CN109758714B

CN109758714B - Method for restoring antibiotic-polluted soil

Info

Publication number: CN109758714B
Application number: CN201910065744.4A
Authority: CN
Inventors: 姚玉元; 饶龙骏; 王文涛; 陈礼坤
Original assignee: Zhejiang University of Technology ZJUT
Current assignee: Zhejiang University of Technology ZJUT
Priority date: 2019-01-23
Filing date: 2019-01-23
Publication date: 2020-12-18
Anticipated expiration: 2039-01-23
Also published as: CN109758714A

Abstract

The invention discloses a method for remedying antibiotic-contaminated soil, and belongs to the technical field of soil remediation. The invention is characterized in that an environment-friendly catalyst and an oxidant are doped into the soil polluted by antibiotics, and a proper amount of water is added to the soil to submerge the soil to react, so that the antibiotics in the soil can be removed. The method is simple and convenient to operate, does not need to prepare a catalyst and pretreat the antibiotic-polluted soil, and has low cost; the reaction condition is mild, the conditions such as ultrasonic illumination and the like are not needed, the treatment period is short, and the soil polluted by antibiotics can be efficiently repaired within 30-300 minutes; the pH adaptation range is wide, and the catalytic activity is high; the environment-friendly metal catalyst has no secondary pollution and can achieve the effect of environmental protection.

Description

Method for restoring antibiotic-polluted soil

Technical Field

The invention relates to a method for remedying antibiotic-contaminated soil, and belongs to the technical field of soil remediation.

Technical Field

Antibiotics are widely used in the treatment and control of bacterial infectious diseases in humans and other animals, and may be used in livestock breeding as feed additives or growth promoters. A large amount of antibiotics continuously enter soil through the ways of organic fertilizer application, sewage irrigation and the like, so that the content of the antibiotics in the soil environment is increased year by year and the variety is increased continuously. Antibiotic pollution can have direct or indirect effects on microorganisms, animals, plants and the like in soil, and antibiotics can be absorbed by plants and affect human health through a food chain. Therefore, how to efficiently repair the soil polluted by antibiotics is a problem to be solved urgently.

The common soil remediation technologies at present are as follows: physical repair techniques including aeration decontamination, heat treatment, and the like; bioremediation techniques including phytoremediation, microbial remediation, and the like; the chemical repairing technology comprises a vacuum separation method, a water vapor stripping method, a chemical cleaning method, a chemical oxidation method and the like. Among these conventional soil remediation techniques, the physical remediation techniques not only require a large amount of manpower and material resources, but also cannot fundamentally treat antibiotics in the soil. At present, the pollutants in soil are mainly removed by means of microbial metabolism in the prior art, but antibiotics can inhibit the activity of microorganisms, so that the remediation technology cannot efficiently achieve the remediation purpose in the soil polluted by the antibiotics. The chemical remediation technology mainly refers to a chemical oxidation remediation method, and aims to remove pollutants by adding an oxidant into soil to enable the oxidant to react with the pollutants in the soil.

In recent years, advanced oxidation technology is considered to be one of the most effective chemical oxidation repair technologies today, and hydrogen peroxide, potassium permanganate, persulfate and peroxymonosulfate are commonly used as oxidants in the technology. The hydrogen peroxide generally generates strong oxidative hydroxyl free radicals (. OH) through reaction with ferrous ions, and degrades most soil pollutants into low-toxicity and easily biodegradable micromolecules so as to achieve the aim of soil remediation. But the hydrogen peroxide is easy to decompose due to unstable chemical properties, the hydrogen peroxide and ferrous ions can only react under the condition that the pH value is 2-4, and the iron ions after the reaction are easy to form sludge to cause secondary pollution to soil. Compared with hydrogen peroxide, potassium permanganate has the characteristics of stronger oxidizing ability, less influence of pH and the like, so that researchers select potassium permanganate to repair soil. For example, application No.: CN 103464455A, "a method for carrying out chemical oxidation remediation on organic contaminated soil by compounding potassium permanganate and hydrogen peroxide", discloses a method for achieving the purposes of advantage complementation and high-efficiency soil remediation by compounding potassium permanganate and hydrogen peroxide. However, the potassium permanganate is easy to cause the change of the soil structure due to the degradation of pollutants in the soil, and strong toxic manganese ions are generated after the reaction, so that the repaired soil is not beneficial to planting, and the practical application of the technology is greatly limited.

