration organic matter compound contaminated soil, and solves the problem of the existing soil restoration;
(2) the method for restoring the organic matter-heavy metal combined polluted soil has a good heavy metal curing effect, wherein the removal rate of leachable arsenic is more than or equal to 85 wt%, the removal rate of organic matters is high, and the removal rate of polycyclic aromatic hydrocarbons is more than or equal to 86 wt%.
Drawings
Fig. 1 is a schematic view of an apparatus for remediating organic matter-heavy metal combined contaminated soil provided in embodiment 1 of the present invention.
In the figure: 1-a crushing unit; 2-a microwave unit; 201-microwave hood; 202-a conveyor belt; 203-a first medicament sprayer; 204-a microwave cavity; 205-a waveguide; 3-an oxidation unit; 301-a first gas inlet; 302-a second gas outlet; 303-a second agent inlet; 304-a second medicament outlet; 4-an activation unit; 401-an activation device; 402-an activation tank; 403-a second gas inlet; 404-a third gas inlet; 405-activated sludge discharge; 406-aeration means; 407-activated sludge inlet; 5-gas buffer tank; 6-a valve; 7-circulating fluidized bed; 701-circulating fluidized bed body; 702-a gas distributor; 703-an air inlet; 704-repairing the soil discharge hole; 705-a separation device; 706-a tail gas purification device; 8-a third medicament dosing device; 9-a fan; 10-flue gas treatment tower.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
First, an embodiment
Example 1
The embodiment provides a device for repairing organic matter-heavy metal combined contaminated soil, as shown in fig. 1, the device comprises a crushing unit 1, a microwave unit 2, an oxidation unit 3, an activation unit 4 and a flue gas treatment unit which are connected in sequence; the microwave unit 2 comprises a microwave device; the microwave unit 2 further comprises a first gas outlet arranged at the upper part of the microwave device and a first soil outlet arranged at the lower part of the microwave device; the first gas outlet is connected with the oxidation unit 3; the device also comprises a fluidization reaction unit connected with the first soil outlet; the fluidization reaction unit is connected with the flue gas treatment unit.
The microwave unit 2 comprises a microwave hood 201 and a microwave cavity 204 arranged at one end of the microwave hood 201; the upper part of the microwave cavity 204 is connected with a microwave generating device (not shown); the top of the microwave cavity 204 is provided with a first gas outlet; a waveguide tube 205 is arranged at the lower part of the microwave cavity 204; three waveguide tubes 205 are provided; a conveyor belt 202 is arranged in the microwave hood 201; a first medicament sprayer 203 is arranged on the upper part of the conveyor belt 202 in the microwave hood 201.
The oxidation unit 3 comprises a counter-current oxidizer; the countercurrent oxidizer is a series three-pass U-shaped tube, and a first gas inlet 301 is formed in the bottom of the countercurrent oxidizer; a second gas outlet 302 is arranged at one end of the countercurrent oxidizer far away from the first gas inlet 301; a second medicament inlet 303 is arranged on one side of one end of the countercurrent oxidizer far away from the first gas inlet 301, which is opposite to the second gas outlet 302; a second medicament outlet 304 is arranged on one side of the countercurrent oxidizer close to the first gas inlet 301 end, and the second medicament outlet 304 is connected with a third medicament adding device.
The activation unit 4 comprises an activation device 401, and a second gas inlet 403 and a third gas inlet 404 are arranged at the bottom of the activation device 401; the third gas inlet 404 is connected to the second gas outlet 302; an aeration device is arranged in the bottom of the activation device 401; the aeration device comprises an aeration pipe; the aeration pipe is connected with the second gas inlet 403; the bottom of the activation device 401 is also provided with an activated sludge discharge port 405; an activation tank 402 is arranged in the activation device 401; an activated sludge inlet 407 is formed in one side of the upper part of the activation device 401; a third gas outlet is also formed in one side of the upper part of the activation device 401; the third gas outlet is connected with a gas buffer tank 5; and a valve 6 is arranged on one side of the gas buffer tank 5 close to the flue gas treatment unit.
