CN112718841A - Soil remediation method by coupling thermal desorption with chemical oxidation - Google Patents
Soil remediation method by coupling thermal desorption with chemical oxidation Download PDFInfo
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- CN112718841A CN112718841A CN202011302049.4A CN202011302049A CN112718841A CN 112718841 A CN112718841 A CN 112718841A CN 202011302049 A CN202011302049 A CN 202011302049A CN 112718841 A CN112718841 A CN 112718841A
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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
- B09C1/06—Reclamation of contaminated soil thermally
- B09C1/065—Reclamation of contaminated soil thermally by pyrolysis
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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
- B09C1/005—Extraction of vapours or gases using vacuum or venting
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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
- B09C1/08—Reclamation of contaminated soil chemically
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- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a soil remediation method by thermal desorption coupled chemical oxidation, which comprises the following steps: screening and crushing polluted soil until the particle size of the soil reaches the feeding particle size required by thermal desorption; soil is leveled, positioned and drilled in a field, a pollution area is determined, sodium persulfate oxidant and tap water are mixed and injected into the pollution area, and a nano zero-valent iron material is synchronously added for catalytic oxidation treatment; then sequentially entering an upper layer predrying section dehydration and a lower layer thermal desorption section pyrolysis organic pollutant of the thermal desorption device, then adjusting the water content of the soil through a tail end humidification system, collecting the flue gas generated by the lower layer thermal desorption section through a spray tower, and discharging or recycling the flue gas after the flue gas is treated to reach the standard. The method adopts the thermal desorption coupling catalytic oxidation technology to repair the soil, can perform chain scission on macromolecular substances, reduce the water content of the soil, improve the treatment efficiency of a subsequent thermal desorption section, reduce the energy consumption and solve the problems of single type and serious secondary pollution of a thermal desorption treatment method.
Description
Technical Field
The invention relates to the technical field of soil in-situ remediation, in particular to a soil remediation method by thermal desorption coupled chemical oxidation.
Background
In recent years, due to rapid economic development, industrial structures are continuously optimized and upgraded, natural ecosystems suffer from serious trauma, and under the concept of ecological protection development, the polluted soil restoration technology is gradually emphasized. The thermal desorption technology is one of the key technologies for soil remediation, and the main mechanism is that pollutants in soil are heated to a certain temperature, and then the pollutants are volatilized from the soil, so that the thermal desorption technology is mainly used for the remediation practice of organic contaminated sites, but the thermal desorption technology has the main defects of high energy consumption, low organic matter removal efficiency and the like, the soil needs to be heated to the boiling point of the pollutants to remove the pollutants in the soil, the soil remediation process needs to treat a large amount of soil, the components in the soil are complex, and the energy consumption required by heating is high. Meanwhile, some organic pollutants have high molecular weight or stable structure and are difficult to volatilize from soil under the condition of common heating temperature, so that high organic matter residue still exists in the soil after common thermal desorption treatment. Therefore, the heat energy utilization efficiency and the recovery efficiency are improved, and meanwhile, the stable organic pollutants are degraded into small molecular compounds before thermal desorption and then enter the thermal desorption treatment, which is the development direction of the thermal desorption treatment of the soil.
At present, methods for improving soil remediation efficiency are divided into two directions:
(1) by adding the iron soil conditioning material, on one hand, the heat conduction and heat transfer performance of the system are improved, and on the other hand, the iron material has a promoting effect on the removal of inorganic matters, organic matters and heavy metals;
(2) the thermal desorption coupling catalytic oxidation/reduction reaction process breaks the molecular chain of target pollutants in the soil, converts macromolecular organic matters with high boiling point into micromolecular organic matters with low boiling point, and improves the reaction efficiency of the subsequent thermal desorption section.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a soil remediation method by using thermal desorption coupled chemical oxidation, which can be used for improving the thermal conduction efficiency and the pollutant treatment efficiency by changing the physicochemical properties of soil pollutants through strengthening synergistic functional materials, and solving the problems of high energy consumption, single pollutant treatment type, serious secondary pollution, low equipment integration degree and high energy consumption of thermal desorption soil remediation technology.