Compared with hydrogen peroxide and potassium permanganate, the persulfate or peroxymonosulfate not only has the characteristics of stable structure, convenient transportation, low price and the like, but also can be activated to generate sulfate radicals with stronger oxidation capability and wider pH application range. In recent years, methods for generating sulfate radicals by activating persulfate or peroxymonosulfate for environmental remediation have been extensively studied. Among the methods for activating persulfate or peroxymonosulfate, the activation of transition metal ions is considered as the most effective activation method with the advantages of no external energy input, low cost, in-situ repair, high efficiency and the like, but because the transition metal ions are extremely toxic, the transition metal ions are not easy to remove after use, and secondary pollution is brought to the environment. In order to avoid the existence of transition metal ions, researchers select a non-metal catalyst to replace the transition metal ions, and certain effect is achieved in the aspect of soil remediation. For example: application No.: CN 109047320 "remediation method of organic contaminated soil" discloses a method for degrading organic contaminants by doping sulfur into organic soil with nanocarbon activated persulfate. Although the heterogeneous non-metal catalyst avoids heavy metal pollution caused by the existence of transition metal ions, the heterogeneous non-metal catalyst has the defects of low catalytic activity, difficulty in-situ repair, difficulty in biodegradation of a matrix material and the like, and the future development of the method is hindered.

Disclosure of Invention

The method aims to overcome the defects of the existing chemical oxidation repair technology for activating persulfate or peroxymonosulfate to generate sulfate radicals, and achieves the purposes of low cost, high efficiency, no secondary pollution to the environment and the like. The inventors of the present invention have conducted extensive studies and finally found that: the use of an environmentally friendly catalyst which reacts with an oxidant to generate active oxygen species has an effect of efficiently remedying the soil contaminated with antibiotics, and thus the present invention has been finally completed. The method for remedying the soil polluted by the antibiotics is characterized in that an environment-friendly catalyst and an oxidant are doped into the soil polluted by the antibiotics, a proper amount of water is added into the soil to submerge the soil, the antibiotics in the soil can be removed through reaction, the environment-friendly catalyst is one or more of metaborate and borohydride, the oxidant is one or more of persulfate or peroxymonosulfate, the adding amount of the environment-friendly catalyst doped into the soil polluted by the antibiotics is 0.05g/kg to 50g/kg of soil, the adding amount of the oxidant is 0.03g/kg to 30g/kg of soil, the reaction temperature is controlled to be 10-100 ℃, and the reaction time is 30-300 minutes. Preferably, the antibiotic in the antibiotic-contaminated soil is one or more of sulfonamide antibiotics or quinolone antibiotics, and the content of the antibiotic is 10mg/kg to 500mg/kg of soil.

Further, the environment-friendly catalyst is one or more of metaborate and borohydride, wherein the metaborate is one or more of sodium metaborate, lithium metaborate, potassium metaborate, magnesium metaborate, calcium metaborate and ammonium metaborate, and the borohydride is one or more of sodium borohydride, potassium borohydride, lithium borohydride or magnesium borohydride.

Further, the oxidant is one or more of persulfate and peroxymonosulfate, wherein the persulfate is one or more of sodium persulfate, potassium persulfate and ammonium persulfate, and the peroxymonosulfate is one or more of sodium peroxymonosulfate, potassium peroxymonosulfate or ammonium peroxymonosulfate.

Further, the dosage of the environment-friendly catalyst is preferably 0.2g/kg to 48.8g/kg of soil, and the dosage of the oxidant is preferably 0.1g/kg to 24.4g/kg of soil. The adding amount of the environment-friendly catalyst and the oxidant is ensured to be in the range, and the antibiotics in the soil polluted by the antibiotics can be efficiently removed.

Furthermore, the sulfanilamide antibiotic in the antibiotic-polluted soil is one or more of sulfadiazine, sulfisoxazole, mafenide and sulfamethazine, and the quinolone antibiotic is one or more of ciprofloxacin, moxifloxacin, enoxacin and lomefloxacin.

Further, the content of the antibiotic in the antibiotic-contaminated soil is more preferably 10mg/kg to 488.6mg/kg of soil. The concentration is ensured to be beneficial to the efficient removal of the antibiotics.

Furthermore, the reaction temperature is generally controlled to be between 10 and 100 ℃, and preferably between 20 and 60 ℃.

The method of the invention has no special limitation on the pH value of the antibiotic-polluted soil, and is suitable for repairing the antibiotic-polluted soil with wide pH range.

Has the advantages that: compared with the prior art, the invention has the advantages that: (1) the operation is simple and convenient, the preparation of a catalyst and the pretreatment of the antibiotic-polluted soil are not needed, and the cost is low; (2) the reaction condition is mild, the conditions such as ultrasonic illumination and the like are not needed, the treatment period is short, and the soil polluted by antibiotics can be efficiently repaired within 30-300 minutes; (3) the pH adaptation range is wide, and the catalytic activity is high; (4) the environment-friendly metal catalyst has no secondary pollution and can achieve the effect of environmental protection.

Description of the drawings:

FIG. 1 is a graph of sodium metaborate activated potassium peroxymonosulfate versus removal of sulfadiazine from soil over time.

FIG. 2 is a graph of sodium borohydride activated sodium persulfate versus time for removal of ciprofloxacin from soil.