The fluidized reaction unit comprises a circulating fluidized bed 7; a third medicament dosing device 8 is arranged on a pipeline between the circulating fluidized bed 7 and the microwave unit 2; the circulating fluidized bed 7 comprises a circulating fluidized bed body 701; a restored soil discharge port 704 is arranged at the bottom of the circulating fluidized bed body 701; an air inlet 703 is formed in one side of the bottom of the circulating fluidized bed body 701; a gas distributor 702 communicated with a gas inlet 703 is arranged in the bottom of the circulating fluidized bed body 701; a separating device 705 is further arranged on one side of the upper part of the circulating fluidized bed body 701; a tail gas purification device 706 is arranged at the upper part of the separation device 705; the upper part of the tail gas purification device 706 is connected with a flue gas treatment unit.
The flue gas treatment unit comprises a fan 9 and a flue gas treatment tower 10 which are connected in sequence.
Example 2
The embodiment provides a device for repairing organic matter-heavy metal combined polluted soil, which comprises a crushing unit, a microwave unit, an oxidation unit, an activation unit and a flue gas treatment unit which are sequentially connected; the microwave unit comprises a microwave device; the microwave unit also comprises a first gas outlet arranged at the upper part of the microwave device and a first soil outlet arranged at the lower part of the microwave device; the first gas outlet is connected with the oxidation unit; the device also comprises a fluidization reaction unit connected with the first soil outlet; the fluidization reaction unit is connected with the flue gas treatment unit.
The microwave unit comprises a microwave cover and a microwave cavity arranged at one end of the microwave cover; the upper part of the microwave cavity is connected with a microwave generating device; the top of the microwave cavity is provided with a first gas outlet; the lower part of the microwave cavity is provided with a waveguide tube; two waveguide tubes are arranged; a conveyor belt is arranged in the microwave hood; and a first medicament sprayer is arranged at the upper part of the conveying belt in the microwave hood.
The oxidation unit comprises a counter-current oxidizer; the countercurrent oxidizer is a serial three-pass U-shaped tube, and a first gas inlet is formed in the bottom of the countercurrent oxidizer; a second gas outlet is arranged at one end of the countercurrent oxidizer, which is far away from the first gas inlet; a second medicament inlet is arranged on one side of one end of the countercurrent oxidizer, which is far away from the first gas inlet, and is opposite to the second gas outlet; and a second medicament outlet is arranged on one side of the countercurrent oxidizer close to the first gas inlet end and is connected with a third medicament adding device.
The activation unit comprises an activation device, and a second gas inlet and a third gas inlet are formed in the bottom of the activation device; the third gas inlet is connected with the second gas outlet; an aeration device is arranged in the bottom of the activation device; the aeration device comprises an aeration pipe; the aeration pipe is connected with the second gas inlet; the bottom of the activation device is also provided with an activated sludge discharge port; an activation tank is arranged in the activation device; an activated sludge inlet is formed in one side of the upper part of the activation device; a third gas outlet is also formed in one side of the upper part of the activation device; the third gas outlet is connected with a gas buffer tank; and a valve is arranged on one side of the gas buffer tank close to the flue gas treatment unit.
The fluidized reaction unit comprises a circulating fluidized bed; a third medicament dosing device is arranged on a pipeline between the circulating fluidized bed and the microwave unit; the circulating fluidized bed comprises a circulating fluidized bed body; a soil remediation discharge outlet is arranged at the bottom of the bed body of the circulating fluidized bed; an air inlet is formed in one side of the bottom of the circulating fluidized bed body; a gas distributor communicated with the gas inlet is arranged in the bottom of the circulating fluidized bed body; a separating device is also arranged on one side of the upper part of the circulating fluidized bed body; a tail gas purification device is arranged at the upper part of the separation device; and the upper part of the tail gas purification device is connected with the flue gas treatment unit.
The flue gas treatment unit comprises a fan and a flue gas treatment tower which are connected in sequence.
