CN115340169A

CN115340169A - Method for treating soil leaching waste liquid by catalyzing monopersulfate through modified activated carbon

Info

Publication number: CN115340169A
Application number: CN202210999324.5A
Authority: CN
Inventors: 周扬; 曾珠; 高源�; 江进; 付俊豪; 胡坚鹏; 江佩; 韦雪珍; 罗芸
Original assignee: Guangdong University of Technology
Current assignee: Guangdong University of Technology
Priority date: 2022-08-19
Filing date: 2022-08-19
Publication date: 2022-11-15
Anticipated expiration: 2042-08-19
Also published as: CN115340169B

Abstract

The invention discloses a method for treating soil leaching waste liquid by catalyzing monopersulfate through modified activated carbon, which comprises the following steps: providing an activated carbon having a modification of a quinone compound; mixing the active carbon modified by the quinone compound with monopersulfate in proportion to obtain a mixed solution; the mixed liquor is contacted with a soil leacheate. The preparation method of the quinone modified activated carbon is suitable for activated carbon with different sources and different shapes, is simple and convenient to operate, has easily obtained raw materials, low price and convenient use, and simultaneously ensures that the activated carbon has the capability of catalyzing monopersulfate. The modified activated carbon activated monopersulfate can effectively generate singlet oxygen, realize the efficient treatment of the organic polluted soil leaching waste liquid, simultaneously does not damage the surfactant in the soil leaching liquid, and is favorable for recycling the surfactant. In addition, the modified activated carbon has long-term catalytic activity, is easy to separate, and is beneficial to recycling of the surfactant.

Description

Method for treating soil leaching waste liquid by catalyzing monopersulfate through modified activated carbon

Technical Field

The invention relates to the field of soil remediation, in particular to a method for treating organic pollutant soil leaching waste liquid by using bonding method modified activated carbon, and particularly relates to a method for treating organic pollutant soil leaching waste liquid by using quinone modified activated carbon catalytic monopersulfate prepared by a bonding method.

Background

The soil is a basic material guarantee for the survival and the proliferation of a plurality of organisms and is a natural resource on which human beings live. With the increase of population and the acceleration of urbanization and industrialization, the organic pollution of soil is increasingly intensified. Persistent organic matters are important pollutants in soil, such as polycyclic aromatic hydrocarbons (such as phenanthrene), organochlorine pesticides (such as pentachlorophenol), brominated flame retardants (such as polybrominated diphenyl ethers) and other hydrophobic organic matters. After entering the soil, the organic pollutants can be adsorbed by soil organic matters and mineral substances, so that the biological effectiveness of the pollutants is remarkably reduced and the pollutants are preserved in the soil for a long time. Most of soil organic pollutants have the characteristics of strong biological enrichment and high toxicity (such as 'three cause' effect and endocrine disrupting effect), seriously threaten the safety of ecological environment and human health, and are one of the soil pollution problems to be solved at present.

Scholars at home and abroad carry out a great deal of research work around the organic contaminated soil remediation technology, wherein the surfactant leaching technology is widely concerned due to the characteristics of simple and convenient operation, high remediation efficiency, short remediation period and the like, and is one of the most potential organic contaminated soil remediation technologies at present. The surfactant leaching remediation technology mainly utilizes the solubilization and flow increasing characteristics of the surfactant to increase the solubility and the fluidity of the hydrophobic organic matters in the water phase and promote the hydrophobic organic matters adsorbed in the soil to enter the water phase, so that the remediation purpose is achieved. The surfactant leaching technology can effectively separate organic chlorine pesticide, polycyclic aromatic hydrocarbon, brominated flame retardant and other hydrophobic organic pollutants from soil, and the aim of soil remediation is fulfilled. It is noteworthy that although surfactant leaching techniques achieve efficient remediation of organically contaminated soil, the organic contaminants simply migrate from the soil into the leachate and are not completely removed. The soil leaching waste liquid contains a large amount of surfactant, and the pollutant removal difficulty is high. How to effectively treat the leaching waste liquid and realize economic and efficient removal of organic pollutants is a key problem in the process of popularizing and applying the soil leaching remediation technology. Properly treating the soil leaching waste liquid can not only reduce the environmental risk of organic pollutants, but also realize the recycling of the leaching liquid, greatly reduce the dosage of the surfactant in the repairing process, and have important environmental and economic significance.

