Composite material for efficiently removing antibiotics in soil and preparation method thereof

Abstract

The invention discloses a composite material for efficiently removing antibiotics in soil, and the composite material comprises the following raw material components: 6-20 parts of activated carbon, 4-8 parts of iron oxide nanoparticles, 2-6 parts of zinc oxide nanoparticles, 1.5-4 parts of tungsten disulfide, 1-4 parts of copper disulfide, 2-6 parts of silica gel, 15-30 parts of gypsum, 10-20 parts of iron tailing sand and 8-12 parts of zeolite. According to the present invention, the active carbon, the iron oxide nanoparticles, the zinc oxide nanoparticles and other raw materials are precisely proportioned so as to improve the efficiency and the effect of removing the antibiotics in the soil, the raw materials and the preparation method are relatively environmentally friendly, and the material can be recycled after the use so as to easily promote the soil purification and the sustainable development.

Description

Technical Field

[0001] The invention relates to the technical field of soil remediation, and in particular to a composite material for efficiently removing antibiotics in soil and a preparation method thereof. Background Art

[0002] Antibiotics in the soil are usually caused by antibiotic residues introduced by human and animal excrement, agricultural and breeding activities, medical waste, etc. These antibiotic residues may have a negative impact on the soil ecosystem and microbial community, and may also cause the spread of antibiotic resistance genes in the soil. The presence of antibiotics in the soil may cause many aspects of harm, including impacts on the soil ecosystem, microbial diversity and human health. The following are some of the hazards that antibiotics may cause in the soil: Promote the formation of resistant strains: Antibiotic residues in the soil may cause bacteria in the soil to develop resistance. These resistance genes can spread between bacteria and promote the formation of resistant strains. Destroy soil microbial communities: Antibiotic residues may destroy the diversity and balance of microorganisms in the soil, affect the function of microorganisms in the soil, and thus have a negative impact on the stability of the ecosystem. Affect crop quality: Antibiotic residues may be absorbed by crops, introduced into the food chain, and ultimately affect human health. In addition, antibiotic residues may also affect crop growth and quality.

[0003] The existing technology mainly uses the Fenton mixed system, that is, peroxide reacts with ferrous ions to generate hydroxyl radicals. The overall degradation and removal are not comprehensive and environmentally friendly. Here we propose a composite material for efficiently removing antibiotics in soil and a preparation method thereof. Summary of the invention

[0004] In order to solve the above technical deficiencies, the present invention adopts a modified technical solution to provide a composite material for efficiently removing antibiotics in soil. The raw material components of the composite material include 6-20 parts of activated carbon, 4-8 parts of iron oxide nanoparticles, 2-6 parts of zinc oxide nanoparticles, 1.5-4 parts of tungsten disulfide, 1-4 parts of copper disulfide, 2-6 parts of silica gel, 15-30 parts of gypsum, 10-20 parts of iron tailings sand and 8-12 parts of zeolite.

[0005] As a further preferred embodiment of the present invention, the raw material components of the composite material include 20 parts of activated carbon, 8 parts of iron oxide nanoparticles, 6 parts of zinc oxide nanoparticles, 4 parts of tungsten disulfide, 4 parts of copper disulfide, 6 parts of silica gel, 15-30 parts of gypsum, 10-20 parts of iron tailings, and 8-12 parts of zeolite.

[0006] As a further preferred embodiment of the present invention, the raw material components of the composite material include 6 parts of activated carbon, 4 parts of iron oxide nanoparticles, 2 parts of zinc oxide nanoparticles, 1.5 parts of tungsten disulfide, 1 part of copper disulfide, 2-6 parts of silica gel, 15 parts of gypsum, 10 parts of iron tailings sand, and 8 parts of zeolite.

[0007] As a further preferred embodiment of the present invention, the specific production steps include the following:

[0008] S1, activated carbon pretreatment: calcining the activated carbon at high temperature to remove impurities and increase its adsorption performance;

[0009] S2, preparation of stable iron oxide nanoparticle solution and zinc oxide nanoparticle solution, synthesized by solvothermal method;

[0010] S3, fully mixing and stirring the iron oxide nanoparticle solution and the zinc oxide nanoparticle solution with all the remaining materials, and then drying them;

[0011] S4, functional modification of the composite surface to enhance its adsorption performance and stability;

[0012] S5, pouring the composite material into a stirring tank, adding the soil from which the antibiotics need to be removed, mixing and stirring for full contact, and realizing efficient removal of the antibiotics.

