Mediating agent as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic pollutant treatment, and particularly relates to a mediating agent as well as a preparation method and application thereof. The invention provides a mediating agent. The mediating agent comprises the following components in percentage by mass: 5-50% of magnesium salt, 3-40% of manganese salt, 5-30% of a rare earth compound and 6-60% of auxiliary metal salt, the magnesium salt and the manganese salt have vacancy defects. The mediating agent provided by the invention has rich oxygen vacancies and surface OH <->, and can efficiently activate peroxide bridge compounds, generate singlet oxygen and synergistically mediate generated SO4 <->, CO3 <->, CL <->,. OH, HO2 <->, RCOO <->, superoxide anion free radicals (O2 <->) and other high-energy and high-activity free radical clusters, so that the oxidation speed of organic pollutants is greatly increased, and mineralization is more thorough.

Description

Technical Field

[0001] The invention belongs to the technical field of organic pollutant treatment, and specifically relates to a mediator and a preparation method and application thereof. Background Art

[0002] Singlet oxygen 1 O2 is an emerging reactive oxygen species (ROS) with active and unstable chemical properties. It is widely present in nature and is one of the most commonly used reactive oxygen species in chemistry, environment, medicine and other fields. It has the characteristics of strong oxidizing ability, high reactivity, short survival time, and no toxic or harmful by-products after oxidation. It is a green and environmentally friendly oxidant.

[0003] However, non-free radical pathways such as singlet oxygen are mostly concentrated on the surface of the mediator, and the action sites and oxidation capabilities are somewhat limited. Independent application will result in incomplete oxidation and incomplete mineralization of complex organic pollutants.

[0004] Therefore, there is an urgent need for a mediator that can completely decompose complex organic pollutants. Summary of the invention

[0005] The purpose of the present invention is to provide a mediator and a preparation method and application thereof. The mediator provided by the present invention can efficiently activate peroxy bridge compounds to generate singlet oxygen and free radical clusters, thereby improving the degradation ability of organic pollutants.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides a mediator, comprising the following components in percentage by weight:

[0008] 5-50% magnesium salt, 3-40% manganese salt, 5-30% rare earth compound and 6-60% auxiliary metal salt;

[0009] The magnesium salt and the manganese salt have vacancy defects.

[0010] Preferably, the magnesium salt comprises magnesium valproate and / or magnesium pyruvate.

[0011] Preferably, the manganese salt includes one or more of sodium permanganate, manganese phosphate and manganese carbonate.

[0012] Preferably, the rare earth compound comprises rare earth oxide and / or rare earth chloride;

[0013] The rare earth oxides include one or more of La2O3, Y2O3, Nd2O3, CeO2, Sm2O3 and Tm2O3; the rare earth chlorides include one or more of LaCl3, RuCl3, SmCl3, CeCl3, YdCl3 and NdCl3.

[0014] Preferably, the auxiliary metal salt includes one or more of calcium formate, magnesium sulfate and potassium phosphate.

[0015] The present invention also provides a method for preparing the mediator described in the above technical solution, comprising the following steps: mixing the components contained in the mediator, and then performing wet ball milling to obtain the mediator.

[0016] Preferably, the wet ball milling condition parameters include: the dispersant used in the wet ball milling is petroleum ether, and the boiling range of the petroleum ether is 90-120° C.; the rotation speed of the wet ball milling is 200-400 rpm, and the time is 0.1-2.0 h.

[0017] The present invention also provides the use of the mediator described in the above technical solution or the mediator prepared by the preparation method described in the above technical solution in the degradation of organic pollutants.

[0018] Preferably, the application comprises the following steps:

[0019] After the mediator and the peroxy bridge compound are mixed, the organic pollutants are degraded;

[0020] The mediator is the mediator described in the above technical solution or the mediator prepared by the preparation method described in the above technical solution.

[0021] Preferably, the peroxy bridge compound includes one or more of sodium sulfate-hydrogen peroxide-sodium chloride adduct, sodium citrate-hydrogen peroxide-sodium chloride adduct, sodium phosphate-hydrogen peroxide-sodium chloride adduct, potassium monopersulfate, calcium peroxide, sodium persulfate, sodium perborate and sodium percarbonate;

[0022] The mass ratio of the mediator to the peroxy bridge compound is 0.005-0.1:100.

