CN111346909B - Petroleum hydrocarbon contaminated soil in-situ remediation method based on foam enhancement - Google Patents
Petroleum hydrocarbon contaminated soil in-situ remediation method based on foam enhancement Download PDFInfo
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- CN111346909B CN111346909B CN202010100299.3A CN202010100299A CN111346909B CN 111346909 B CN111346909 B CN 111346909B CN 202010100299 A CN202010100299 A CN 202010100299A CN 111346909 B CN111346909 B CN 111346909B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
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Abstract
The invention provides an in-situ remediation method for petroleum hydrocarbon contaminated soil based on foam enhancement. Mixing Tween 80 with water, and stirring uniformly to prepare a solubilizer solution, wherein the proportion range of the volume (mL) of Tween 80 to the volume (L) of water is as follows: (1-100) to 1; adding pyrocatechol and ferrous sulfate into a prepared solubilizer solution, wherein the mass (g) of the pyrocatechol, the mass (g) of the ferrous sulfate and the volume (L) of the solubilizer solution are in the range of 1 to (2-8) to (0.01-1), uniformly stirring to obtain a solubilizing activator solution, and foaming the solubilizing activator solution; injecting the prepared foam into soil along the foam injection well; uniformly mixing sodium percarbonate and water to prepare a sodium percarbonate aqueous solution, wherein the ratio of the mass (g) of the sodium percarbonate to the volume (L) of the water is as follows: (50-300) to 1; an aqueous sodium percarbonate solution is injected into the soil along a foam injection well.
Description
Technical Field
The invention relates to the field of soil remediation, in particular to an in-situ remediation method for petroleum hydrocarbon contaminated soil based on foam enhancement.
Background
Soil is an important component of ecological environment, is one of main resources on which human beings live, and is particularly important for countries with a large number of people in China. Petroleum has become one of the most important energy sources for human beings, and as the demand of petroleum products increases, a large amount of petroleum and processed products thereof enter soil, so that the petroleum pollution to the soil is more and more serious, which has become a worldwide environmental problem.
In the processes of petroleum production, storage and transportation, refining, processing and use, petroleum overflows and is discharged due to accidents, abnormal operation, maintenance and the like, so that the environment (soil, ground and underground water) is polluted. At present, more than 400 oil fields and oil-gas fields which are explored and developed in China are distributed in 25 provincial and municipal districts and autonomous regions in China, and the main working range of the oil fields is nearly 20 km and ten thousand km2The area of the covered area reaches 32 km2About 3% of the total area of the land, wherein 480 ten thousand hm2The oil content of the land may exceed safe values. In China, the current annual oil yield exceeds 1.8X 1011kg, 1.0 x 10 of newly polluted soil every year8And (kg). The data show that the oil pollution intensity can reach 1 for oil well site soil which stably runs for about 5 years.0×103～1.0×104mg/kg, the content of petroleum hydrocarbon in the soil of the main petrochemical and oil field areas in China is up to 5 to 9.4 percent, and the content of petroleum hydrocarbon in the soil near the well mouth of the petroleum exploitation area is 5.3 to 7.5 percent.
The petroleum pollutants can block soil pores, reduce the air permeability and water permeability of the soil, kill microorganisms in the soil, change soil components and cause changes of soil microbial communities and local systems. The petroleum pollutants can also disturb the normal growth and development of crops, reduce the lodging resistance and insect pest resistance of the crops and cause the large-scale yield reduction of grains. In addition, some components in petroleum hydrocarbon can generate carcinogenic, teratogenic and mutagenic effects after entering animals or human bodies through biological enrichment, for example, fused ring aromatic hydrocarbon can cause carcinogenic and mutagenic effects, benzene series can cause anemia, blood leukemia and the like.
The petroleum polluted soil remediation technology can be basically divided into three types in nature, namely: physical, biological and chemical techniques. The physical repair technology comprises the following steps: soil-changing method, photocatalysis method, soil gas-phase extraction method, hot-melting vitrification method and incineration method. Although the physical repair technology is fast, the energy consumption is high, and the physical repair technology does not fundamentally solve the pollution problem. The main principle of the bioremediation technology is as follows: certain plants or microorganisms have a degrading effect on certain soil pollutants and these organisms can break down the pollutants by metabolism. Bioremediation techniques are generally applicable to the remediation of soils with low levels of contamination. Microorganisms are difficult to survive under high pollution conditions, and thus the removal capacity of soil pollutants is limited. The bioremediation technology is sensitive to the soil environment, and has long remediation period and poor stability. Chemical remediation techniques involve the addition of chemical agents to the soil that contact and interact with the contaminants, ultimately causing the contaminants in the soil to be oxidized, reduced, separated, decomposed, or otherwise converted or even removed. The chemical repairing method comprises the following steps: chemical oxidation, solvent solubilization, leaching and washing, etc. The chemical oxidation method is to add an oxidant into the soil and remove soil pollutants through oxidation reaction. Compared with physical and biological remediation technologies, the chemical oxidation remediation technology has the advantages of high remediation speed, low requirements on soil application conditions, wide application range on pollutant types and pollution degrees, capability of treating petroleum-polluted soil with high pollution degree and the like, but the chemical method needs to consume a large amount of chemicals, has high treatment cost, and is easy to cause secondary pollution due to chemical residue.