The above object of the present invention is achieved by the following technical solutions:
a thermal desorption coupled chemical oxidation soil remediation method comprises the following steps:
(1) pretreatment: screening and crushing polluted soil until the particle size of the soil reaches the feeding particle size required by thermal desorption;
(2) chemical oxidation: the method comprises the following steps that (1) the polluted soil after pretreatment is subjected to site leveling, positioning and drilling to determine a polluted area, sodium persulfate oxidant and tap water are mixed and then injected into the polluted area, and a nano zero-valent iron material is synchronously added for catalytic oxidation treatment;
(3) thermal desorption: the polluted soil after the chemical oxidation treatment in the step (2) sequentially enters an upper layer predrying section of a thermal desorption device for dehydration and a lower layer thermal desorption section for high-temperature decomposition of organic pollutants;
(4) and (3) post-treatment: and (4) adjusting the water content of the soil after the thermal desorption treatment in the step (3) by a tail end humidifying system, collecting the flue gas generated by the lower thermal desorption section by a spray tower, passing the liquid generated in the tower through a gas-liquid separator, passing the liquid phase to a wastewater treatment unit, sending the gas phase to a waste gas treatment unit, and discharging or recycling after the gas phase reaches the standard.
In the step (1), the polluted soil pretreatment is carried out in a pretreatment greenhouse, the caking materials in the polluted soil are screened into different magnitudes by a vibrating screen, and the polluted soil is crushed and screened by an ALLU hopper.
In the step (1), the method also comprises the step of mixing and stirring the oxidizing agent in the polluted soil after crushing and screening.
In the step (2), the mass ratio of the sodium persulfate oxidant to the tap water is 1:1-100, and the mass ratio of the nano zero-valent iron to the mixed medicament is 1: 0.1-10.
In the step (3), the temperature of the upper pre-drying section is 150-.
In the invention, the advantages of the iron-based conditioning material nano zero-valent iron catalytic oxidation/reduction process coupled with soil remediation are as follows:
(1) the nano zero-valent iron has a promoting effect on removing heavy metals and organic pollutants. The mechanism of removing heavy metal by the nano zero-valent iron is related to the standard electrode potential of the metal, the toxicity of the heavy metal is reduced by changing the existing valence state of the heavy metal ions, and when the standard electrode potential of the heavy metal ions is lower than Fe, the adsorption effect is dominant; when the Fe content is far greater than that of the Fe, the reduction effect is dominant; in between, adsorption and reduction occur simultaneously. With Cu2+、Hg2+、Ag+For example, the redox potential is higher than Fe, which can serve as an electron donor to transfer electrons and reduce three metal ions; cd [ Cd ]2+、Ni2+、Pb2+The removal mechanism of the iron is different from that of copper, silver and mercury ions, and the nano zero-valent iron is in Fe-H2Hydrolysis in O system to OH-Further, Fe (OH) is produced2Precipitation, while Ni, Pb and Cd are easy to generate Ni (OH) under alkaline condition2、Pb(OH)2And Cd (OH)2And precipitating, thereby removing. And then the common Cr in the soil6+For example, chromium ions are more harmful to the environment than Cr due to their high water solubility and toxicity3+Therefore, the control method is generally to reduce the trivalent chromium ions under acidic conditions and then precipitate the trivalent chromium ions under basic conditions. Hexavalent chromium ions are in the range of 1.0<pH<At 6.0, Cr is mainly HCrO4 -Form exists when pH is higher>At 6.0, CrO is mainly used4 2-The nanometer zero-valent iron can respectively react HCrO under the acidic and alkaline conditions4 -And CrO4 2-And conversion to Cr3+。
In the case of nitrobenzene, for example, high-concentration (200mg/L) nitrobenzene wastewater can be reduced to nitrosobenzene, aniline, azobenzene, azoxybenzene, etc., and nitrosobenzene, azobenzene, and azoxybenzene are converted to aniline which is easily degraded by microorganisms as the reaction time is prolonged. For the removal of chlorine-containing organic matters, chlorine-containing organic matters are mainly reduced into low-toxicity matters through dechlorination and hydrogenation, for example, polychlorinated biphenyl can accept electrons released by Fe so as to complete dechlorination, and therefore, the nano zero-valent iron also has a certain promotion effect on the removal of organic pollutants.
(2) The promotion effect of the nano zero-valent iron on the chemical oxidation process. Taking sodium persulfate as an example, in the process of removing 2, 4-dichlorophenol, trichloroethylene, 1, 2-methyl tert-butyl ether, naphthalene and chlorobenzene, the persulfate activated by the nano zero-valent iron has better effect on removing organic pollutants than the persulfate or zero-valent iron used alone, and the promotion effect of the nano zero-valent iron on the activation of the persulfate is proved. Chemical oxidation can also be achieved using hydrogen peroxide as a strong oxidant, with iron as a catalyst and hydrogen peroxide as an oxidant, and the fenton reaction that occurs under strongly acidic conditions can promote the generation of hydroxyl radicals, and thus the removal of metal ions.