The traditional surfactant leaching waste liquid treatment method mainly comprises a physical method and a biological method. Physical methods such as air stripping, solvent extraction, adsorption, membrane filtration and the like are mainly based on the principle of physical separation, and can not realize degradation and detoxification of pollutants. Biological methods generally have a long period and cannot achieve rapid and efficient treatment. In summary, the physical and biological methods for treating the waste solution from soil leaching have certain limitations. In recent years, a soil leacheate treatment method based on advanced oxidation has received much attention. The method generally utilizes photocatalysis, electrocatalysis, fenton reaction and the like to generate hydroxyl radical (. OH) and/or sulfate radical (SO) ₄ And-), the degradation and removal of organic pollutants in the soil leacheate are realized by utilizing the strong oxidizing property of free radicals. However, background components (such as surfactant, humus, halogen ions and the like) of the leaching waste liquid have a capturing effect on free radicals, and easily interfere with the pollutant degradation process. In addition, organic pollutants in the leacheate are mainly wrapped in the surfactant micelles, and the difficulty of oxidizing and removing the organic pollutants is increased due to the limitation that free radicals are difficult to enter the micelles. Therefore, in order to ensure the effect of removing the pollutants, the yield of the free radicals has to be increased, which increases the treatment cost on the one hand, and on the other hand, the surfactant in the leacheate is oxidized by the free radicals along with the pollutants, which is not beneficial to the recycling of the leacheate. To sum upIn consideration of the non-selective oxidation characteristic of free radicals and the water quality characteristics of the soil leacheate, the method for treating the soil leacheate by using the free radical oxidation technology has certain limitations.

Disclosure of Invention

Aiming at partial problems in the prior art, in particular to the actual problem that the leaching waste liquid of the organic polluted soil is difficult to treat and recover, the inventor carries out deep research, provides a method for catalyzing monopersulfate to generate singlet oxygen by utilizing quinone modified activated carbon, utilizes the characteristic that singlet oxygen is easy to enrich in hydrophobic interior of a surfactant micelle and the characteristic that singlet oxygen oxidation is slightly influenced by water quality background components, realizes high-efficiency removal of organic pollutants coated by the surfactant under the condition of not damaging the surfactant molecules, and provides an effective method for treating and recycling soil leacheate. Specifically, the present invention includes the following.

The first aspect of the invention provides a method for treating organic pollutant soil leaching waste liquid by using bonding modified activated carbon to catalyze monopersulfate, which comprises the following steps:

(1) Providing activated carbon having a modification of a quinone compound, wherein the quinone compound contains at least one amino substituent;

(2) Mixing the active carbon modified by the quinone compound with monopersulfate in proportion to obtain a mixed solution;

(3) Contacting the mixed liquor with a soil leacheate.

In certain embodiments, the method according to the present invention, wherein the mass ratio of the activated carbon with quinone compound modification to monopersulfate is 1.

In certain embodiments, the method according to the present invention, wherein the quinone compound comprises anthraquinone, naphthoquinone or their derivatives containing at least one amino substituent.

In certain embodiments, the method according to the present invention, wherein the monopersulfate comprises sodium monopersulfate, potassium monopersulfate, or any other agent that provides a salt of monopersulfate.

In certain embodiments, the method according to the present invention, wherein the activated carbon with quinone compound modification of step (1) is prepared by the following steps:

a. providing a quinone compound aqueous solution containing at least one amino substituent and activated carbon;

b. providing magnetic nanoparticles;

c. mixing and filtering the magnetic nanoparticles with an aqueous solution of activated carbon;

d. and c, adding a quinone compound aqueous solution into the filtered substances in the step c for reaction to obtain the active carbon modified by the quinone compound.

In certain embodiments, the method according to the present invention, wherein the temperature used for preparing the magnetic nanoparticles in step b is between 20 ℃ and 40 ℃

In certain embodiments, the method according to the present invention, wherein the mass ratio of the quinone compound to the activated carbon is 1.

In certain embodiments, the method according to the present invention, wherein the pH in step d is controlled to be 5-9.

In certain embodiments, the process according to the invention, wherein the reaction temperature in step d is between 60 and 100 ℃.

In a second aspect of the present invention, there is provided a composition for treating organic contaminated soil washing waste liquid, comprising: activated carbon and monopersulfates having a modification of a quinone compound, wherein the quinone compound contains at least one amino substituent.

Technical effects of the present invention include, but are not limited to:

(1) The preparation method of the quinone modified activated carbon is suitable for activated carbon with different sources and different shapes, and has the advantages of simple and convenient operation, easily obtained raw materials, low price and convenient use.

(2) The quinone compound containing amino and the carboxyl and lactone groups on the surface of the active carbon undergo dehydration condensation reaction to form a stable chemical bond, so that the active carbon has the capability of catalyzing monopersulfate.

(3) The modified activated carbon activated monopersulfate can effectively generate singlet oxygen, so that the high-efficiency treatment of the organic polluted soil leaching waste liquid is realized, meanwhile, the surfactant in the soil leaching liquid is not damaged, and the recycling of the surfactant is facilitated.

(4) The modified activated carbon has long-term catalytic activity, is easy to separate, and is beneficial to the recovery of the surfactant.