[0023] The present invention provides a mediator, comprising the following components in percentage by mass: 5-50% magnesium salt, 3-40% manganese salt, 5-30% rare earth compound and 6-60% auxiliary metal salt; the magnesium salt and manganese salt have vacancy defects. The mediator provided by the present invention has abundant oxygen vacancies and surface OH-, can efficiently activate peroxy bridge compounds, produce singlet oxygen and synergistically mediate the generation of high-energy and highly active free radical clusters such as SO4·-, CO3·-, CL·, ·OH, HO2·, RCOO·, superoxide anion free radical (O2-·), thereby greatly improving the oxidation rate of organic pollutants and making mineralization more thorough.

[0024] The present invention also provides a method for preparing the mediator described in the above technical solution. The preparation method provided by the present invention has a simple and rapid process and mild reaction conditions, and is suitable for industrial production. DETAILED DESCRIPTION

[0025] The present invention provides a mediator, comprising the following components in percentage by weight:

[0026] 5-50% magnesium salt, 3-40% manganese salt, 5-30% rare earth compound and 6-60% auxiliary metal salt;

[0027] The magnesium salt and the manganese salt have vacancy defects.

[0028] The mediator provided by the present invention comprises a magnesium salt having a mass percentage of 5 to 50%, specifically 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%. In the present invention, the magnesium salt has a vacancy defect. In the present invention, the magnesium salt preferably comprises magnesium valproate and / or magnesium pyruvate.

[0029] The mediator provided by the present invention comprises a manganese salt having a mass percentage of 3 to 40%, specifically 3%, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40%. In the present invention, the manganese salt has a vacancy defect. In the present invention, the manganese salt preferably comprises one or more of sodium permanganate, manganese phosphate and manganese carbonate.

[0030] The mediator provided by the present invention comprises a rare earth compound with a mass percentage of 5 to 30%, specifically 5%, 10%, 15%, 20%, 25% or 30%. In the present invention, the rare earth compound preferably comprises rare earth oxides and / or rare earth chlorides; the rare earth oxides preferably comprise one or more of La2O3, Y2O3, Nd2O3, CeO2, Sm2O3 and Tm2O3; the rare earth chlorides preferably comprise one or more of LaCl3, RuCl3, SmCl3, CeCl3, YdCl3 and NdCl3.

[0031] The mediator provided by the present invention comprises an auxiliary metal salt having a mass percentage of 6 to 60%, specifically 6%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60%. In the present invention, the auxiliary metal salt preferably comprises one or more of calcium formate, magnesium sulfate and potassium phosphate.

[0032] In the present invention, the particle size of the mediator is preferably 0.5 to 200 μm.

[0033] The present invention also provides a method for preparing the mediator described in the above technical solution, comprising the following steps: mixing the components contained in the mediator, and then wet ball milling to obtain the mediator.

[0034] In the present invention, the wet ball milling condition parameters preferably include: the dispersant used in the wet ball milling is petroleum ether, the boiling range of the petroleum ether is 90-120°C; the speed of the wet ball milling is 200-400rpm, and the time is 0.1-2.0h. In the present invention, the wet ball milling is preferably carried out under a nitrogen atmosphere, and the wet ball milling is preferably carried out in a rolling ball mill.

[0035] After the wet ball milling, the present invention also preferably includes filtering and drying the obtained system.

[0036] The present invention also provides the use of the mediator described in the above technical solution or the mediator prepared by the preparation method described in the above technical solution in the degradation of organic pollutants.

[0037] In the present invention, the application preferably comprises the following steps:

[0038] After the mediator and the peroxy bridge compound are mixed, the organic pollutants are degraded;

[0039] The mediator is the mediator described in the above technical solution or the mediator prepared by the preparation method described in the above technical solution.

[0040] In the present invention, the peroxy bridge compound preferably includes one or more of sodium sulfate-hydrogen peroxide-sodium chloride adduct, sodium citrate-hydrogen peroxide-sodium chloride adduct, sodium phosphate-hydrogen peroxide-sodium chloride adduct, potassium monopersulfate, calcium peroxide, sodium persulfate, sodium perborate and sodium percarbonate.

[0041] In the present invention, the organic pollutants include one or more of antibiotics, organic dyes and VOCs. The present invention has no special requirements on the form of the organic pollutants, which may be gas, solid or liquid.

[0042] In the present invention, the mass ratio of the mediator to the peroxy bridge compound is preferably 0.005-0.1:100.

[0043] Unless otherwise specified, the materials and equipment used in the present invention are all commercially available products in the art.