(3) Chemical oxidation-thermal desorption coupling repairing effect. Under the condition of proper soil moisture content, the coupling repair efficiency is enhanced whether the concentration of the oxidant is increased or the heating temperature of the thermal desorption section is increased. Chemical oxidation can carry out the chain scission effect with macromolecular substance, reduces soil moisture content to promote the treatment effeciency of later stage thermal desorption, reduce energy resource consumption. The catalytic oxidation/reduction treatment efficiency of the polluted soil is provided by recycling the waste heat of the thermal desorption system, and the molecular chain of target pollutants (such as TPH, PCB, PAH and the like) in the soil is broken, so that the molecular chain is converted from high-boiling-point macromolecular compounds into low-boiling-point micromolecular compounds, the reaction efficiency of a subsequent thermal desorption section is improved, and the heating temperature, the system energy consumption and the operation cost are reduced.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adopts thermal desorption coupling catalytic oxidation treatment technology to repair the soil, so that the treatment efficiency of the polluted soil can reach not less than 10 tons/hour, the consumption of natural gas is not higher than 35 standard/ton of soil, and the removal rate of organic pollutants in the soil is not less than 95 percent.
(2) On the basis of thermal desorption soil remediation, the chemical oxidation treatment is adopted to break chains of macromolecular substances, reduce the water content of the soil, improve the treatment efficiency of a subsequent thermal desorption section, reduce the energy consumption and solve the problems of single type and serious secondary pollution of the thermal desorption treatment method.
(3) The nanometer zero-valent iron material has different action mechanisms for removing heavy metals and organic pollutants, but has good catalytic action, can improve the heat conduction efficiency, and improves the pollutant treatment efficiency in the thermal desorption treatment section.
(4) The nanometer zero-valent iron material has an activation promoting effect on sodium persulfate oxidant and a catalytic effect on chemical oxidation treatment soil remediation, and under a strong acid condition, iron is used as a catalyst, hydrogen peroxide is used as an oxidant, a Fenton reaction can be generated, generation of hydroxyl is promoted, and removal of metal ions is promoted.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The invention discloses a thermal desorption coupled chemical oxidation soil remediation method, which comprises the following steps:
(1) pretreatment: screening and crushing polluted soil until the particle size of the soil reaches the feeding particle size required by thermal desorption;
(2) chemical oxidation: the method comprises the following steps that (1) the polluted soil after pretreatment is subjected to site leveling, positioning and drilling to determine a polluted area, sodium persulfate oxidant and tap water are mixed and then injected into the polluted area, and a nano zero-valent iron material is synchronously added for catalytic oxidation treatment;
(3) thermal desorption: the polluted soil after the chemical oxidation treatment in the step (2) sequentially enters an upper layer predrying section of a thermal desorption device for dehydration and a lower layer thermal desorption section for high-temperature decomposition of organic pollutants;
(4) and (3) post-treatment: and (4) adjusting the water content of the soil after the thermal desorption treatment in the step (3) by a tail end humidifying system, collecting the flue gas generated by the lower thermal desorption section by a spray tower, passing the liquid generated in the tower through a gas-liquid separator, passing the liquid phase to a wastewater treatment unit, sending the gas phase to a waste gas treatment unit, and discharging or recycling after the gas phase reaches the standard.
The following is further illustrated by specific application examples.
Example 1
The soil remediation method adopting thermal desorption coupled chemical oxidation comprises the following steps:
(1) pretreatment: the polluted soil is screened and crushed for pretreatment, so that the particle size of the soil meets the requirement of the feeding particle size of thermal desorption equipment, and impurities are prevented from being mixed. The operation can be completed in a pretreatment greenhouse by utilizing a vibrating screen and an ALLU hopper, the vibrating screen screens materials caked in soil into different magnitudes, the ALLU hopper can crush and screen polluted soil, and the polluted soil is mixed with an oxidizing agent.
(2) Chemical oxidation: and (3) leveling, positioning and drilling the pretreated polluted soil in a field, determining a polluted area, and adding a sodium persulfate oxidant and tap water in a mass ratio of 1:20 into a medicament stirring device to prepare a medicament. After the preparation is finished, a water pipe is taken by a high-pressure water pump and is connected with a stirring device, the medicament is injected into a polluted area, and at the moment, the nano zero-valent iron material is synchronously added, wherein the mass ratio of the nano zero-valent iron material to the mixed medicament is 10: 1.