In conclusion, the prior art still does not perfectly solve the problem of repairing the petroleum-polluted soil.
Disclosure of Invention
The invention aims to provide an in-situ remediation method of petroleum hydrocarbon contaminated soil based on foam enhancement, which is characterized by comprising the following steps:
1) constructing a foam injection well at the central position of a petroleum hydrocarbon polluted site;
2) foaming treatment
2.1) uniformly mixing Tween 80 with water to prepare a solubilizer solution;
2.2) adding pyrocatechol and ferrous sulfate into the solubilizer solution prepared in the step 2.1) to obtain a solubilizing activator solution;
2.3) foaming the solubilizing activator solution;
2.4) injecting the foam prepared in the step 2.3) into soil along the foam injection well in the step 1);
3) chemical oxidation treatment of soil
3.1) uniformly mixing sodium percarbonate and water to prepare a sodium percarbonate aqueous solution;
3.2) injecting the sodium percarbonate aqueous solution prepared in the step 3.1) into soil along the foam injection well in the step 1) to finish remediation.
Further, in the step 1), the inner diameter of the wellhead of the foam injection well ranges from 0.01 to 1 (in m), and the soil volume V which can be processed by each foam injection well is S multiplied by H multiplied by C (in m)3) Wherein S is the area of the field (in m)2) H is the depth (unit is m) of a foam injection well, C is an inspection coefficient, and the value range is 0.1-1;
further, in step 2.1), when tween 80 and water are uniformly mixed to prepare the solubilizer solution, the ratio of the volume (mL) of tween 80 to the volume (L) of water is in the range: (1-100) to 1;
further, in the step 2.2), when the catechol and the ferrous sulfate are added into the solubilizer solution prepared in the step 2.1), the mass (g) of the catechol, the mass (g) of the ferrous sulfate and the volume (L) of the solubilizer solution are in the range of 1: 2-8: 0.01-1, and the solubilizing activator solution is obtained by uniformly stirring;
further, in the step 2.3), when the solubilization activator solution is foamed, the aeration stone is placed in the solubilization activator solution and air is introduced to generate foam, wherein the air flow range is 1.8L/min-200L/min, and the pore size range of the aeration stone is 0.1 mm-10 mm.
Further, in the step 2.4), when the foam prepared in the step 2.3) is injected into soil along the foam injection well in the step 1), the ratio of the petroleum hydrocarbon concentration (mg/kg) of each cubic meter of soil to the volume (L) of the solubilizing activator solution to be injected into each cubic meter of soil is 125: 1-2, namely for the soil with the petroleum hydrocarbon concentration of 10000mg/kg, 80-160L of solubilizing activator solution is injected into each cubic meter of soil; the volume of soil for each foam injection well was determined as described above for V ═ sxh × C.
Further, in the step 3.1), when sodium percarbonate is uniformly mixed with water to prepare a sodium percarbonate aqueous solution, the ratio of the mass (g) of the sodium percarbonate to the volume (L) of the water is in the range: (50-300): 1.
Further, in the step 3.2), when the sodium percarbonate aqueous solution prepared in the step 3.1) is injected into soil along the foam injection well in the step 1), the ratio of the concentration (mg/kg) of petroleum hydrocarbon in each cubic meter of soil to the volume (L) of the sodium percarbonate aqueous solution to be injected in each cubic meter of soil is 50: 1-5, namely, 200-1000L of the sodium percarbonate aqueous solution is injected into each cubic meter of soil with the concentration of the petroleum hydrocarbon of 10000 mg/kg. The volume of soil for each foam injection well was determined as described above for V ═ sxh × C.
The technical effects of the present invention are undoubted, and the present invention has the following advantages:
1) the method is generally used for treating the polluted soil with the total petroleum hydrocarbon concentration of 20000mg/kg or less, and the removal rate of the petroleum hydrocarbon in the polluted soil can reach more than 60 percent within 24 hours.
2) Catechol, also known as catechol, is extracted from CatechuThe compound exists widely in nature in the form of derivatives, can complex ferrous ions, and has acidic aqueous solution. In the invention, the ferrous catechol complex is carried into the soil by the Tween 80 foam, so that the desorption process of petroleum hydrocarbon in the soil environment is enhanced on one hand, and the ferrous catechol is more uniformly distributed in the polluted soil on the other hand. After the sodium percarbonate aqueous solution is injected into soil, ferrous ions can catalyze hydrogen peroxide released by sodium percarbonate to form Fenton reaction to remove petroleum hydrocarbon pollutants, and H generated in the aqueous solution and the petroleum hydrocarbon degradation process+Can be mixed with CO3 2-Reaction to CO2And OH produced by Fenton reaction-Neutralizing the produced water to produce CO2The gas can drive the surfactant solution in the soil to generate foam for the second time, and the mass transfer of the medicament is enhanced. After remediation, only the phenolate and tween 80 remain in the soil, and tween 80 is easily biodegradable.
