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CN112872015B - Method for restoring and treating phthalate-polluted soil by pulse electrochemical production of hydrogen peroxide - Google Patents

Method for restoring and treating phthalate-polluted soil by pulse electrochemical production of hydrogen peroxide Download PDF

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Publication number
CN112872015B
CN112872015B CN202110031821.1A CN202110031821A CN112872015B CN 112872015 B CN112872015 B CN 112872015B CN 202110031821 A CN202110031821 A CN 202110031821A CN 112872015 B CN112872015 B CN 112872015B
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phthalate
soil
aqueous solution
hydrogen peroxide
bicarbonate
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CN112872015A (en
Inventor
刘坤
何辉超
杨杉
柯改利
李洪刚
程敏
范例
李雨桐
王健
曾磊
周炼川
宾灯辉
苏毅
尹华
张艺
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Chongqing Academy Of Eco-Environmental Sciences
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Chongqing Academy Of Eco-Environmental Sciences
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/08Reclamation of contaminated soil chemically
    • B09C1/085Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C2101/00In situ

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention relates to a method for restoring and treating phthalate ester contaminated soil by pulse electrochemical hydrogen peroxide generation, and belongs to the technical field of soil restoration. The method specifically comprises the following steps: the method comprises the steps of crushing the phthalate polluted soil, adding the crushed phthalate polluted soil into an aqueous solution containing bicarbonate radical, uniformly mixing, inserting two carbon electrodes, and applying square-wave pulse voltage to the two carbon electrodes to carry out electrochemical restoration treatment. According to the method, air does not need to be introduced into the soil, a reaction electrode does not need to be replaced regularly, dissolved bicarbonate in the soil is activated through electrochemistry, water is mediated to be oxidized into hydrogen peroxide, and therefore the phthalate polluted soil is continuously and efficiently repaired and treated.