[0013] As a further preferred embodiment of the present invention, in step S1, the pretreatment of the activated carbon is as follows: first, oxidation treatment is performed to expose the activated carbon to chlorine dioxide at a temperature of 200-250°C for a treatment time of 2-4 hours, acid and alkali washing is performed, a sodium hydroxide solution with a concentration of 48-53% is used, and the washing time is 4-6 hours, and then heat treatment is performed at a high temperature of 700-1000°C for a treatment time of 1-2 hours, ammonia or ammonia gas is used to treat the surface of the activated carbon, the activated carbon is repeatedly washed with pure water, and then dried at a low temperature.

[0014] As a further preferred embodiment of the present invention, in step S2, the solvothermal method for preparing the iron oxide nanoparticle solution is as follows: prepare iron chloride, ethylene glycol, and octylamine, mix the raw materials in a reaction bottle and stir evenly, the stirring speed is generally 500-800 rpm, put the reaction bottle in an oil bath, heat to 95°C, maintain for 2-4 hours, and after cooling, collect the precipitate, wash and dry to obtain iron oxide nanoparticles.

[0015] As a further preferred embodiment of the present invention, in step S4, the surface modification includes the following steps: preparing a silane coupling agent solution, the silane coupling agent concentration is in the range of 1-5%, the silane coupling agent is aminosilane or hydroxysilane, coating the prepared silane coupling agent solution on the surface of the composite material, and controlling the thickness between 6-50um, and finally drying the material at a temperature of 50-120°C for 10-20h for drying and curing.

[0016] As a further preferred embodiment of the present invention, in step S5, the rotation speed is controlled between 120 r / min and 220 r / min during the stirring process, and the temperature is controlled between 80 and 125°C during the stirring process.

[0017] The beneficial effects achieved by the present invention are as follows: the present invention adopts the steps of activated carbon pretreatment, preparation of stable iron oxide nanoparticles and zinc oxide nanoparticles, surface functional modification, etc., to improve the adsorption performance and stability of the composite material, can efficiently remove antibiotics in the soil, help purify the soil environment, and reduce the impact of antibiotics on the ecosystem. The raw materials and preparation methods are relatively environmentally friendly, and the materials may be recyclable and reused after use, which helps promote soil purification and sustainable development. DETAILED DESCRIPTION

[0018] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. 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.

[0019] The invention provides a technical solution: a composite material for efficiently removing antibiotics in soil. The raw material components of the composite material include 6-20 parts of activated carbon, 4-8 parts of iron oxide nanoparticles, 2-6 parts of zinc oxide nanoparticles, 1.5-4 parts of tungsten disulfide, 1-4 parts of copper disulfide, 2-6 parts of silica gel, 15-30 parts of gypsum, 10-20 parts of iron tailings sand and 8-12 parts of zeolite.

[0020] The raw material components of the composite material include 20 parts of activated carbon, 8 parts of iron oxide nanoparticles, 6 parts of zinc oxide nanoparticles, 4 parts of tungsten disulfide, 4 parts of copper disulfide, 6 parts of silica gel, 15-30 parts of gypsum, 10-20 parts of iron tailings sand, and 8-12 parts of zeolite.

[0021] The raw material components of the composite material include 6 parts of activated carbon, 4 parts of iron oxide nanoparticles, 2 parts of zinc oxide nanoparticles, 1.5 parts of tungsten disulfide, 1 part of copper disulfide, 2-6 parts of silica gel, 15 parts of gypsum, 10 parts of iron tailings sand and 8 parts of zeolite.

[0022] The specific production steps include the following:

[0023] S1, activated carbon pretreatment: calcining the activated carbon at high temperature to remove impurities and increase its adsorption performance;

[0024] S2, preparation of stable iron oxide nanoparticle solution and zinc oxide nanoparticle solution, synthesized by solvothermal method;

[0025] S3, fully mixing and stirring the iron oxide nanoparticle solution and the zinc oxide nanoparticle solution with all the remaining materials, and then drying them;

[0026] S4, functional modification of the composite surface to enhance its adsorption performance and stability;

[0027] S5, pouring the composite material into a stirring tank, adding the soil from which the antibiotics need to be removed, mixing and stirring for full contact, and realizing efficient removal of the antibiotics.

[0028] In step S1, the activated carbon is pretreated as follows: first, oxidation treatment is performed to expose the activated carbon to chlorine dioxide at a temperature of 200-250°C for 2-4 hours, acid and alkali washing is performed, a sodium hydroxide solution with a concentration of 48-53% is used, and the washing time is 4-6 hours, and then heat treatment is performed at a high temperature of 700-1000°C for 1-2 hours.

[0029] The surface of activated carbon is treated with ammonia or ammonia gas, and the activated carbon is repeatedly washed with pure water and then dried at low temperature.

[0030] In step S2, the solvothermal method for preparing the iron oxide nanoparticle solution is as follows: prepare iron chloride, ethylene glycol, and octylamine, mix the raw materials in a reaction bottle and stir evenly, the stirring speed is generally 500-800 rpm, put the reaction bottle into an oil bath, heat to 95°C, maintain for 2-4 hours, cool, collect the precipitate, wash and dry to obtain iron oxide nanoparticles.