Drawings
FIG. 1 is a flow chart of a process for foam-enhanced in-situ remediation of petroleum-contaminated soil.
Detailed Description
The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
An in-situ remediation method for petroleum hydrocarbon contaminated soil based on foam enhancement is characterized by comprising the following steps:
1) the embodiment is completed by the petroleum hydrocarbon polluted soil in-situ remediation simulation device constructed in a laboratory according to the invention. The simulation restoration device is a cuboid with the length of 25cm, the width of 5cm and the height of 5cm, 800g of artificially prepared polluted soil is contained, the pollution concentration of petroleum hydrocarbon is 14749mg/kg, foam is injected from the bottom end of the cuboid in the length direction, the injection well is 4cm in depth, and the inner diameter is 1 cm.
2) Foaming treatment
2.1) the foam generating pool adopted in the embodiment is a cylinder with the inner diameter of 15cm and the height of 50cm, 1mL of Tween 80 and 0.05L of water are placed in the cylinder for mixing, and the mixture is uniformly stirred to prepare a solubilizer solution;
2.2) adding 0.55g of catechol and 1.39g of ferrous sulfate into the solubilizer solution prepared in the step 2.1), and uniformly stirring to obtain a solubilizing activator solution;
2.3) placing the aerated stone in the solubilization activator solution obtained in the step 2.2) and introducing air to generate foam, wherein the air flow is 5L/min, and the average pore diameter of the aerated stone is 1 mm.
2.4) injecting all foams prepared in the step 2.3) into soil along the foam injection well in the step 1);
3) chemical oxidation treatment of soil
3.1) uniformly mixing 62.8g of sodium percarbonate and 0.45L of water to prepare a sodium percarbonate aqueous solution;
3.2) injecting the sodium percarbonate aqueous solution prepared in the step 3.1) into the soil along the foam injection well in the step 1), wherein the petroleum hydrocarbon concentration in the soil after 24 hours is 5304mg/kg, and the degradation rate is 64%.
Claims (4)
1. An in-situ remediation method for petroleum hydrocarbon contaminated soil based on foam enhancement is characterized by comprising the following steps:
1) constructing a foam injection well at the central position of a petroleum hydrocarbon polluted site; the value range of the inner diameter of a wellhead of the foam injection well is 0.01-1, and the unit is m;
2) foaming treatment:
2.1) uniformly mixing Tween 80 with water to prepare a solubilizer solution;
2.2) adding pyrocatechol and ferrous sulfate into the solubilizer solution prepared in the step 2.1) to obtain a solubilizing activator solution;
2.3) introducing air to foam the solubilizing activator solution;
2.4) injecting the foam prepared in the step 2.3) into soil along the foam injection well in the step 1);
3) chemical oxidation treatment of soil:
3.1) uniformly mixing sodium percarbonate and water to prepare a sodium percarbonate aqueous solution;
3.2) injecting the sodium percarbonate aqueous solution prepared in the step 3.1) into soil along the foam injection well in the step 1) to finish remediation.
2. The in-situ remediation method for petroleum hydrocarbon contaminated soil based on foam enhancement as claimed in claim 1, wherein:
in the step 1), the value range of the inside diameter of a wellhead of the foam injection well is 0.01-1, the unit is m, the soil volume which can be processed by each foam injection well is V = S multiplied by H multiplied by C, and the unit of V is m3Wherein S is the area of the field, and the unit of S is m2H is the depth of a foam injection well, the unit of H is m, C is an inspection coefficient, and the value range is 0.1-1.
3. The in-situ remediation method for petroleum hydrocarbon contaminated soil based on foam enhancement as claimed in claim 2, wherein: in the step 2.4), when the foam prepared in the step 2.3) is injected into soil along the foam injection well in the step 1), the ratio of the petroleum hydrocarbon concentration of each cubic meter of soil to the volume of the solubilizing activator solution to be injected into each cubic meter of soil is 125: 1-2, the unit of the petroleum hydrocarbon concentration of each cubic meter of soil is mg/kg, and the unit of the volume of the solubilizing activator solution is L.
4. The in-situ remediation method for petroleum hydrocarbon contaminated soil based on foam enhancement as claimed in claim 1 or 3, wherein: in the step 3.2), when the sodium percarbonate aqueous solution prepared in the step 3.1) is injected into soil along the foam injection well in the step 1), the ratio of the petroleum hydrocarbon concentration of each cubic meter of soil to the volume of the sodium percarbonate aqueous solution to be injected into each cubic meter of soil is 50 to (1-5), the unit of the volume of the sodium percarbonate aqueous solution is L, and the unit of the petroleum hydrocarbon concentration of each cubic meter of soil is mg/kg.
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