Example 3
The embodiment provides a device for repairing organic matter-heavy metal combined contaminated soil, which is the same as that in embodiment 1 except that the first dosing device is arranged outside a dosing pipe arranged at the upper part of the front end of a conveyor belt.
Example 4
The embodiment provides a device for repairing organic matter-heavy metal combined contaminated soil, which is the same as the device in embodiment 1 except that the countercurrent oxidizer is a straight-tube type countercurrent oxidizer.
Example 5
The embodiment provides a device for repairing organic matter-heavy metal combined contaminated soil, and the device is the same as the device in embodiment 1 except that the second agent outlet is not connected with a third dosing device.
Comparative example 1
The comparative example provides a device for remedying the organic matter-heavy metal combined contaminated soil, which is the same as that in example 1 except that the fluidized reaction unit is replaced by a stirring reaction kettle.
The device specifically comprises a crushing unit, a microwave unit, an oxidation unit, an activation unit and a flue gas treatment unit which are connected in sequence; the microwave unit comprises a microwave device; the microwave unit also comprises a first gas outlet arranged at the upper part of the microwave device and a first soil outlet arranged at the lower part of the microwave device; the first gas outlet is connected with the oxidation unit; the device also comprises a fluidization reaction unit connected with the first soil outlet; the fluidization reaction unit is connected with the flue gas treatment unit.
The microwave unit comprises a microwave cover and a microwave cavity arranged at one end of the microwave cover; the upper part of the microwave cavity is connected with a microwave generating device; the top of the microwave cavity is provided with a first gas outlet; the lower part of the microwave cavity is provided with a waveguide tube; three waveguide tubes are arranged; a conveyor belt is arranged in the microwave hood; and a first medicament sprayer is arranged at the upper part of the conveying belt in the microwave hood.
The oxidation unit comprises a counter-current oxidizer; the countercurrent oxidizer is a serial three-pass U-shaped tube, and a first gas inlet is formed in the bottom of the countercurrent oxidizer; a second gas outlet is arranged at one end of the countercurrent oxidizer, which is far away from the first gas inlet; a second medicament inlet is arranged on one side of one end of the countercurrent oxidizer, which is far away from the first gas inlet, and is opposite to the second gas outlet; and a second medicament outlet is arranged on one side of the countercurrent oxidizer close to the first gas inlet end and is connected with a third medicament adding device.
The activation unit comprises an activation device, and a second gas inlet and a third gas inlet are formed in the bottom of the activation device; the third gas inlet is connected with the second gas outlet; an aeration device is arranged in the bottom of the activation device; the aeration device comprises an aeration pipe; the aeration pipe is connected with the second gas inlet; the bottom of the activation device is also provided with an activated sludge discharge port; an activation tank is arranged in the activation device; an activated sludge inlet is formed in one side of the upper part of the activation device; a third gas outlet is also formed in one side of the upper part of the activation device; the third gas outlet is connected with a gas buffer tank; and a valve is arranged on one side of the gas buffer tank close to the flue gas treatment unit.
An air inlet is formed in one side of the bottom of the stirring reaction kettle; a feed inlet is formed in the upper part of the stirring reaction kettle, and a soil remediation discharge outlet is formed in one side of the bottom of the stirring reaction kettle, which is opposite to the air inlet; a third medicament dosing device is arranged on a pipeline between the stirring reaction kettle and the microwave unit; a tail gas purification device is arranged on one side of the stirring reaction kettle opposite to the feed inlet; and the upper part of the tail gas purification device is connected with the flue gas treatment unit.
The flue gas treatment unit comprises a fan and a flue gas treatment tower which are connected in sequence.