[0031] In step S4, the surface modification includes the following steps: preparing a silane coupling agent solution, the silane coupling agent concentration is in the range of 1-5%, the silane coupling agent is aminosilane or hydroxysilane, coating the prepared silane coupling agent solution on the surface of the composite material, and controlling the thickness between 6-50um, and finally drying the material at a temperature of 50-120°C for 10-20h for drying and curing.

[0032] In step S5, the rotation speed is controlled between 120 r / min and 220 r / min during the stirring process, and the temperature is controlled between 80 and 125° C. during the stirring process.

[0033] Embodiment 1

[0034] The raw material components of the composite material include 20 parts of activated carbon, 8 parts of iron oxide nanoparticles, 6 parts of zinc oxide nanoparticles, 4 parts of tungsten disulfide, 4 parts of copper disulfide, 6 parts of silica gel, 15-30 parts of gypsum, 10-20 parts of iron tailings sand, and 8-12 parts of zeolite.

[0035] The specific production steps include the following:

[0036] Activated carbon pretreatment: calcine the activated carbon at high temperature to remove impurities and increase its adsorption performance. The pretreatment of activated carbon is as follows: first, oxidize the activated carbon and expose it to chlorine dioxide at a temperature of 250°C for 4 hours. Use acid and alkali washing, use a 53% sodium hydroxide solution for 6 hours, and then heat treat it at a high temperature of 1000°C for 2 hours. Use ammonia or ammonia gas to treat the surface of the activated carbon, repeatedly wash the activated carbon with pure water, and then dry it at a low temperature; prepare stable iron oxide nanoparticle solutions and zinc oxide nanoparticle solutions, and synthesize them by solvothermal method. The solvothermal preparation of iron oxide nanoparticle solutions is as follows: prepare iron chloride, ethylene glycol, and octylamine, mix the raw materials in a reaction bottle and stir evenly. The stirring speed is generally 800rpm. Put the reaction bottle in an oil bath, heat it to 95°C, and keep it for 4h , after cooling, collecting the precipitate, washing and drying to obtain iron oxide nanoparticles; fully mixing the iron oxide nanoparticle solution and the zinc oxide nanoparticle solution with all the remaining materials, and then drying; functionally modifying the surface of the composite material, the surface modification includes the following steps: preparing a silane coupling agent solution, the silane coupling agent concentration is within the range of 5%, the silane coupling agent is aminosilane or hydroxysilane, coating the prepared silane coupling agent solution on the surface of the composite material, and the thickness is controlled between 50um, and finally drying the material, drying and curing at a temperature of 120°C for 20 hours to enhance its adsorption performance and stability; pouring the composite material into a stirring tank, and adding the soil from which the antibiotics need to be removed to mix and stir for full contact, the speed is controlled between 220r / min during the stirring process, and the temperature is controlled at 125°C during the stirring process to achieve efficient removal of antibiotics.

[0037] Embodiment 2

[0038] The raw material components of the composite material include 6 parts of activated carbon, 4 parts of iron oxide nanoparticles, 2 parts of zinc oxide nanoparticles, 1.5 parts of tungsten disulfide, 1 part of copper disulfide, 2-6 parts of silica gel, 15 parts of gypsum, 10 parts of iron tailings sand and 8 parts of zeolite.

[0039] The specific production steps include the following: activated carbon pretreatment: calcining the activated carbon at high temperature to remove impurities and increase its adsorption performance. The pretreatment of activated carbon is as follows: first, oxidation treatment is performed to expose the activated carbon to chlorine dioxide at a temperature of 200°C for 2 hours, acid and alkali washing is performed, and a 48% sodium hydroxide solution is used for washing for 4 hours, and then heat treatment is performed at a high temperature of 700°C for 1 hour. The surface of the activated carbon is treated with ammonia or ammonia gas, and the activated carbon is repeatedly washed with pure water, and then dried at a low temperature; prepare a stable iron oxide nanoparticle solution and a zinc oxide nanoparticle solution, and synthesize them by a solvent thermal method. The solvothermal preparation of the iron oxide nanoparticle solution is as follows: prepare iron chloride, ethylene glycol, and octylamine, mix the raw materials in a reaction bottle and stir evenly, the stirring speed is generally 500rpm, and the reaction bottle is placed in an oil bath and heated to 95°C. degree, keep it for 2 hours, after cooling, collect the precipitate, wash and dry it to obtain iron oxide nanoparticles; fully mix and stir the iron oxide nanoparticle solution and the zinc oxide nanoparticle solution with all the remaining materials, and then dry it; functionally modify the surface of the composite material, the surface modification includes the following steps, prepare a silane coupling agent solution, the silane coupling agent concentration is within the range of 1%, the silane coupling agent is aminosilane or hydroxysilane, the prepared silane coupling agent solution is coated on the surface of the composite material, the thickness is controlled between 6um, and finally the material is dried and cured at a temperature of 50°C for 10 hours to enhance its adsorption performance and stability; the composite material is poured into a stirring tank, and the soil from which the antibiotics need to be removed is added for mixing and stirring for full contact, the speed is controlled between 120r / min during the stirring process, and the temperature is controlled at 80°C during the stirring process to achieve efficient removal of antibiotics.

