CN111672893A - Indirect thermal desorption process for contaminated soil remediation - Google Patents
Indirect thermal desorption process for contaminated soil remediation Download PDFInfo
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- CN111672893A CN111672893A CN202010265695.1A CN202010265695A CN111672893A CN 111672893 A CN111672893 A CN 111672893A CN 202010265695 A CN202010265695 A CN 202010265695A CN 111672893 A CN111672893 A CN 111672893A
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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
- B09C1/062—Reclamation of contaminated soil thermally by using electrode or resistance heating elements
-
- 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
-
- 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
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
-
- 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
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
Abstract
The invention relates to an indirect thermal desorption process for repairing contaminated soil, which adds repairing components into the soil and comprises the following steps: adding a reinforcer into the polluted soil, adding the reinforcer into the polluted soil/underground water, treating benzene series, halogenated hydrocarbon, nitroaromatic and phenol organic pollutants in a polluted source region or a polluted plume, adding an activating agent, activating persulfate ions, generating free radical ions with stronger oxidizing capability to oxidize more difficult-to-degrade organic pollutant solid characters, and heating the soil polluted by organic matters to the boiling point of the organic matters in a direct or/and indirect heating mode of heating a brick kiln; taking out particulate matter from the tail gas through a filtering device, continuously cooling the particulate matter through a quenching device, performing oil-water separation on a cooling kettle through an oil-water separator, discharging oil into an oil tank, discharging clean tail gas through a dehydration device, and recovering clean water through a water treatment device; then, the reagent reaction is carried out, and the organic pollutants are strongly degraded under the catalytic condition.
Description
Technical Field
The invention relates to a contaminated soil treatment process.
Background
In a natural environment, according to site survey reports and restoration technical schemes, soil attention pollutants of large sites are divided into five main classes, the first class is semi-volatile organic pollutants (SVOCs), the distribution range of the pollutants is the widest, and polycyclic aromatic hydrocarbons (benzo [ a ] pyrene, benzo [ a ] anthracene, benzo [ b ] fluoranthene, diphenyl [ a, h ] anthracene, indeno [1,2,3-Cd ] pyrene and the like), benzidine and bis (2-chloroethyl) ether are mainly contained; the second category is volatile organic pollutants (VOCs) mainly benzene, vinyl chloride and 1, 2-dichloroethane; the third kind is pesticide, mainly comprising isocarbophos, iprobenfos, tolfenphos and tebuconazole; the fourth is Total Petroleum Hydrocarbons (TPH); the fifth group is heavy metals, mainly nickel.
The field soil pollution condition is more serious, as can be seen from the field soil pollution condition table, the pollution type of the No. X plot is complex, the polycyclic aromatic hydrocarbon pollution is distributed in a large area, all layers are distributed, but a heavy pollution area is concentrated in a 0-2m area, the maximum concentration of benzo [ a ] pyrene is 8.01mg/kg, the maximum concentration of benzo [ a ] anthracene is 9.34mg/kg, and the maximum concentration of benzo [ b ] fluoranthene is 10.27 mg/kg; the pesticide is mainly distributed in a partial area of 0-2m, wherein the concentration of iprobenfos is 1.42mg/kg, the concentration range of isocarbophos is 0.224-33.4 mg/kg, the concentration of metocloprid is 2.22mg/kg, and the concentration of tebuconazole is as high as 21500 mg/kg; the distribution range of VOCs is small, the concentrations of 0-2m benzene at the points of XDNY-71 and XDNY-72 exceed the standard, the concentrations of 2-4 m benzene and 1, 2-dichloroethane at the point of NY-30 exceed the standard, and the concentrations of 7.5-10.5 m chloroethylene at the point of NY-29 exceed the standard. Pollution near NY-34 point in the No. X plot is the most complex, and relates to polycyclic aromatic hydrocarbon, pesticide, nickel and TPH composite pollution, the pollution degree is the heaviest, and the pollution degree of polycyclic aromatic hydrocarbon near XDNY-48 is the heaviest.