Second, application example
Application example 1
The application example provides a method for restoring organic matter-heavy metal combined polluted soil, which comprises the following steps:
(1) the method comprises the steps of enabling soil to be repaired (total arsenic in the soil is 103.2 mg/kg; the content of polycyclic aromatic hydrocarbon is 2965.3mg/kg) to enter a crushing unit, crushing the soil to reach the grain size of less than or equal to 10mm, enabling the soil to enter a microwave unit, carrying out microwave treatment at 300 ℃ for 30min, spraying a sodium ferrite solution with the mass percentage of 15 wt% in the microwave treatment, wherein the liquid-solid ratio of the sodium ferrite solution to the crushed soil is 0.2mL:1 g;
(2) gas generated by the microwave treatment enters the oxidation unit from the first gas outlet to be in countercurrent contact with the Fenton reagent, and is subjected to oxidation treatment for 2min at 70 ℃; h in the Fenton reagent2O2The concentration is 30 g/L; FeSO4The concentration is 40 g/L; the proportion of Fenton's reagent to gas generated by microwave treatment in the oxidation treatment is 1L:1m3(ii) a The Fenton reagent is discharged and enters a third medicine adding device to be used as a third medicine;
the gas after oxidation treatment is sent into an activation unit for activation treatment, air is introduced into an aeration device in the activation treatment process, and the gas after activation treatment enters a gas buffer tank for storage and buffering and is sent into a flue gas treatment unit for flue gas treatment;
(3) discharging the soil subjected to microwave treatment through a first soil outlet, mixing the soil with a third agent in a pipeline, feeding the mixture into a fluidization reaction unit for fluidization reaction to obtain repaired soil, and discharging the repaired soil from a repaired soil discharge outlet; the gas generated by the fluidization reaction unit is sent to a flue gas treatment unit for flue gas treatment;
the third agent is a fenton reagent; h in the third agent2O2The concentration is 150 g/L; FeSO4The concentration is 400 g/L; the ratio of the third agent to the soil after microwave treatment is 3mL to 1 g; introducing ozone into the fluidized reaction; the ratio of ozone to the soil after microwave treatment in the fluidization reaction is 80mL:1 g; the temperature of the fluidization reaction is 90 ℃;
performing bioremediation on the repaired soil by using centipede fern, and transferring heavy metal.
Application example 2
The application example provides a method for restoring organic matter-heavy metal combined polluted soil, which comprises the following steps:
(1) the method comprises the steps of enabling soil to be repaired (total arsenic in the soil is 62.5mg/kg, polycyclic aromatic hydrocarbon is 1453mg/kg) to enter a crushing unit, crushing the soil until the particle size is smaller than or equal to 8mm, enabling the soil to enter a microwave unit, carrying out microwave treatment at 400 ℃ for 60min, spraying a sodium ferrite solution with the mass percentage of 25 wt% in the microwave treatment, wherein the liquid-solid ratio of the sodium ferrite solution to the crushed soil is 0.25mL:1 g;
(2) gas generated by the microwave treatment enters the oxidation unit from the first gas outlet to be in countercurrent contact with the Fenton reagent, and is subjected to oxidation treatment for 10min at 90 ℃; h in the Fenton reagent2O2The concentration is 10 g/L; FeSO4The concentration is 20 g/L; the ratio of Fenton's reagent to gas generated by microwave treatment in the oxidation treatment is 0.5L:1m3；
The gas after oxidation treatment is sent into an activation unit for activation treatment, air is introduced into an aeration device in the activation treatment process, and the gas after activation treatment enters a gas buffer tank for storage and buffering and is sent into a flue gas treatment unit for flue gas treatment;
(3) discharging the soil subjected to microwave treatment through a first soil outlet, mixing the soil with a third agent in a pipeline, feeding the mixture into a fluidization reaction unit for fluidization reaction to obtain repaired soil, and discharging the repaired soil from a repaired soil discharge outlet; the gas generated by the fluidization reaction unit is sent to a flue gas treatment unit for flue gas treatment;
the third agent is a fenton reagent; h in the third agent2O2The concentration is 300 g/L; FeSO4The concentration is 450 g/L; the ratio of the third agent to the soil after microwave treatment is 12mL to 1 g; introducing ozone into the fluidized reaction; the ratio of ozone to the soil after microwave treatment in the fluidization reaction is 20mL:1 g; the temperature of the fluidization reaction is 200 ℃;
performing bioremediation on the repaired soil by using centipede fern, and transferring heavy metal.