Detailed Description

A method for remediating antibiotic-contaminated soil according to the present invention is further described below with reference to examples.

Example 1

Taking 50g of soil polluted by antibiotics, wherein the content of sulfadiazine is 10mg/kg to 488.6mg/kg of soil. Sodium metaborate is added into the soil according to the proportion of 0.2g/kg to 48.8g/kg, and potassium peroxymonosulfate is added into the soil according to the proportion of 0.1g/kg to 24.4 g/kg. And adding water into the soil, wherein the water is added in an amount of submerging the soil, reacting for 30-300 minutes at the temperature of 20-60 ℃, and the removal rate of sulfadiazine in the soil is up to more than 90%. The test results refer to fig. 1.

Examples 2 to 10

According to the invention, one of lithium metaborate, potassium metaborate, magnesium metaborate, calcium metaborate, ammonium metaborate, sodium borohydride, potassium borohydride, lithium borohydride and magnesium borohydride in the environment-friendly catalyst is used for replacing sodium metaborate in the embodiment 1, other conditions are consistent with those of the embodiment 1, and the removal rate of sulfadiazine can reach more than 90%.

Examples 11 to 15

The potassium peroxymonosulfate in the embodiment 1 is replaced by one of sodium persulfate, potassium persulfate, ammonium persulfate, sodium peroxymonosulfate and ammonium peroxymonosulfate in the oxidizing agent, other conditions are consistent with those of the embodiment 1, and the removal rate of sulfadiazine in soil can reach more than 90%.

Example 16

Taking 50g of soil polluted by antibiotics, wherein the content of the ciprofloxacin is 10-488.6 mg/kg of soil. Sodium borohydride in an amount of 0.2g/kg to 48.8g/kg of soil and sodium persulfate in an amount of 0.1g/kg to 24.4g/kg of soil are added thereto. And adding water into the soil, wherein the water is added in an amount of submerging the soil, reacting for 30-300 minutes at the temperature of 20-60 ℃, and the removal rate of the ciprofloxacin in the soil is up to more than 98%. The test results refer to fig. 2.

Examples 17 to 25

According to the invention, one of lithium metaborate, sodium metaborate, magnesium metaborate, calcium metaborate, ammonium metaborate, sodium borohydride, potassium borohydride, lithium borohydride and magnesium borohydride in the environment-friendly catalyst is used for replacing the sodium borohydride in the embodiment 16, other conditions are consistent with those in the embodiment 16, and the removal rate of the ciprofloxacin in the soil is up to more than 98%.

Examples 26 to 30

The sodium persulfate in the embodiment 1 is replaced by one of potassium persulfate, ammonium persulfate, sodium peroxymonosulfate, potassium peroxymonosulfate or ammonium peroxymonosulfate in the oxidant, other conditions are consistent with those in the embodiment 16, and the removal rate of the ciprofloxacin in the soil is up to more than 98%.

The above description is only a part of the embodiments of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and does not represent all technical solutions under the concept of the present invention. It should be noted that those skilled in the art, upon being motivated by this patent conception and specific embodiment, may recognize numerous additions and modifications which may be made without departing from the principles of the present invention, such as insubstantial modifications of determining different catalyst and oxidant amounts, different temperatures, etc., based on different wastewater and contaminant concentrations, and such modifications and refinements are considered to be within the scope of the present invention.

Claims

1. A method for remedying the soil polluted by antibiotics is characterized in that an environment-friendly catalyst and an oxidant are mixed into the soil polluted by the antibiotics, water is added until the soil is submerged, the antibiotics in the soil are removed through reaction,

the environment-friendly catalyst is one or more of metaborate and borohydride, the oxidant is one or more of persulfate or peroxymonosulfate, the adding amount of the environment-friendly catalyst added into the soil to be repaired is 0.05g/kg to 50g/kg of soil, the adding amount of the oxidant is 0.03g/kg to 30g/kg of soil, the reaction temperature is controlled to be 10-100 ℃, and the reaction time in the soil is 30-300 minutes;

the metaborate is one or more of sodium metaborate, lithium metaborate, potassium metaborate, magnesium metaborate, calcium metaborate or ammonium metaborate;

the borohydride is one or more of sodium borohydride, potassium borohydride, lithium borohydride, magnesium borohydride or calcium borohydride;

the persulfate is one or more of sodium persulfate, potassium persulfate or ammonium persulfate.

2. The method for remediating antibiotic-contaminated soil as recited in claim 1, wherein said peroxymonosulfate salt is one or more of sodium peroxymonosulfate, potassium peroxymonosulfate, and ammonium peroxymonosulfate.

3. The method for remediating the antibiotic-contaminated soil as recited in claim 1, wherein the antibiotic in the soil is one or more of sulfonamide antibiotics and quinolone antibiotics, and the content of the antibiotic is 10mg/kg to 500mg/kg of soil.