Description

Method for restoring and treating phthalate-polluted soil by pulse electrochemical generation of hydrogen peroxide
Technical Field
The invention belongs to the technical field of soil remediation, and particularly relates to a method for remediating phthalate-contaminated soil by pulse electrochemical generation of hydrogen peroxide.
Background
Phthalate compounds are important chemical raw materials and are widely used in the fields of plasticizers, pesticide carriers and the like. At the initial stage of the application of phthalate compounds, scholars at home and abroad mostly consider that the phthalate compounds have low toxicity and no side effect on human health and ecological environment, so the phthalate compounds are widely produced and applied. Since 2000, a number of studies have found that: various phthalates (e.g., diisononyl phthalate, di-n-butyl phthalate, dimethyl phthalate, etc.) enriched in animals have a risk of causing gene mutation, tissue carcinogenesis and teratogenicity. Unfortunately, agricultural mulching films used in large quantities in early stages of China contain phthalate components, which cause large-area agricultural soil pollution. Because the phthalic acid ester in the soil is difficult to biodegrade, the effective remediation treatment is urgently needed for the soil pollution caused by the phthalic acid ester.
At present, the main methods for remedying the phthalate ester contaminated soil are phytoremediation (such as alfalfa planting remediation), microbial remediation (such as yeast degradation remediation), chemical oxidation remediation (such as activated persulfate oxidation remediation, photocatalytic oxidation degradation remediation and the like), and physical adsorption remediation (such as charcoal adsorption remediation). The above methods have different repairing principles, and have long and insufficient effects. For example, phytoremediation methods are simple to operate, but the planting period is long, which affects normal agricultural production; the microorganism remediation method has good selectivity, but the cost for culturing microorganisms is high, and the requirements on soil temperature, humidity, components and the like are strict; the chemical oxidation repairing method needs to add an oxidant, has higher cost and is easy to introduce new pollutants; the physical adsorption repair method has the disadvantages of slow speed and limited effect. Therefore, it is very necessary to develop a new method for the remediation of phthalate-contaminated soil.
The electro-Fenton oxidation method is an advanced oxidation technology for effectively degrading organic pollutants, and the general working principle of the electro-Fenton oxidation method is that: first, oxygen is reduced to hydrogen peroxide at the cathode of the cell and an iron-containing anode is electrolyzed to produce ferrous iron (Fe)2+) (ii) a Then, hydrogen peroxide and Fe2+The reaction is carried out to generate a large amount of high-activity substances such as hydroxyl free radicals, superoxide radicals and the like; finally, the organic pollutants react with the high-activity free radicals and are gradually degraded and mineralized. It is worth noting that the electro-Fenton oxidation technology is mainly used for degradation of organic pollutants in acidic aqueous solution, and requires continuous air introduction and periodic anode replacement to maintain the reaction. As is known, soil is solid with clay mineral as main component and has limited water content and gas permeability, so that the traditional electro-fenton technology has unsatisfactory effect in treating soil polluted by organic matters.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for repairing and treating phthalate ester contaminated soil by pulse electrochemical generation of hydrogen peroxide.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for restoring and treating phthalate ester contaminated soil by pulse electrochemical hydrogen peroxide generation comprises the following steps:
adding the aqueous solution containing bicarbonate radical into the crushed phthalate polluted soil, uniformly mixing, inserting the mixture into two carbon electrodes, and then applying square wave pulse voltage to the two carbon electrodes to carry out electrochemical repair treatment.
Preferably, the mass ratio of the bicarbonate-containing aqueous solution to the phthalate-contaminated soil is 1:10-100, and the concentration of the bicarbonate in the bicarbonate-containing aqueous solution is 0.1-0.3M.
Preferably, the aqueous solution containing bicarbonate is NaHCO3Aqueous solution or KHCO3An aqueous solution.
Preferably, the carbon electrode is made of graphite or carbon cloth.
Preferably, the carbon electrode has the following dimensions: 30-40cm × 10-15cm × 0.2-2cm, length × width × thickness.
Preferably, the distance between the two carbon electrodes is 10-100 cm.
Preferably, the square wave pulse voltage is +/-5.0V to +/-15.0V, and the pulse width is 10-60 s.
Preferably, the time of the electrochemical remediation treatment is determined by the quality of the phthalate-contaminated soil.
The main principle and basis of the invention are as follows: bicarbonate radical (HCO) in solution in the soil3 -) Can be oxidized to bicarbonate (HCO) at the anode of the electrolytic cell4 -) I.e. HCO3 --2e-+H2O→HCO4 -+2H+,ER.he. 1.80vvs. Due to HCO4 -Strongly oxidizing, which can mediate the oxidation of water to produce hydrogen peroxide, i.e., HCO4 -+H2O→H2O2+HCO3 -. Because the soil contains Fe2+Plasma of metal ions, H produced by the above process2O2With Fe2+The reaction is carried out to generate a large amount of OH (hydroxyl radical) and O2-(oxyanion free radical) and the like, thereby degrading and mineralizing the dissolved phthalate in the soil (see figure 1).
The invention has the beneficial effects that: the invention provides a method for restoring and treating phthalate polluted soil by pulse electrochemical hydrogen peroxide generation, which is characterized in that air is not required to be introduced into the soil, a reaction electrode is not required to be replaced regularly, and dissolved bicarbonate in the soil is activated by electrochemistry mainly mediating water to be oxidized and converted into hydrogen peroxide, so that the phthalate polluted soil is restored and treated continuously and efficiently. In addition, in the treatment process, the two electrodes in the electrolytic cell respectively play an anode role in different time periods by applying regularly changed square wave pulse voltage on the electrodes, and hydrogen peroxide can be generated at the two ends of the electrolytic cell, so that the problem of low efficiency in electrochemical degradation at the anode fixing end of the electrolytic cell due to low concentration of phthalate in soil is solved. Due to HCO in the whole reaction process3 -The cyclic reaction can generate hydrogen peroxide continuously through water oxidation without air, thereby the method is usedThe method has the characteristics of simplicity, convenience, greenness and high efficiency when used for repairing and treating the phthalate polluted soil.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic diagram of the principle of remediation of phthalate-contaminated soil by pulsed electrochemical generation of hydrogen peroxide according to the present invention;
FIG. 2 is a comparative liquid chromatography chart of di-n-butyl phthalate in soil leacheate of paddy field before and after 4h of treatment in example 1;
FIG. 3 is a graph of a square wave pulse voltage signal applied in example 2;
FIG. 4 is a comparative liquid chromatogram of dimethyl phthalate in soil leacheate for vegetable farm land before and after 2.5h of treatment in example 2;
FIG. 5 is a graph showing the change of the concentration of diisononyl phthalate and the degradation rate with electrolysis time in the soil of a paddy field treated in example 3.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Example 1
1.5L of 0.5M NaHCO3Adding 20kg of the aqueous solution, pulverizingThe Chongqing rice farmland soil polluted by di-n-butyl phthalate is uniformly mixed, two graphite plates with the size of 30 (length) cm multiplied by 15 (width) cm multiplied by 1 (thickness) cm are inserted as electrodes, the distance between the two electrodes is 30cm, square wave pulse voltage of +/-6.0V is applied to the two electrodes, the pulse width is 20s, and electrochemical restoration treatment is carried out for 4 h.
And (3) leaching the treated paddy field soil with water, collecting leacheate, filtering, performing liquid chromatography, and comparing the paddy field soil before treatment with the reference paddy field soil, wherein the result is shown in figure 2, and data before and after comparison treatment show that 95% of di-n-butyl phthalate in the paddy field soil is degraded and mineralized.
Example 2
Adding 1.0L KHCO with concentration of 1.0M3Adding 15kg of crushed water solution into vegetable field soil polluted by dimethyl phthalate in Chongqing land, uniformly mixing, burying two carbon cloths with the size of 30 (length) cm multiplied by 10 (width) cm multiplied by 0.2 (thickness) cm as electrodes, wherein the distance between the two electrodes is 20cm, applying square wave pulse voltage of +/-8.0V on the two electrodes, wherein the pulse width is 10s (shown in figure 3), and carrying out electrochemical repair treatment for 2.5 h.
And (3) leaching the treated vegetable field soil with water, collecting leacheate, filtering, performing liquid chromatography, and comparing the vegetable field soil before treatment with the vegetable field soil before treatment, wherein the result is shown in figure 4, and data before and after comparison treatment show that 90% of dimethyl phthalate in the vegetable field soil is degraded and mineralized.
Example 3
2.0L of 1.5M NaHCO3Adding 30kg of crushed Chongqing rice farmland soil polluted by diisononyl phthalate into 30kg of crushed Chongqing rice farmland soil, uniformly mixing, inserting two graphite plates with the size of 40 (length) cm multiplied by 15 (width) cm multiplied by 2 (thickness) cm as electrodes, wherein the distance between the two electrodes is 35cm, then applying square wave pulse voltage of +/-10.0V on the two electrodes, wherein the pulse width is 40s, and carrying out electrochemical repair treatment for 5 h. Wherein, the change rule of the concentration and the degradation rate of the diisononyl phthalate in the paddy farmland soil along with the electrolysis time is shown in figure 5, and as can be seen from figure 5, the concentration of the diisononyl phthalate gradually increases along with the reaction timeAnd decreases.
And (3) leaching the treated paddy field soil with water, collecting leacheate, filtering, performing liquid chromatography, and comparing data before and after treatment by using the paddy field soil before treatment as a reference to find that 92% of diisononyl phthalate in the paddy field soil is degraded and mineralized.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.

