CN110576032B - Method for degrading polycyclic aromatic hydrocarbon in soil by adopting mechanochemical method - Google Patents
Method for degrading polycyclic aromatic hydrocarbon in soil by adopting mechanochemical method Download PDFInfo
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- CN110576032B CN110576032B CN201910808636.1A CN201910808636A CN110576032B CN 110576032 B CN110576032 B CN 110576032B CN 201910808636 A CN201910808636 A CN 201910808636A CN 110576032 B CN110576032 B CN 110576032B
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Abstract
The invention provides a method for degrading polycyclic aromatic hydrocarbon in soil by adopting a mechanochemical method, which is used for solving the problem of higher cost of the existing chemical remediation technology. The method comprises the steps of naturally drying soil polluted by polycyclic aromatic hydrocarbon, and putting the soil into a ball mill with grinding balls, wherein the ball-to-material ratio is 10-20: 1; simultaneously adding a double-ball-milling main agent consisting of a solid oxidant and reduced iron powder and a ball-milling auxiliary agent into a grinding tank, grinding at a set rotating speed for a set time, and discharging after ball milling is finished so as to achieve the purpose of degrading organic pollutants; wherein, the solid oxidant is one or more of percarbamide, percarbonate, carbamide peroxide and calcium peroxide; the method has the characteristics of low degradation cost, environmental friendliness, convenience, high efficiency and the like.
Description
Technical Field
The invention belongs to the field of soil remediation application, and particularly relates to a method for degrading polycyclic aromatic hydrocarbons in soil by adopting a mechanochemical method.
Background
Polycyclic Aromatic Hydrocarbons (PAHs) are a class of hydrocarbons with carcinogenic, teratogenic, and mutagenic properties. With the development of industry, PAHs discharged in large quantity are enriched in soil under the action of dry sedimentation and wet sedimentation, and the pollution to the soil environment is increasingly serious, so that an effective method for treating the PAHs is urgently required to be searched.
At present, the common PAHs polluted soil remediation technologies include a physical remediation technology, a biological remediation technology and a chemical remediation technology.
The physical remediation technology is mainly used for removing or separating various organic pollutants in soil by physical means, and the remediation technology is high in cost and cannot really achieve the purpose of eliminating the pollutants from the environment.
Although the bioremediation technology is low in cost, it is susceptible to factors such as soil quality and environment, and the processing capacity is unstable.
The chemical remediation technology refers to the oxidation, reduction, catalysis and the like of some chemical substances, which can convert or degrade the pollutants in the soil into low-toxicity or non-toxic substances, and currently, a chemical oxidation method, an electrochemical remediation method and a sonochemical remediation method are mainly adopted; the chemical oxidation method has the characteristics of convenience and high degradation efficiency, but has the problems of large oxidant input amount, long repair time and high cost in actual repair; while the electrochemical repair method and the sonochemical repair method belong to a green repair technology, have small risk of secondary pollution and are environment-friendly, but have the problems of high energy consumption and high cost.
Disclosure of Invention
The invention aims to solve the problems of high cost and long restoration time of the existing chemical restoration technology, and provides a method for degrading polycyclic aromatic hydrocarbon in soil by adopting a mechanochemical method.
In order to achieve the purpose, the technical solution provided by the invention is as follows:
a method for degrading polycyclic aromatic hydrocarbon in soil by adopting a mechanochemical method is characterized by comprising the following steps:
1) air-drying the soil polluted by the polycyclic aromatic hydrocarbon, placing the soil in a ball mill, wherein the ball-to-material ratio is 10-20: 1, and when the balls and the soil are prepared according to the proportion, the ball milling effect is good;
2) adding a ball milling main agent and a ball milling auxiliary agent into a ball mill, and grinding;
the ball milling main agent comprises a solid oxidant and reduced iron powder;
the solid oxidant is one or more of percarbamide, percarbonate, carbamide peroxide and calcium peroxide;
3) and discharging after the ball milling is finished.