Application example 3
The application example provides a method for restoring organic matter-heavy metal combined polluted soil, which comprises the following steps:
(1) the method comprises the steps of enabling soil to be repaired (total arsenic in the soil is 88.3 mg/kg; the content of polycyclic aromatic hydrocarbon is 2245.0mg/kg) to enter a crushing unit, crushing the soil until the particle size is smaller than or equal to 10mm, enabling the soil to enter a microwave unit, carrying out microwave treatment at 200 ℃ for 20min, spraying a sodium ferrite solution with the mass percentage of 2 wt% in the microwave treatment, wherein the liquid-solid ratio of the sodium ferrite solution to the crushed soil is 0.15mL:1 g;
(2) gas generated by the microwave treatment enters the oxidation unit from the first gas outlet to be in countercurrent contact with the Fenton reagent, and is subjected to oxidation treatment for 2.5min at 50 ℃; h in the Fenton reagent2O2The concentration is 100 g/L; FeSO4The concentration is 200 g/L; the proportion of Fenton's reagent to gas generated by microwave treatment in the oxidation treatment is 2L:1m3；
The gas after oxidation treatment is sent into an activation unit for activation treatment, air is introduced into an aeration device in the activation treatment process, and the gas after activation treatment enters a gas buffer tank for storage and buffering and is sent into a flue gas treatment unit for flue gas treatment;
(3) discharging the soil subjected to microwave treatment through a first soil outlet, mixing the soil with a third agent in a pipeline, feeding the mixture into a fluidization reaction unit for fluidization reaction to obtain repaired soil, and discharging the repaired soil from a repaired soil discharge outlet; the gas generated by the fluidization reaction unit is sent to a flue gas treatment unit for flue gas treatment;
the third agent is a fenton reagent; h in the third agent2O2The concentration is 50 g/L; FeSO4The concentration is 450 g/L; the ratio of the third agent to the soil after microwave treatment is 12mL to 1 g; introducing ozone into the fluidized reaction; the ratio of ozone to the soil after microwave treatment in the fluidization reaction is 100mL:1 g; the temperature of the fluidization reaction is 80 ℃;
performing bioremediation on the repaired soil by using centipede fern, and transferring heavy metal.
Application example 4
The application example provides a method for restoring organic matter-heavy metal combined contaminated soil, and the method is the same as the application example 1 except that the device provided in the embodiment 3 is adopted.
Application example 5
The application example provides a method for restoring organic matter-heavy metal combined contaminated soil, and the method is the same as the application example 1 except that the device provided in the embodiment 4 is adopted for oxidation treatment for 30 s.
Application example 6
The application example provides a method for restoring organic matter-heavy metal combined contaminated soil, and the method is the same as the application example 1 except that the device provided by the example 5 is adopted, and the material at the outlet of the second medicament does not enter the third medicament adding device.
Application example 7
The application example provides a method for restoring organic matter-heavy metal combined contaminated soil, and the method is the same as the method in the embodiment 1 except that the sodium ferrite solution in the step (1) is replaced by the ferric chloride solution.
Application example 8
The application example provides a method for restoring organic matter-heavy metal combined contaminated soil, and the method is the same as the method in the embodiment 1 except that the ratio of the ozone to the soil subjected to microwave treatment in the fluidization reaction in the step (3) is 10mL to 1 g.
Application example 9
The application example provides a method for restoring organic matter-heavy metal combined contaminated soil, and the method is the same as the method in the embodiment 1 except that the ratio of the ozone to the soil subjected to microwave treatment in the fluidization reaction in the step (3) is 100mL to 1 g.
Application comparative example 1
The application comparative example provides a method for restoring organic matter-heavy metal combined contaminated soil, and the method is the same as the application example 1 except for the step (3).