[0040] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It is obvious to those skilled in the art that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic features of the present invention. Therefore, no matter from which point of view, the embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes that fall within the meaning and scope of the equivalent elements of the claims are included in the present invention.

[0041] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A composite material for efficiently removing antibiotics from soil, characterized in that: The raw materials of the composite material include 6-20 parts of activated carbon, 4-8 parts of iron oxide nanoparticles, 2-6 parts of zinc oxide nanoparticles, 1.5-4 parts of tungsten disulfide, 1-4 parts of copper disulfide, 2-6 parts of silica gel, 15-30 parts of gypsum, 10-20 parts of iron tailings sand and 8-12 parts of zeolite.

2. The composite material for efficiently removing antibiotics in soil according to claim 1, characterized in that: The raw material components of the composite material include 20 parts of activated carbon, 8 parts of iron oxide nanoparticles, 6 parts of zinc oxide nanoparticles, 4 parts of tungsten disulfide, 4 parts of copper disulfide, 6 parts of silica gel, 15-30 parts of gypsum, 10-20 parts of iron tailings sand, and 8-12 parts of zeolite.

3. The composite material for efficiently removing antibiotics in soil according to claim 1, characterized in that: The raw material components of the composite material include 6 parts of activated carbon, 4 parts of iron oxide nanoparticles, 2 parts of zinc oxide nanoparticles, 1.5 parts of tungsten disulfide, 1 part of copper disulfide, 2-6 parts of silica gel, 15 parts of gypsum, 10 parts of iron tailings sand and 8 parts of zeolite.

4. The method for preparing a composite material for efficiently removing antibiotics in soil according to claim 1, characterized in that: The specific production steps include the following: S1, activated carbon pretreatment: calcining the activated carbon at high temperature to remove impurities and increase its adsorption performance; S2, preparation of stable iron oxide nanoparticle solution and zinc oxide nanoparticle solution, synthesized by solvothermal method; S3, fully mixing and stirring the iron oxide nanoparticle solution and the zinc oxide nanoparticle solution with all the remaining materials, and then drying them; S4, functional modification of the composite surface to enhance its adsorption performance and stability; S5, pouring the composite material into a stirring tank, adding the soil from which the antibiotics need to be removed, mixing and stirring for full contact, and realizing efficient removal of the antibiotics.

5. The method for preparing a composite material for efficiently removing antibiotics in soil according to claim 1, characterized in that: In step S1, the pretreatment of the activated carbon is as follows: first, oxidation treatment is performed to expose the activated carbon to chlorine dioxide at a temperature of 200-250°C for a treatment time of 2-4 hours, acid and alkali washing is performed, a sodium hydroxide solution with a concentration of 48-53% is used, and the washing time is 4-6 hours, and then heat treatment is performed at a high temperature of 700-1000°C for a treatment time of 1-2 hours, ammonia or ammonia gas is used to treat the surface of the activated carbon, the activated carbon is repeatedly washed with pure water, and then dried at a low temperature.

6. The method for preparing a composite material for efficiently removing antibiotics in soil according to claim 1, characterized in that: In step S2, the solvothermal method for preparing the iron oxide nanoparticle solution is as follows: prepare iron chloride, ethylene glycol, and octylamine, mix the raw materials in a reaction bottle and stir evenly, the stirring speed is generally 500-800 rpm, put the reaction bottle into an oil bath, heat to 95°C, maintain for 2-4 hours, cool, collect the precipitate, wash and dry to obtain iron oxide nanoparticles.

7. The method for preparing a composite material for efficiently removing antibiotics in soil according to claim 1, characterized in that: In step S4, the surface modification includes the following steps: preparing a silane coupling agent solution, the silane coupling agent concentration is in the range of 1-5%, the silane coupling agent is aminosilane or hydroxysilane, coating the prepared silane coupling agent solution on the surface of the composite material, and controlling the thickness between 6-50um, and finally drying the material at a temperature of 50-120°C for 10-20h for drying and curing.

8. The method for preparing a composite material for efficiently removing antibiotics in soil according to claim 1, characterized in that: In step S5, the rotation speed is controlled between 120 r / min and 220 r / min during the stirring process, and the temperature is controlled between 80 and 125° C. during the stirring process.