Further, in the step 2), the addition amount of the ball milling main agent is 5.00-30.00% of the mass of the polluted soil; the mass ratio of the solid oxidant to the reduced iron powder is 4-12: 1; in the feeding range, most of polycyclic aromatic hydrocarbon pollutants in soil can be effectively removed without increasing the cost, and the economical efficiency is better.
Further, in the step 2), the ball-milling auxiliary agent is quartz sand, has high hardness and can help grinding, and simultaneously can generate free radicals which can strengthen mechanochemical reaction together with the ball-milling main agent; the mass ratio of the ball milling main agent to the ball milling auxiliary agent is 2-5: 1.
Further, in the step 1), the soil polluted by the polycyclic aromatic hydrocarbon is naturally air-dried to enable the water content of the soil to be lower than 15%, and after impurity removal and sterilization, the soil is crushed and sieved by a 60-mesh sieve, so that the subsequent operation is facilitated, and the removal effect of pollutants can be improved.
Furthermore, the rotating speed of the ball mill is 300 rpm-800 rpm, and the grinding time is 2.0 h-12.0 h.
Further, the ball mill adopts a planetary ball mill.
Further, in the step 1) and the step 3), a gas chromatography-mass spectrometer is adopted to analyze the concentration content of the polycyclic aromatic hydrocarbon in the soil, namely the concentration content of the polycyclic aromatic hydrocarbon in the soil is analyzed before and after grinding, and the concentration content is used for calculating the degradation rate and screening out the optimal degradation condition.
The principle of the invention is as follows:
the polycyclic aromatic hydrocarbon in the soil is rapidly degraded by a mechanochemical method under a double-ball-milling main agent system matched with a solid oxidant and reduced iron powder. In the high-speed fine grinding process, material particles are continuously refined, so that a huge surface effect is generated, and the activity of chemical reaction is greatly increased along with continuous generation of new unsaturated bonds, free ions and electrons. Meanwhile, under the action of mechanical force, covalent bonds on the surface of the material crystal are broken to generate new active centers, the material crystal can be disordered due to the defect of the material crystal, and the ordered structure of the crystal lattice of the material is distorted along with the extension of grinding force or time to form a crystal lattice defect and generate an amorphous layer, so that organic matters are decomposed and the purpose of degradation is achieved. On one hand, the solid oxidant can release free radicals with strong oxidizing property, on the other hand, the reduced iron powder in the reaction system and the free radicals of the solid oxidant can form a system similar to Fenton, under the double actions of mechanochemical action and Fe catalytic action, the solid oxidant is promoted to be decomposed to generate more peroxy radicals, and the peroxy radicals can gradually oxidize and degrade macromolecular organic pollutants into nontoxic CO2、H2Small molecular compounds such as O, and the like, thereby achieving the purpose of degradationThe purpose is.
The invention has the advantages that:
the invention adopts the solid oxidant and the reduced iron powder as the main ball-milling agent, and accelerates the mechanochemical method for decomposing the high-concentration polycyclic aromatic hydrocarbon in the soil under the ball-milling system simultaneously containing the ball-milling auxiliary agent, the method has simple operation and lower cost, only needs to be mixed together for ball milling, greatly reduces the repair time, reduces the energy consumption, fully exerts the characteristic of high disposal capability of the mechanochemical method, realizes the rapid and full degradation treatment of the high-concentration polycyclic aromatic hydrocarbon pollutant in the complex environment of the soil, and provides a feasible technology for repairing the persistent organic pollutant of the soil. Meanwhile, the double-ball-milling main agent is adopted as the main additive, so that the degradation effect is better, the overall economy is better, and the double-ball-milling main agent is used as the optimal exogenous additive to provide reference for laboratory research and practical application.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples:
in order to facilitate the researchers to quickly perform the targeted test, the following examples all adopt self-made contaminated soil as the test soil sample.