(3) Discharging the soil subjected to microwave treatment through a first soil outlet, mixing the soil with a third agent in a pipeline, feeding the mixture into a stirring reaction kettle for stirring reaction to obtain repaired soil, and discharging the repaired soil from a repaired soil discharge outlet; the gas generated by the fluidization reaction unit is sent to a flue gas treatment unit for flue gas treatment;
the third agent is a fenton reagent; h in the third agent2O2The concentration is 150 g/L; FeSO4The concentration is 400 g/L; the ratio of the third agent to the soil after microwave treatment is 3mL to 1 g; introducing ozone into the stirring reaction; the proportion of the ozone to the soil after microwave treatment in the stirring reaction is 80mL:1 g; the temperature of the fluidization reaction is 90 ℃;
performing bioremediation on the repaired soil by using centipede fern, and transferring heavy metal.
Third, test and results
The test method comprises the following steps: the soil after the treatment and before bioremediation was subjected to a leaching experiment according to the Method of USEPASW846Method1312, the arsenic concentration in the leachate was analyzed by ICP-OES, and the removal rate of leachable arsenic (wherein the removal rate of arsenic is a portion including arsenic which is not leached after solidification) was calculated. Detecting the content of the polycyclic aromatic hydrocarbon in the soil after the remediation but before the bioremediation by using national standard HJ784-2016, and calculating the removal rate of the polycyclic aromatic hydrocarbon.
The test results of the above application examples and comparative application examples are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) it can be seen from comprehensive application examples 1 to 9 that the method for repairing the organic matter-heavy metal combined contaminated soil provided by application examples 1 to 9 can effectively solidify arsenic and realize removal of organic matter polycyclic aromatic hydrocarbons, wherein the removal rate of leachable arsenic is not less than 85 wt%, the removal rate of polycyclic aromatic hydrocarbons is not less than 86 wt%, and the soil repair effect is good;
(2) it can be seen from the comprehensive application examples 1 and 4 that the first agent is added by spraying in the application example 1, compared with the method of adding chemicals through a chemical adding pipe in the application example 4, the removal rate of the leachable arsenic in the application example 1 is 98.6 wt%, the removal rate of the polycyclic aromatic hydrocarbon is 99.4 wt%, and the removal rate of the leachable arsenic in the application example 4 is 98.0 wt%, and the removal rate of the polycyclic aromatic hydrocarbon is 92.1 wt%, so that the soil remediation effect is improved by adopting the method of adding chemicals by spraying;
(3) it can be seen from the comprehensive application examples 1 and 5 that, compared with the application example 5 in which a straight-tube type countercurrent oxidizer is used, the application example 1 in which a U-tube type countercurrent oxidizer is used has a better polycyclic aromatic hydrocarbon removal effect than the application example 5, which indicates that the U-tube type countercurrent oxidizer is preferably used in the invention, so that the oxidation time can be increased and the polycyclic aromatic hydrocarbon removal effect can be improved;
(4) the comprehensive application examples 1 and 6 show that the soil remediation effects of the two are not changed greatly, but the Fenton reagent in the oxidation unit in the application example 6 is wasted seriously, so that the Fenton reagent at the outlet of the oxidation unit is returned to the third reagent feeding device, the usage amount of the Fenton reagent is saved, and the whole process is more economic;
(5) it can be seen from the comprehensive application examples 1 and 8-9 that the ratio of ozone to soil after microwave treatment in the fluidized reaction of application example 1 is 80mL:1g, compared with the application examples 8-9 of 10mL:1g and 100mL:1g respectively, the treatment effect in application example 1 is equivalent to that of application example 9, the remediation effect is better than that of application example 8, and the ozone dosage in application example 1 is less, thereby showing that the treatment effect and the ozone dosage are better balanced by controlling the ozone and the soil after microwave treatment in a specific ratio.
(6) By combining application example 1 and application comparative example 1, it can be seen that the fluidized reaction unit is adopted in application example 1, and compared with the stirred tank reactor adopted in application comparative example 1, the removal rate of leachable arsenic in application example 1 is 98.6 wt%, the removal rate of polycyclic aromatic hydrocarbon is 99.4 wt%, and the removal rate of leachable arsenic in application comparative example 1 is 78.5 wt%, and the removal rate of polycyclic aromatic hydrocarbon is 81.2 wt%, so that the soil remediation effect is greatly improved by adopting a fluidized reaction mode.