Claims (8)

1. A method for restoring and treating phthalate ester contaminated soil by pulse electrochemical hydrogen peroxide generation is characterized by comprising the following steps:
adding the aqueous solution containing bicarbonate radical into the crushed phthalate polluted soil, uniformly mixing, inserting the mixture into two carbon electrodes, and then applying square wave pulse voltage to the two carbon electrodes to carry out electrochemical repair treatment.
2. The method according to claim 1, wherein the mass ratio of the bicarbonate containing aqueous solution to the phthalate-contaminated soil is 1:10 to 100, and the concentration of the bicarbonate in the bicarbonate containing aqueous solution is 0.1 to 0.3M.
3. The method of claim 2, wherein the aqueous solution containing bicarbonate is NaHCO3Aqueous solution or KHCO3An aqueous solution.
4. The method of claim 1 wherein the carbon electrode is graphite or carbon cloth.
5. The method of claim 1 wherein the carbon electrode has dimensions of: 30-40cm × 10-15cm × 0.2-2cm, length × width × thickness.
6. The method of claim 1 wherein the two carbon electrodes are spaced apart by 10-100 cm.
7. The method of claim 1, wherein the square wave pulse voltage is ± 5.0V to ± 15.0V, and the pulse width is 10-60 s.
8. The method of claim 1, wherein the time of the electrochemical remediation process is based on the quality of the phthalate-contaminated soil.
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CN103316908B (en) * 2013-07-05 2015-02-25 华北电力大学 Device and method for restoring soil polluted by polychlorinated biphenyl
CN105457996B (en) * 2015-12-18 2018-04-06 广东工业大学 A kind of method of microwave cooperating SODIUM PERCARBONATE renovation of organic pollution place soil
CN105817474B (en) * 2016-03-21 2019-04-09 玉溪师范学院 A device, method and application for remediating soil composite pollution

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