Disclosure of Invention
The invention aims to provide a contaminated soil remediation indirect thermal desorption process which is simple in contaminated soil remediation process, high in treatment efficiency and capable of improving the soil structure.
In order to solve the problems, the invention provides an indirect thermal desorption process for repairing contaminated soil, which adds repairing components into the soil and comprises the following steps:
the method comprises the following steps: adding a reinforcer into the polluted soil, wherein the reinforcer comprises: 900 parts of persulfate, 60-180 parts of Fenton reagent, 30-60 parts of ozone, 8-12 parts of hydrogen peroxide and 25-35 parts of potassium permanganate; the persulfate is in a solid state and is directly stirred for use or is prepared into a solution state and then is injected into an aquifer for treating benzene series, halogenated hydrocarbon, nitroaromatic hydrocarbon and phenol organic pollutants in a polluted source region or a polluted plume.
Step two: an activator is also added, the activator comprising: 3-8 parts of alkali, 20-38 parts of ferrous ions and 28-37 parts of hydrogen peroxide, wherein persulfate ions are activated to generate free radical ions with stronger oxidizing capability to oxidize more solid characters of more difficult-to-degrade organic pollutants, the soil polluted by organic matters is heated to the boiling point of the organic matters in a direct or/and indirect heating mode by heating a brick kiln, the soil is discharged and treated, the pollutants are volatilized into gaseous state and then separated, and the treated soil is backfilled for continuous utilization; taking out particulate matter from the tail gas through a filtering device, continuously cooling the tail gas through a quenching device, performing oil-water separation on the cooled material through an oil-water separator, discharging the oil into an oil tank, discharging clean tail gas through a dehydration device, and recovering clean water through a water treatment device;
step three: the medicament reaction is as follows: persulfate salts in water8Ionization to produce persulfate ions S2O2-The standard oxidation-reduction potential of the catalyst is E0 ═ 2.01V, which is close to ozone (E0 ═ 2.07V), the molecule of the catalyst contains peroxy-O-O-, which is a kind of oxidant with strong oxidizability, under the catalysis condition, S is oxidized into the form of the catalyst2O2-Can be activated and decomposed into SO4-，·SO4-contains a lone pair of electrons, and the standard oxidation-reduction potential E0 is +2.60V and is far higher than S2O2-(E0 ═ 2.01V), close to the hydroxyl radical (E0 ═ 2.80V), thus pairingThe organic pollutants have strong degradation capability.
The contaminated soil is heated to a temperature higher than the boiling point of a target pollutant contained in the contaminated soil through heat transfer, the pollutants are selectively gasified and volatilized by controlling the temperature of the system and the residence time of the materials, the pollutants are separated from soil particles, and the volatilized organic pollutants are removed by combustion, condensation or other modes to eliminate the pollution and can repair the site soil polluted by the organic matters.
The soil is heated to the volatilization temperature of the target pollutant, so that the target pollutant is effectively separated from the soil surface or soil gaps, and then extracted to the ground surface by the extraction system for separation treatment.
In the second step, six-phase or three-phase electrode heating is adopted to convert volatile and semi-volatile pollutants in soil and underground water into gas phase, and then a gas phase extraction well is utilized to carry out vacuum extraction on waste gas, wherein the heating temperature is designed to be 70-350 ℃.
The mixing is carried out by adopting two modes of injection and stirring, the medicament is added in a solution form by in-situ injection, the medicament solution or solid state can be added into the polluted soil during in-situ stirring, so as to realize the uniform diffusion and distribution of the remediation medicament in the soil, and the stirring and kneading are carried out for 3-5 h.
Compared with the prior art, the invention has the following advantages.