Selecting Shanxi yellow cotton soil as test soil, naturally drying the yellow cotton soil to ensure that the water content is lower than 15%, removing impurities and sterilizing, sieving by a 60-mesh sieve, adding a certain amount of mixed solution of naphthalene, fluoranthene, pyrene and acetone (the mass ratio of the naphthalene, fluoranthene and pyrene to the acetone is 1:2), placing the mixed solution in a dark environment, and preparing a polluted soil sample after the acetone is completely volatilized. And (5) aging the polluted soil for one month, and storing for later use. The actual content of polycyclic aromatic hydrocarbon in the aging-polluted soil is measured by adopting a gas chromatography-mass spectrometer (GCMS), and the results are 284mg/kg of naphthalene, 361mg/kg of fluoranthene and 309mg/kg of pyrene.
Example one
The method for degrading the polycyclic aromatic hydrocarbon in the soil by adopting a mechanochemical method comprises the following steps:
1) putting 20 parts of polluted soil into a planetary ball mill, and adding agate grinding balls according to the ball-to-material ratio of 10: 1;
2) adding 0.80 part of carbamide peroxide, 0.20 part of reduced iron powder and 0.50 part of ball-milling auxiliary agent quartz sand into a ball mill, and carrying out ball milling for 4.0h at the rotating speed of 300 rpm;
3) discharging after ball milling is finished, and analyzing the residual concentration of the polycyclic aromatic hydrocarbon in the soil by adopting GCMS (GCMS), wherein the content of naphthalene in the soil is 104.1mg/kg, the content of fluoranthene in the soil is 98.8mg/kg, and the content of pyrene in the soil is 103.6 mg/kg.
Example two
The method for degrading the polycyclic aromatic hydrocarbon in the soil by adopting a mechanochemical method comprises the following steps:
1) putting 20 parts of polluted soil into a planetary ball mill, and adding agate grinding balls according to the ball-to-material ratio of 20: 1;
2) adding 0.90 part of carbamide peroxide, 0.10 part of reduced iron powder and 0.20 part of milling auxiliary agent quartz sand into a ball mill, and performing ball milling for 6.0h at the rotating speed of 500 rpm;
3) discharging after ball milling is finished, and analyzing the residual concentration of the polycyclic aromatic hydrocarbon in the soil by adopting GCMS (GCMS), wherein naphthalene is 80.4mg/kg, fluoranthene is 95.3mg/kg, and pyrene is 93.1 mg/kg.
EXAMPLE III
The method for degrading the polycyclic aromatic hydrocarbon in the soil by adopting a mechanochemical method comprises the following steps:
1) putting 20 parts of polluted soil into a planetary ball mill, and adding agate grinding balls according to the ball-to-material ratio of 15: 1;
2) adding 2.40 parts of carbamide peroxide, 0.60 part of reduced iron powder and 1.0 part of ball-milling auxiliary agent quartz sand into a ball mill, and carrying out ball milling for 2.0h at the rotating speed of 600 rpm;
3) discharging after ball milling is finished, and analyzing the residual concentration of the polycyclic aromatic hydrocarbon in the soil by adopting GCMS (GCMS), wherein the content of naphthalene in the soil is 69.1mg/kg, the content of fluoranthene in the soil is 72.8mg/kg, and the content of pyrene in the soil is 75.2 mg/kg.
Example four
The method for degrading the polycyclic aromatic hydrocarbon in the soil by adopting a mechanochemical method comprises the following steps:
1) putting 20 parts of polluted soil into a planetary ball mill, and adding agate grinding balls according to the ball-to-material ratio of 10: 1;
2) adding 2.70 parts of calcium peroxide as a main ball-milling agent, 0.30 part of reduced iron powder and 1.50 parts of ball-milling auxiliary agent quartz sand into a ball mill, and carrying out ball milling for 12 hours at the rotating speed of 300 rpm;
3) discharging after ball milling is finished, and analyzing the residual concentration of the polycyclic aromatic hydrocarbon in the soil by adopting GCMS, wherein naphthalene is 61.3mg/kg, fluoranthene is 62.1mg/kg, and pyrene is 58.3 mg/kg.