In conclusion, the device and the method for restoring the organic matter-heavy metal combined contaminated soil can better restore the heavy metal-organic matter combined contaminated soil, the removal rate of the leachable arsenic in the soil after primary restoration is more than or equal to 85 wt%, the removal rate of the polycyclic aromatic hydrocarbon is more than or equal to 86 wt%, and the restoration effect is good.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The device for restoring the organic matter-heavy metal composite polluted soil is characterized by comprising a crushing unit, a microwave unit, an oxidation unit, an activation unit and a flue gas treatment unit which are sequentially connected;
the microwave unit comprises a microwave device;
the microwave unit also comprises a first gas outlet arranged at the upper part of the microwave device and a first soil outlet arranged at the lower part of the microwave device;
the first gas outlet is connected with the oxidation unit;
the device also comprises a fluidization reaction unit connected with the first soil outlet;
the fluidization reaction unit is connected with the flue gas treatment unit.
2. The apparatus of claim 1, wherein the microwave unit comprises a microwave hood and a microwave cavity disposed at one end of the microwave hood;
preferably, a microwave generating device is connected to the upper part of the microwave cavity;
preferably, the top of the microwave cavity is provided with a first gas outlet;
preferably, a waveguide tube is arranged at the lower part of the microwave cavity;
preferably, the wave guides are provided in at least two;
preferably, a transmission part is arranged in the microwave hood;
preferably, the conveying member is a conveyor belt;
preferably, a first medicament adder is arranged at the upper part of the conveying part in the microwave hood;
preferably, the first medicament adder is a first medicament sprayer.
3. The apparatus of claim 1 or 2, wherein the oxidation unit comprises a counter current oxidizer;
preferably, a first gas inlet is arranged at the bottom of the countercurrent oxidizer;
preferably, a second gas outlet is arranged at one end of the countercurrent oxidizer far away from the first gas inlet;
preferably, a second medicament inlet is arranged at one end of the countercurrent oxidizer far away from the first gas inlet and on the side opposite to the second gas outlet;
preferably, a second medicament outlet is arranged on one side of the countercurrent oxidizer close to the first gas inlet end.
4. The device according to any one of claims 1 to 3, wherein the activation unit comprises an activation device, and a second gas inlet and a third gas inlet are arranged at the bottom of the activation device;
preferably, an aeration device is arranged in the bottom of the activation device;
preferably, the aeration device comprises an aeration pipe;
preferably, the bottom of the activation device is also provided with an activated sludge discharge port;
preferably, an activation pool is arranged in the activation device;
preferably, an activated sludge inlet is arranged on one side of the upper part of the activation device;
preferably, a third gas outlet is further arranged on one side of the upper part of the activation device;
preferably, the third gas outlet is connected to the flue gas treatment unit.
5. The apparatus according to any one of claims 1 to 4, wherein the fluidized reaction unit comprises a circulating fluidized bed;
preferably, a third medicament dosing device is arranged on a pipeline between the circulating fluidized bed and the microwave unit;
preferably, the circulating fluidized bed comprises a circulating fluidized bed;
preferably, a soil remediation discharge outlet is arranged at the bottom of the circulating fluidized bed body;
preferably, an air inlet is formed in one side of the bottom of the circulating fluidized bed body;
preferably, a gas distribution device communicated with the gas inlet is arranged at the bottom of the circulating fluidized bed body;
preferably, a separating device is further arranged on one side of the upper part of the bed body of the circulating fluidized bed;
preferably, an exhaust gas purification device is arranged at the upper part of the separation device;
preferably, the upper part of the tail gas purification device is connected with a flue gas treatment unit.
6. The device according to any one of claims 1 to 5, wherein the flue gas treatment unit comprises a fan and a flue gas treatment tower which are connected in sequence;
preferably, a gas buffering device is arranged between the flue gas treatment unit and the activation unit;
preferably, the gas buffer device is a gas buffer tank;
preferably, a valve is arranged on one side of the gas buffering device, which is close to the flue gas treatment unit.