Adding a reinforcer into the polluted soil, wherein the reinforcer comprises: 900 parts of persulfate, 60-180 parts of Fenton reagent, 30-60 parts of ozone, 8-12 parts of hydrogen peroxide and 25-35 parts of potassium permanganate; adding the compound into polluted soil/underground water, when an oxidant contacts pollutants, chemically decomposing and oxidizing the pollutants into products with lower toxicity or nontoxic products, directly stirring the persulfate to use or preparing the persulfate into a solution state and injecting the solution into an aquifer for treating benzene series, halogenated hydrocarbon, nitroaromatic hydrocarbon and phenol organic pollutants in a polluted source region or a polluted plume, and adding an activating agent, wherein the activating agent comprises: 3-8 parts of alkali, 20-38 parts of ferrous ions and 28-37 parts of hydrogen peroxide, wherein persulfate ions are activated to generate free radical ions with stronger oxidizing capability to oxidize more solid characters of more difficult-to-degrade organic pollutants, the soil polluted by organic matters is heated to the boiling point of the organic matters in a direct or/and indirect heating mode by heating a brick kiln, the soil is discharged and treated, the pollutants are volatilized into gaseous state and then separated, and the treated soil is backfilled for continuous utilization; taking out particulate matters from the tail gas through a filtering device, continuously cooling the tail gas through a quenching device, performing oil-water separation on the cooled urheen through an oil-water separator, discharging the oil into an oil tank, discharging clean tail gas through a dehydration device, and recovering clean water through a water treatment device, wherein the repair period is relatively short after the process is adopted, and the general reaction needs 1-2 months; the repair efficiency is high; when normal position chemical oxidation engineering construction, need not construction such as foundation ditch excavation, precipitation, effectively reduce the engineering degree of difficulty, can handle simultaneously and pollute soil and groundwater, save repair time and place and occupy, strong adaptability: pollutants in soil/groundwater can be treated in combination with chemical oxidation; long-acting: the chemical oxidation effect of the medicament has long duration and can last for 2-3 months; strong oxidizability, broad spectrum: can treat a plurality of refractory compounds. The change of the soil texture is not obvious,
in addition, the equipment is designed in a container type, so that the occupied area is small, and the mobility is strong; the equipment is convenient to assemble, the debugging period is short, and the construction period is saved; the sealing feeding and discharging and micro negative pressure design is safe and reliable, and gas leakage cannot be caused; the automation degree is high, the early warning system is perfect, and the operation management is convenient; has complete waste gas and waste water treatment facilities and no secondary pollution.
Detailed Description
Strong oxidizing agents (such as persulfates, fenton's reagent, ozone, hydrogen peroxide, potassium permanganate, etc.) are added to the contaminated soil/groundwater, and when the oxidizing agent comes into contact with the contaminant, the contaminant is chemically decomposed (oxidized) into less toxic or non-toxic products (such as carbon dioxide, water, or chloride ions, etc.). The main methods of chemical oxidation technology are in-situ chemical oxidation (ISCO) and ex-situ chemical oxidation. Because the in-situ chemical oxidation technology is relatively safe, the in-situ chemical oxidation technology is only considered to be adopted for the polluted underground water of the project.
The medicine mixing in the repairing process can be carried out by adopting two modes of injection and stirring. The in-situ injection adds the medicament in a solution form, and the medicament solution or solid state can be added into the polluted soil during in-situ stirring so as to realize the uniform diffusion and distribution of the remediation medicament in the soil, thereby fully improving the use efficiency of the medicament. Has the following advantages:
the repair period is relatively short, and the general reaction needs 1-2 months; the repair efficiency is high; during in-situ chemical oxidation engineering construction, construction such as foundation pit excavation, precipitation and the like is not needed, so that the engineering difficulty is effectively reduced; meanwhile, the polluted soil and underground water are treated, and the restoration time and the occupied site are saved.
In addition to oxidizing and decomposing pollutants in soil and underground water, the in-situ chemical oxidation can also obviously increase the mass transfer speed between the soil and the underground water in a saturation zone, thereby accelerating the reduction of the total amount of the pollutants. The repairing effect of the technology is influenced by various factors, including pollutant types and concentrations, oxidant types and adding proportions, the transmission of the oxidant in underground water, the change of the demand of the oxidant caused by non-pollutants (such as underground water organic matters, reducing metals and other components), and the like. The selection and injection mode of the chemical oxidation agent are the core problems of the implementation of the chemical oxidation repair technology.