[0044] The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0045] Example 1

[0046] In this embodiment, the mediator includes the following components in percentage by weight: 35% magnesium valproate, 3% sodium permanganate, 17% manganese carbonate, 15% La2O3, 20% calcium formate, and 10% magnesium sulfate;

[0047] Put the weighed magnesium valproate, sodium permanganate, manganese carbonate, calcium formate, magnesium sulfate and La2O3 into a stainless steel rolling ball mill;

[0048] Introduce petroleum ether into the rolling ball mill and seal it;

[0049] Nitrogen was injected to expel the air in the ball mill and then ball milling was performed; the speed of the ball mill was 350 rpm and the time was 0.5 h; after ball milling, the mixture was filtered and dried in air in sequence to obtain a mediator with an average particle size of 60 to 120 μm.

[0050] Example 2

[0051] In this embodiment, the mediator includes the following components in percentage by weight: 30% magnesium valproate, 4% sodium permanganate, 19% manganese carbonate, 16% La2O3, 16% calcium formate, and 15% magnesium sulfate;

[0052] Put the weighed magnesium valproate, sodium permanganate, manganese carbonate, calcium formate, magnesium sulfate and La2O3 into a stainless steel rolling ball mill;

[0053] Introduce petroleum ether into the rolling ball mill and seal it;

[0054] Nitrogen was injected to expel the air in the ball mill and then ball milling was performed; the speed of the ball mill was 330 rpm and the time was 1.0 h; after ball milling, the mixture was filtered and dried in air in sequence to obtain a mediator with an average particle size of 80 to 150 μm.

[0055] Performance Testing

[0056] Using an ORP (oxidation-reduction potential) online detector, the mediator obtained in Example 1 or Example 2 was added to different peroxy bridge compounds to test the oxidation capacity before and after the addition. The test process is: the peroxy bridge compound and the mediator are mixed to prepare an aqueous solution with a mass concentration of 1%, and the ORP value is tested;

[0057] The test results are shown in Tables 1 and 2 respectively;

[0058] Table 1 Synergistic mediating ability of the mediators obtained in Example 1

[0059]

[0060]

[0061] Table 2 Synergistic mediating ability of the mediators obtained in Example 2

[0062]

[0063] It can be seen from Table 1 and Table 2 that after adding the mediator provided by the present invention, the oxidation ability of the peroxy bridge compound is greatly improved, and a high ORP value represents a strong ability to degrade organic pollutants.

[0064] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A mediator, characterized in that Includes the following components in percentage by mass: 5-50% magnesium salt, 3-40% manganese salt, 5-30% rare earth compound and 6-60% auxiliary metal salt; The magnesium salt and the manganese salt have vacancy defects.

2. The mediator according to claim 1, characterized in that The magnesium salts include magnesium valproate and / or magnesium pyruvate.

3. The mediator according to claim 1, characterized in that The manganese salt includes one or more of sodium permanganate, manganese phosphate and manganese carbonate.

4. The mediator according to claim 1, characterized in that The rare earth compound includes rare earth oxide and / or rare earth chloride; The rare earth oxides include one or more of La2O3, Y2O3, Nd2O3, CeO2, Sm2O3 and Tm2O3; the rare earth chlorides include one or more of LaCl3, RuCl3, SmCl3, CeCl3, YdCl3 and NdCl3.

5. The mediator according to claim 1, characterized in that The auxiliary metal salt includes one or more of calcium formate, magnesium sulfate and potassium phosphate.

6. The method for preparing the mediator according to any one of claims 1 to 5, characterized in that: The following steps are involved: The components contained in the mediator are mixed and then subjected to wet ball milling to obtain the mediator.

7. The preparation method according to claim 6, characterized in that: The wet ball milling condition parameters include: the dispersant used in the wet ball milling is petroleum ether, and the boiling range of the petroleum ether is 90-120° C.; the rotation speed of the wet ball milling is 200-400 rpm, and the time is 0.1-2.0 h.

8. Use of the mediator according to any one of claims 1 to 5 or the mediator prepared by the preparation method according to claim 6 or 7 in the degradation of organic pollutants.

9. The use according to claim 8, characterized in that: The application comprises the following steps: After the mediator and the peroxy bridge compound are mixed, the organic pollutants are degraded; The mediator is the mediator according to any one of claims 1 to 5 or the mediator prepared by the preparation method according to claim 6 or 7.

10. The use according to claim 9, characterized in that: The peroxy bridge compound includes one or more of sodium sulfate-hydrogen peroxide-sodium chloride adduct, sodium citrate-hydrogen peroxide-sodium chloride adduct, sodium phosphate-hydrogen peroxide-sodium chloride adduct, potassium monopersulfate, calcium peroxide, sodium persulfate, sodium perborate and sodium percarbonate; The mass ratio of the mediator to the peroxy bridge compound is 0.005-0.1:100.

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