Detailed Description

Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that the upper and lower limits of the range, and each intervening value therebetween, is specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control. Unless otherwise indicated, "%" is percent by weight.

Method for treating organic pollutant soil leaching waste liquid

The invention provides a method for treating organic pollutant soil leaching waste liquid by using modified activated carbon modified by a bonding method to catalyze monopersulfate, which comprises the following steps:

(1) Providing an activated carbon having a modification of a quinone compound, wherein said quinone compound contains at least one amino substituent;

(3) Contacting the mixed liquor with a soil leacheate.

In the step (1), the activated carbon of the quinone compound-modified activated carbon may be any of those known in the art in terms of shape and size.

In the present invention, the quinone compound includes anthraquinone, naphthoquinone or their derivatives having at least one amino substituent. The quinone compound containing amino functional group and the carboxyl and lactone group on the surface of the carbon-based material are subjected to condensation reaction, and the quinone compound is bonded to the surface of the carbon-based material to complete quinone modification. In a specific embodiment, the quinone compound having at least one amino substituent according to the present invention is at least one selected from the group consisting of 1-aminoanthraquinone, 2-amino-3-chloro-1, 4-naphthoquinone.

The term "derivative" refers to a compound formed by substituting an atom or group of atoms in the molecule of the parent compound with another atom or group of atoms, and the substituent of the derivative useful in the present invention may be at least one or a combination of the following substituents: halogen, methyl, methylene, alkoxy, hydroxyl, aldehyde group, carboxyl, nitro, sulfonic group and amino, wherein examples of the halogen include but are not limited to fluorine, chlorine, bromine and iodine.

In step (2) of the present invention, the ratio of the activated carbon having a quinone compound modification to monopersulfate is 1. The term "monopersulfate" as used herein is intended to include sodium monopersulfate, potassium monopersulfate, and any other agent that can provide a salt of monopersulfate.

The invention further provides a preparation method of the active carbon modified by the quinone compound, which comprises the following steps:

a. providing a quinone compound aqueous solution and activated carbon;

b. providing magnetic nanoparticles;

c. mixing the magnetic nanoparticles with the aqueous solution of activated carbon and filtering;

In step a, the aqueous solution of the quinone compound has a pH of 5 to 9, for example a pH of 5, 6, 7, 8 or 9. The mass ratio of the quinone compound to the activated carbon is 1.

In step b, the magnetic nanoparticles comprise Fe with a diameter of 1-100 nm ₂ O ₃ And/or Fe ₃ O ₄ Magnetic nanoparticles. Preferably, the magnetic nanoparticles are iron oxide nanoparticles. In a particular embodiment, a 0.1-0.8M sodium hydroxide solution, preferably a 0.3-0.6M sodium hydroxide solution, and a 0.1-0.5M iron sulfate solution, preferably a 0.1-0.2M iron sulfate solution, are mixed. The sodium hydroxide solution is added dropwise to the ferric sulfate solution and stirred at 20-40 c, preferably 25-35 c for 5-9 hours to form iron oxide nanoparticles.

In step c, the magnetic nanoparticles are mixed with the aqueous solution of activated carbon and filtered, the reaction temperature being 60-100 ℃, preferably 70-90 ℃, and further preferably 75-85 ℃. The stirring time is 12-36h, preferably 20-24h.

And d, adding the substance filtered in the step c into a quinone compound aqueous solution for reaction to obtain the active carbon modified by the quinone compound. The reaction temperature is 60 to 100 ℃, preferably 70 to 90 ℃, and further preferably 75 to 85 ℃. The stirring time is 12-36h, preferably 24-36h. The pH of the reaction is controlled to be 5-9, for example, pH 5, 6, 7, 8 or 9.

It is noted that other steps or operations may be included before, after, or between steps (1) - (3) or (a) - (d) of the present invention, for example, to further optimize and/or improve the methods of the present invention. In certain embodiments, further comprising the step of washing the filtered and dried with water.

Example 1

1g of 2-amino-3-chloro-1, 4-naphthoquinone (e.g., 1-aminoanthraquinone, 2-amino-3-chloro-1, 4-naphthoquinone, etc.) was dissolved in water, and pH =9 was controlled. Weighing the activated carbon according to the mass ratio of the quinone to the activated carbon of 1. A0.5M sodium hydroxide solution and a 0.1M ferric sulfate solution were combined in a 250mL flask. The sodium hydroxide solution was added dropwise to the ferric sulfate solution, and stirred at 30 ℃ for 5-9 hours to form iron oxide nanoparticles. Adding the water solution containing the activated carbon, stirring at 80 ℃ for 24 hours, filtering, adding the quinone solution, and continuing stirring for 36 hours. And cooling the reaction mixture to room temperature, washing with water for multiple times, and drying at 60 ℃ to obtain the quinone modified activated carbon. Taking 1g of quinone modified activated carbon, and when in use, mixing the quinone modified activated carbon and monopersulfate according to the weight ratio of 1: the proportion of 10 is added into the soil leacheate to be treated, so that the effective treatment of the soil leacheate can be realized.