The chemical oxidation agent comprises fenton reagent, potassium permanganate, ozone or activated persulfate and the like. Oxidants such as fenton's reagent, ozone, activated persulfate and the like mainly rely on free radicals (radicals) generated by the oxidants to oxidize organic pollutants. The free radicals have very strong oxidizing ability and can oxidize various organic pollutants, but the oxidizing process is not selective, and the existence time of the free radicals in underground water is very short, so how to effectively inject the oxidizing agent into a repairing area and ensure that the generated free radicals can be timely and fully contacted with the pollutants is very important for the repairing effect.
The chemical oxidation agent is K agent (the main component is persulfate), the solid state can be directly stirred for use, and the K agent can also be prepared into a solution state and then injected into a water-bearing layer for treating benzene series, halogenated hydrocarbon, nitroaromatic hydrocarbon and phenol organic pollutants in a polluted source region or a polluted plume. The adaptability is strong: pollutants in soil/groundwater can be treated in combination with chemical oxidation; long-acting: the chemical oxidation effect of the medicament has long duration and can last for 2-3 months; strong oxidizability, broad spectrum: can treat a plurality of refractory compounds. Has no obvious change to soil texture.
Common activators include high heat, alkali, Fe2+And H2O2And the like, by activating persulfate ions, more refractory organic contaminants can be oxidized by generating more oxidizing free radical ions. Compared with other activation methods, the method has the advantages that the alkali is used as the activation method, and the method is more economical, continuous, safe and effective. The project aims to adopt the medicament B as an activating agent in the in-situ injection (high-pressure rotary spraying) process of the polluted underground water.
The persulfate ionizes in water to produce persulfate ions S2O2-The standard oxidation-reduction potential of the catalyst is E0 ═ 2.01V, which is close to ozone (E0 ═ 2.07V), the molecule of the catalyst contains peroxy-O-O-, which is a kind of oxidant with strong oxidizability, under the catalysis condition, S is oxidized into the form of the catalyst2O2-Can be activated and decomposed into SO4-，·SO4-contains a lone pair of electrons, and the standard oxidation-reduction potential E0 is +2.60V and is far higher than S2O2-(E0 ═ 2.01V), close to hydroxyl radical (E0 ═ 2.80V), and thus have a strong ability to degrade organic pollutants.
The soil polluted by organic matters is heated to a temperature above the boiling point of the organic matters in a direct or indirect heating mode, the pollutants are volatilized into gas, then separation treatment is carried out, and the treated soil can be backfilled for continuous utilization. The thermal desorption technology selectively volatilizes the pollutants by controlling the temperature of the system and the retention time of the materials without damaging the organic pollutants, can effectively remove volatile organic matters such as benzene series, chlorinated solvents, volatilized petroleum hydrocarbon aromatic hydrocarbons and the like, can also effectively remove low-volatility, high-boiling-point and difficult-to-decompose organic pollutants such as polychlorinated biphenyl, dichlorodiphenyl, organochlorine pesticides and dioxin and the like, and can heat and treat the organic pollutants containing various different boiling points once to achieve the target repairing value.
Also through indirect heating's mode, soil can not direct and flame contact, will pollute soil heating to above the boiling point of its target pollutant that contains through thermal transmission, volatilize through control system temperature and material dwell time selective promotion pollutant gasification, reach pollutant and soil particle separation, the organic pollutant of volatilizing can adopt burning, condensation or other modes to eliminate dirty.