(3) Thermal desorption: the contaminated soil in the chemical oxidation treatment section enters an upper layer pre-drying section (the temperature is 150 ℃ F. and 200 ℃ C.) through a feed hopper and an auger so as to remove water in the soil. The dehydrated soil enters a lower thermal desorption section (the temperature is 850-.
(4) And (3) post-treatment: the soil after being treated by the thermal desorption section is adjusted to the target value by the tail end humidifying system so as to avoid the problem of secondary pollution caused by dust. The flue gas generated in the lower thermal desorption section is collected by the spray tower, the liquid generated in the tower passes through the gas-liquid separator, the liquid phase is sent to the wastewater treatment unit, the gas phase is sent to the waste gas treatment unit, and the liquid reaches the standard and is recycled in the thermal desorption section so as to reduce the energy consumption.
The soil remediation method is used for remedying an industrial polluted land plot in Baoshan district of Shanghai city, and can ensure that the treatment efficiency of the polluted soil is not less than 10 tons/hour, the consumption of natural gas is not higher than 35 standard/ton soil, and the removal rate of organic pollutants in the soil is not less than 95%.
Example 2
The soil remediation method by thermal desorption coupled chemical oxidation in this example is the same as that in example 1, except that the mass ratio of the sodium persulfate oxidant to the tap water is 1:100, and the mass ratio of the nano zero-valent iron material to the mixed chemical is 1: 10. The soil remediation method is used for remediating an agricultural polluted land in Qingpu district of Shanghai city, and can ensure that the treatment efficiency of the polluted soil is not lower than 10 tons/hour, the consumption of natural gas is not higher than 35 standard/ton soil, and the removal rate of organic pollutants in the soil is not lower than 95%.
Example 3
The soil remediation method by thermal desorption coupled chemical oxidation in this example is the same as that in example 1, except that the mass ratio of the sodium persulfate oxidant to the tap water is 1:60, and the mass ratio of the nano zero-valent iron material to the mixed chemical is 1: 2. The soil remediation method is used for remedying the polluted soil of aquaculture in a Pudong new area in Shanghai, and can ensure that the treatment efficiency of the polluted soil is not lower than 10 tons/hour, the consumption of natural gas is not higher than 35 standard/ton of soil, and the removal rate of organic pollutants in the soil is not lower than 95 percent.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments. Those skilled in the art should appreciate that many modifications and variations are possible in light of the above teaching without departing from the scope of the invention.
Claims (5)
1. A soil remediation method by coupling thermal desorption and chemical oxidation is characterized by comprising the following steps:
(1) pretreatment: screening and crushing polluted soil until the particle size of the soil reaches the feeding particle size required by thermal desorption;
(2) chemical oxidation: the method comprises the following steps that (1) the polluted soil after pretreatment is subjected to site leveling, positioning and drilling to determine a polluted area, sodium persulfate oxidant and tap water are mixed and then injected into the polluted area, and a nano zero-valent iron material is synchronously added for catalytic oxidation treatment;
(3) thermal desorption: the polluted soil after the chemical oxidation treatment in the step (2) sequentially enters an upper layer predrying section of a thermal desorption device for dehydration and a lower layer thermal desorption section for high-temperature decomposition of organic pollutants;
(4) and (3) post-treatment: and (4) adjusting the water content of the soil after the thermal desorption treatment in the step (3) through a tail end humidifying system, collecting the flue gas generated in the lower thermal desorption section through a spray tower, and discharging or recycling the flue gas after the treatment reaches the standard.
2. The soil remediation method of claim 1 wherein in step (1) the contaminated soil is pre-treated in a pre-treatment greenhouse, the agglomerated material in the contaminated soil is screened by a vibrating screen to different levels, and the contaminated soil is crushed and screened by an ALLU hopper.
3. The soil remediation method of claim 1 further comprising the step of mixing the oxidizing agent with the crushed and sieved contaminated soil in step (1).
4. The soil remediation method of claim 1 wherein, in step (2), the mass ratio of the sodium persulfate oxidant to the tap water is from 1:1 to 100, and the mass ratio of the nanoscale zero-valent iron to the mixed chemical is from 1:0.1 to 10.
5. The soil remediation method of claim 1 wherein, in step (3), the temperature of the upper predrying section is 150-200 ℃ and the temperature of the lower thermal desorption section is 800-1000 ℃, which are determined according to the type of organic pollutants.
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| CN114570763A (en) * | 2022-03-15 | 2022-06-03 | 生态环境部南京环境科学研究所 | Excavation soil remediation method for building construction contaminated soil |
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Application publication date: 20210430 |