Example 2

This example is another exemplary method for treating waste soil washing liquid, and is different from example 1 in that hydrochloric acid is added to control the pH of the quinone modified activated carbon preparation process to be 5.

Example 3

This example is another exemplary method for treating waste soil washing liquid, and is different from example 1 in that hydrochloric acid is added to control the pH of the quinone modified activated carbon preparation process to be 7.

Example 4

This example is another exemplary method for treating a waste solution from soil washing, and is different from example 1 in that the mass ratio of the quinone compound to the activated carbon in this example is 1.

Example 5

The embodiment is another exemplary method for treating the waste soil washing liquid, and is different from the embodiment 1 in that the mass ratio of the quinone compound to the activated carbon is 1.

Example 6

Example 7

Example 8

This example is another exemplary method for treating a waste soil washing solution, and is different from example 1 in that the ratio of the quinone modified activated carbon to monopersulfate is 1.

Example 9

This example is another exemplary method for treating a waste soil washing solution, and differs from example 1 in that the ratio of the quinone modified activated carbon to monopersulfate is 1.

Example 10

Test example

Table 1 shows the removal rates of organic contaminants measured by the treatment methods of examples 1 to 3.

TABLE 1

Table 2 shows the removal rates of organic contaminants measured by the treatment methods of examples 4 to 7.

TABLE 2

Table 3 shows the removal rates of organic contaminants measured by the treatment methods of examples 8 to 10.

TABLE 3

As can be seen from the results of example 1 and examples 2 to 3 in Table 1 above, pH affects the treatment effect of the method of the present invention, which is more preferable when pH is 9 under alkaline conditions, i.e., pH is controlled to be 8 to 9. Too low or too high pH is disadvantageous for catalyzing dehydration condensation reaction, resulting in a decrease in reaction rate and thus a reduction in treatment effect.

From the results of example 1 and examples 4 to 7 in Table 2 above, it is understood that the mass ratio of the quinone compound to the activated carbon also affects the treatment effect. When the mass ratio of the quinone compound to the activated carbon is 1. If the mass ratio of the quinone compound to the activated carbon is too low, the content of quinone adsorbed on the surface of the activated carbon is reduced, and the processing capacity of the modified activated carbon is reduced; if the content is too high, the bonding reaction can not completely occur, but the active carbon occupies the adsorption sites of the active carbon, and the generation of the quinone modified active carbon is influenced.

From the results of example 1 and examples 8 to 10 in table 3 above, it is clear that the ratio of quinone-modified activated carbon to monopersulfate affects the treatment effect. When the ratio of the quinone modified activated carbon to the monopersulfate is 1. The singlet oxygen content generated by catalysis is low in proportion, and organic matters in the leaching waste liquid cannot be completely treated; when the ratio is too high, the amount of the catalyst is relatively small, so that the catalytic rate is slow, and the efficiency of generating singlet oxygen in the same reaction time is reduced.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Many modifications and variations may be made to the exemplary embodiments of the present description without departing from the scope or spirit of the present invention. The scope of the claims is to be accorded the broadest interpretation so as to encompass all modifications and equivalent structures and functions.

Claims

1. A method for treating soil leaching waste liquid by using modified activated carbon to catalyze monopersulfate is characterized by comprising the following steps:

(3) Contacting the mixed liquor with a soil leacheate.

2. The method according to claim 1, wherein the mass ratio of the activated carbon with the quinone compound modification to the monopersulfate is 1.

3. The method of claim 2, wherein the quinone compound comprises anthraquinone, naphthoquinone or their derivatives having at least one amino substituent.

4. The method of claim 3, wherein the monopersulfate salt comprises sodium monopersulfate, potassium monopersulfate, or any other agent that provides a salt of monopersulfate.

5. The method according to any one of claims 1 to 4, wherein the activated carbon having a quinone compound modification of step (1) is prepared by the following steps:

b. providing magnetic nanoparticles;

d. and d, adding a quinone compound aqueous solution into the filtered substances in the step c for reaction to obtain the active carbon modified by the quinone compound.

6. The method according to claim 5, wherein the temperature used for preparing the magnetic nanoparticles in step b is 20-40 ℃.

7. The method according to claim 6, wherein the mass ratio of the quinone compound to the activated carbon is 1.

8. The method of claim 7, wherein the pH in step d is controlled to be 5 to 9.

9. The process according to claim 8, wherein the reaction temperature in step d is 60-100 ℃.

10. A composition for treating an organic contaminant, soil washing effluent, comprising: activated carbon and monopersulfates having a modification of a quinone compound, wherein the quinone compound contains at least one amino substituent.