EXAMPLE five
The method for degrading the polycyclic aromatic hydrocarbon in the soil by adopting a mechanochemical method comprises the following steps:
1) putting 20 parts of polluted soil into a planetary ball mill, and adding agate grinding balls according to the ball-to-material ratio of 15: 1;
2) adding 5.25 parts of carbamide peroxide as a main ball-milling agent, 0.75 part of reduced iron powder and 3.0 parts of quartz sand as a ball-milling auxiliary agent into a ball mill, and carrying out ball milling for 4 hours at the rotating speed of 400 rpm;
3) discharging after ball milling is finished, and analyzing the residual concentration of polycyclic aromatic hydrocarbon in the soil by adopting GCMS, wherein naphthalene is 48.9mg/kg, fluoranthene is 56.4mg/kg, and pyrene is 53.8 mg/kg.
EXAMPLE six
The method for degrading the polycyclic aromatic hydrocarbon in the soil by adopting a mechanochemical method comprises the following steps:
1) putting 20 parts of polluted soil into a planetary ball mill, and adding agate grinding balls according to the ball-to-material ratio of 15: 1;
2) adding 4.00 parts of percarbamide, 1.53 parts of carbamide peroxide, 0.47 part of reduced iron powder and 3.0 parts of quartz sand serving as a ball-milling auxiliary agent into a ball mill, and carrying out ball milling for 8 hours at the rotating speed of 400 rpm;
3) discharging after ball milling is finished, and analyzing the residual concentration of the polycyclic aromatic hydrocarbon in the soil by adopting GCMS (GCMS), wherein naphthalene is 45.2mg/kg, fluoranthene is 49.1mg/kg, and pyrene is 47.3 mg/kg.
According to the detection results of the embodiments, when the method is used for soil remediation, the amount of the added ball milling main agent and the amount of the added ball milling auxiliary agent are very small, the input cost of materials can be greatly reduced, the remediation time is short, the remediation effect is good (namely, more than 60% of polycyclic aromatic hydrocarbon in soil can be degraded through short-time remediation for 2-12 hours, the efficiency is high), and the method has a certain reference value for laboratory research and practical application.
While the invention has been described with reference to specific embodiments, the invention is not limited thereto, and various equivalent modifications or substitutions can be easily made by those skilled in the art within the technical scope of the present disclosure.
Claims (5)
1. A method for degrading polycyclic aromatic hydrocarbon in soil by adopting a mechanochemical method is characterized by comprising the following steps:
1) air-drying the soil polluted by the polycyclic aromatic hydrocarbon, and putting the soil into a ball mill with a ball-to-material ratio of 10-20: 1;
the air-drying degree of the soil is that the water content of the soil is lower than 15%;
2) adding a ball milling main agent and a ball milling auxiliary agent into a ball mill, and grinding;
the addition amount of the ball milling main agent is 5.00-30.00% of the mass of the soil polluted by the polycyclic aromatic hydrocarbon; the ball-milling auxiliary agent is quartz sand; the mass ratio of the ball milling main agent to the ball milling auxiliary agent is 2-5: 1;
the ball milling main agent comprises a solid oxidant and reduced iron powder, and the mass ratio of the solid oxidant to the reduced iron powder is 4-12: 1;
the solid oxidant is one or more of percarbamide, percarbonate, carbamide peroxide and calcium peroxide;
3) and discharging after the ball milling is finished.
2. The method for degrading polycyclic aromatic hydrocarbons in soil by adopting the mechanochemical method according to claim 1, wherein the method comprises the following steps:
in the step 1), after impurity removal and sterilization, crushing and sieving by a 60-mesh sieve.
3. The method for degrading polycyclic aromatic hydrocarbons in soil by adopting the mechanochemical method according to claim 2, wherein the method comprises the following steps: the rotation speed of the ball mill is 300-800 rpm, and the grinding time is 2.0-12.0 h.
4. The method for degrading polycyclic aromatic hydrocarbons in soil by using a mechanochemical method according to claim 3, wherein: the ball mill adopts a planetary ball mill.
5. The method for degrading polycyclic aromatic hydrocarbons in soil by adopting the mechanochemical method according to claim 1, wherein the method comprises the following steps: and analyzing the concentration content of the polycyclic aromatic hydrocarbon in the soil by adopting a gas chromatography-mass spectrometer in both the step 1) and the step 3).
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