Has the following characteristics: the equipment is designed in a container type, so that the occupied area is small, and the mobility is strong; the equipment is convenient to assemble, the debugging period is short, and the construction period is saved; the sealing feeding and discharging and micro negative pressure design is safe and reliable, and gas leakage cannot be caused; the automation degree is high, the early warning system is perfect, and the operation management is convenient; has complete waste gas and waste water treatment facilities and no secondary pollution
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
Claims (6)
1. An indirect thermal desorption process for contaminated soil remediation, which is characterized in that: adding a remediation component to soil, comprising the steps of:
the method comprises the following steps: adding a reinforcer into the polluted soil, wherein the reinforcer comprises: 900 parts of persulfate, 60-180 parts of Fenton reagent, 30-60 parts of ozone, 8-12 parts of hydrogen peroxide and 25-35 parts of potassium permanganate; adding the aqueous solution into polluted soil/underground water, wherein when an oxidant contacts with pollutants, the pollutants are chemically decomposed and oxidized into products with lower toxicity or nontoxic products, persulfate is in a solid state and is directly stirred for use or is prepared into a solution state to be injected into an aquifer for treating benzene series, halogenated hydrocarbon, nitroaromatic hydrocarbon and phenol organic pollutants in a polluted source region or a polluted plume;
step two: an activator is also added, the activator comprising: 3-8 parts of alkali, 20-38 parts of ferrous ions and 28-37 parts of hydrogen peroxide, wherein persulfate ions are activated to generate free radical ions with stronger oxidizing capability to oxidize more solid characters of more difficult-to-degrade organic pollutants, the soil polluted by organic matters is heated to the boiling point of the organic matters in a direct or/and indirect heating mode by heating a brick kiln, the soil is discharged and treated, the pollutants are volatilized into gaseous state and then separated, and the treated soil is backfilled for continuous utilization; taking out particulate matter from the tail gas through a filtering device, continuously cooling the tail gas through a quenching device, performing oil-water separation on the cooled material through an oil-water separator, discharging the oil into an oil tank, discharging clean tail gas through a dehydration device, and recovering clean water through a water treatment device;
step three: the medicament reaction is as follows: persulfate salts in water8Ionization to produce persulfate ions S2O2-The standard oxidation-reduction potential of the catalyst is E0 ═ 2.01V, which is close to ozone (E0 ═ 2.07V), the molecule of the catalyst contains peroxy-O-O-, which is a kind of oxidant with strong oxidizability, under the catalysis condition, S is oxidized into the form of the catalyst2O2-Can be activated and decomposed into SO4-，·SO4-contains a lone pair of electrons, and the standard oxidation-reduction potential E0 is +2.60V and is far higher than S2O2-(E0 ═ +2.01V), close to the hydroxyl radical (E0 ═ 2.80V).
2. The contaminated soil remediation indirect thermal desorption process of claim 1, wherein: the contaminated soil is heated to a temperature higher than the boiling point of a target pollutant contained in the contaminated soil through heat transfer, the pollutants are selectively gasified and volatilized by controlling the temperature of the system and the residence time of the materials, the pollutants are separated from soil particles, and the volatilized organic pollutants are removed by combustion, condensation or other modes to eliminate the pollution and can repair the site soil polluted by the organic matters.
3. The contaminated soil remediation indirect thermal desorption process of claim 1, wherein: the soil is heated to the volatilization temperature of the target pollutant, so that the target pollutant is effectively separated from the soil surface or soil gaps, and then extracted to the ground surface by the extraction system for separation treatment.
4. The contaminated soil remediation indirect thermal desorption process of claim 1, wherein: in the second step, six-phase or three-phase electrode heating is adopted to convert volatile and semi-volatile pollutants in soil and underground water into gas phase, and then a gas phase extraction well is utilized to carry out vacuum extraction, collection and treatment on waste gas.
5. The contaminated soil remediation indirect thermal desorption process of claim 1, wherein: the heating temperature is designed to be 70-350 ℃.
6. The contaminated soil remediation indirect thermal desorption process of claim 1, wherein: the mixing is carried out by adopting two modes of injection and stirring, the medicament is added in a solution form by in-situ injection, the medicament solution or solid state can be added into the polluted soil during in-situ stirring, so as to realize the uniform diffusion and distribution of the remediation medicament in the soil, and the stirring and kneading are carried out for 3-5 h.
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| CN114192566A (en) * | 2021-12-07 | 2022-03-18 | 南京万德斯环保科技股份有限公司 | Process for efficiently repairing organic contaminated soil |
| CN115716083A (en) * | 2022-10-09 | 2023-02-28 | 常州大学 | Harmless and recycling treatment method for petroleum-polluted soil |
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Application publication date: 20200918 |
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| RJ01 | Rejection of invention patent application after publication |