7. The method for restoring the organic matter-heavy metal combined polluted soil is characterized by comprising the following steps of:
(1) the soil to be repaired enters a crushing unit, is crushed and then enters a microwave unit for microwave treatment;
(2) gas generated by the microwave treatment sequentially enters the oxidation unit from the first gas outlet, is subjected to oxidation treatment, is sent into the activation unit, is subjected to activation treatment, and is sent into the flue gas treatment unit for flue gas treatment;
(3) the soil after the microwave treatment is sent to a fluidization reaction unit through a first soil outlet to carry out fluidization reaction, and the restored soil is obtained; and the gas generated by the fluidization reaction unit is sent to a flue gas treatment unit for flue gas treatment.
8. The method according to claim 7, wherein the particle size of the crushed soil in the step (1) is less than or equal to 10 mm;
preferably, the temperature of the microwave treatment is 200-400 ℃;
preferably, the residence time of the microwave treatment is 20-60 min;
preferably, a first medicament is added in the microwave treatment;
preferably, the first medicament is added by spraying;
preferably, the first agent comprises an organic matter degradation catalyst, preferably comprising ferrite;
preferably, the mass percentage of the ferrite in the first medicament is 2-25 wt%;
preferably, the liquid-solid ratio of the first medicament to the crushed soil is 0.1-0.25 mL:1 g.
9. The method according to claim 7 or 8, wherein the oxidation treatment in step (2) comprises: the gas generated by the microwave treatment is in countercurrent contact with a second medicament for oxidation treatment;
preferably, the second agent comprises fenton's reagent;
preferably, H in the second agent2O2The concentration is 10 g/L-100 g/L; FeSO4The concentration is 20 g/L-200 g/L;
preference is given toThe ratio of Fenton's reagent to gas generated by microwave treatment in the oxidation treatment is 0.5-2L: 1m3；
Preferably, the temperature of the oxidation treatment is 50-90 ℃;
preferably, the residence time of the oxidation treatment is 1-10 min;
preferably, air is introduced during the activation treatment;
preferably, the activated sludge is discharged from an activated sludge discharge port;
preferably, in the step (2), before the flue gas treatment, the activated gas enters a gas buffering device for storage.
10. The method according to any one of claims 7 to 9, wherein the soil after the microwave treatment in the step (3) is mixed with a third agent and then enters a fluidization reaction unit for fluidization reaction;
preferably, the third agent is fenton's reagent;
preferably, H in the third agent2O2The concentration is 50 g/L-300 g/L; FeSO4The concentration is 40 g/L-450 g/L;
preferably, the ratio of the third agent to the soil after microwave treatment is 2.5-12: 1, preferably 2.8-3.5: 1;
preferably, ozone is introduced into the fluidized reaction;
preferably, the ratio of the ozone to the soil after microwave treatment in the fluidization reaction is 20-100 mL:1 g;
preferably, the temperature of the fluidization reaction is 80-200 ℃;
preferably, the soil after remediation is subjected to bioremediation and heavy metal transfer;
preferably, the bioremediation comprises: performing bioremediation by using centipede fern and transferring heavy metal.
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| CN202010941342.9A CN112007945A (en) | 2020-09-09 | 2020-09-09 | Device and method for repairing organic matter-heavy metal combined contaminated soil |
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| CN202010941342.9A CN112007945A (en) | 2020-09-09 | 2020-09-09 | Device and method for repairing organic matter-heavy metal combined contaminated soil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114032104A (en) * | 2021-12-06 | 2022-02-11 | 深圳市万创青绿环境工程有限公司 | Bioremediation liquid, preparation method thereof and method for remedying soil heavy metals |
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| CN102527711A (en) * | 2012-03-02 | 2012-07-04 | 武汉都市环保工程技术股份有限公司 | Movable type contaminated soil remediation system adopting recirculating fluidized bed |
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Application publication date: 20201201 |