阅读说明：本技术 一种CoFeOCl材料的制备方法及其应用方法 (Preparation method and application method of CoFeOCl material ) 是由 谈超群 崔鑫鑫 徐庆龙 吴昊天 蹇薪持 于 2019-10-28 设计创作，主要内容包括：本发明提供了一种CoFeOCl材料的制备方法,步骤如下：1)将三氯化铁和无水氯化钴置于水溶液中,超声处理后烘干；2)将烘干的材料在氮气氛围下密封加热,冷却后取出研磨,经洗涤后真空干燥并冷却至室温,即得。上述材料应用于降解水体中抗生素,步骤如下：1)将乙酰苯胺类抗生素溶于水中,加入磷酸盐调节pH；2)将CoFeOCl加入有乙酰苯胺类抗生素的水溶液中得混合溶液；3)向混合溶液中加入过氧单硫酸氢钾,隔一定时间吸取一定量样品过滤,滤液进行后续分析,过滤后残留的固体清洗后真空干燥得到再生的CoFeOCl。本发明提升了FeOCl催化过氧单硫酸氢钾的效率,提高了其降解水体中抗生素的速度,降低了成本。(The invention provides a preparation method of a CoFeOCl material, which comprises the following steps: 1) putting ferric trichloride and anhydrous cobalt chloride into an aqueous solution, performing ultrasonic treatment, and drying; 2) and sealing and heating the dried material in a nitrogen atmosphere, cooling, taking out and grinding, washing, vacuum drying and cooling to room temperature to obtain the material. The material is applied to degrading antibiotics in water and comprises the following steps: 1) dissolving acetanilide antibiotics in water, and adding phosphate to adjust the pH value; 2) adding CoFeOCl into an aqueous solution containing acetanilide antibiotics to obtain a mixed solution; 3) and adding potassium hydrogen peroxymonosulfate into the mixed solution, sucking a certain amount of sample at certain intervals, filtering, performing subsequent analysis on the filtrate, cleaning the residual solid after filtering, and performing vacuum drying to obtain the regenerated CoFeOCl. The method improves the efficiency of catalyzing potassium hydrogen peroxymonosulfate by FeOCl, improves the speed of degrading antibiotics in water and reduces the cost.)

1. A preparation method of CoFeOCl material is characterized in that: the method comprises the following steps:

1) putting ferric trichloride and anhydrous cobalt chloride into an aqueous solution, performing ultrasonic treatment, and drying;

2) sealing and heating the material dried in the step 1) in a nitrogen atmosphere, cooling, taking out, fully grinding, washing, vacuum drying and cooling to room temperature to obtain a black powdery CoFeOCl material.

2. The method of claim 1, wherein the CoFeOCl material is prepared by: the mass ratio of the ferric trichloride to the anhydrous cobalt chloride in the step 1) is 1: 1.5-1: 1.6.

3. The method of claim 1, wherein the CoFeOCl material is prepared by: in the drying after the ultrasonic treatment in the step 1), the drying refers to drying in an oven at the temperature of 40-60 ℃ for 10-10.5 h.

4. The method of claim 1, wherein the CoFeOCl material is prepared by: the step 2) of sealing and heating in the nitrogen atmosphere refers to sealing and heating in a muffle furnace in the nitrogen atmosphere, heating the muffle furnace to 250-270 ℃ for 80-90 min at a constant temperature, wherein the heating rate is 2-4 ℃/min.

5. The method of claim 1, wherein the CoFeOCl material is prepared by: the vacuum drying in the step 2) refers to drying for 10 to 10.5 hours in a vacuum drying oven at the temperature of between 60 and 70 ℃.

6. A method of using the coffeocl material produced according to claim 1, wherein: the CoFeOCl material is applied to degrading antibiotics in water and can be recycled, and the specific steps are as follows:

1) dissolving acetanilide antibiotics in water, and then adding phosphate to adjust the pH value of the solution to 6.5-7.5 to obtain an aqueous solution containing the acetanilide antibiotics;

2) mixing powdery CoFeOCl with an aqueous solution containing acetanilide antibiotics to obtain a mixed solution;

3) adding potassium hydrogen peroxymonosulfate KHSO into the mixed solution₅Reacting, sucking a certain amount of sample at regular intervals, filtering, analyzing filtrate, and distilling residual solidAnd washing with water and ethanol, and drying in vacuum to obtain regenerated CoFeOCl powder.

7. The method of claim 6 for applying a CoFeOCl material, wherein: the acetanilide antibiotics comprise phenacetin or paracetamol.

8. The method of claim 6 for applying a CoFeOCl material, wherein: the powdered CoFeOCl and the potassium hydrogen peroxymonosulfate KHSO₅The mass ratio of (A) to (B) is 1: 1.4-1: 1.6.

9. The method of claim 6 for applying a CoFeOCl material, wherein: in the step 3) of absorbing a certain amount of sample for filtration, the filter membrane used for filtration is the filter membrane with the aperture less than or equal to 0.45 mu m.

10. The method of claim 6 for applying a CoFeOCl material, wherein: and 3) in the regenerated CoFeOCl powder obtained by vacuum drying in the step 3), the vacuum drying refers to vacuum drying for 11 to 12 hours in an oven at the temperature of between 60 and 70 ℃.

Technical Field

The invention relates to a preparation method and an application method of a CoFeOCl material, belonging to the technical field of water treatment.

Background

Antibiotics and personal care products (PPCPs) are a new class of emerging organic pollutants including various antibiotics, hormones, anti-inflammatory agents, antiepileptic antibiotics, lipid regulators, β receptor blockers, contrast agents and cytostatic agents, as well as antibacterial agents, synthetic musk, insect repellents, antiseptics, fragrances, sunscreens and the like personal care products.

Advanced Oxidation Processes (AOPs) are characterized by the production of highly reactive free radicals, which degrade most organic species and are fast in reaction rate. Researchers have been concerned recently with the generation of SO₄ ^·-Is used for degrading micro-organic micro-pollutants, controlling the formation of disinfection byproducts and inactivating microorganisms. Although OH and SO₄ ^·-Is comparable, but SO₄ ^·-More selective than OHAnd (3) degrading the organic micro-polluted substrate. To generate SO₄ ^·-Typically, heat, alkali, Ultraviolet (UV), ultrasonic, transition metal, and the like are used to deactivate Peroxodisulfate (PDS) or Peroxomonosulfate (PMS). Transition metals are considered effective and viable activators compared to other processes due to their high catalytic efficiency, low energy consumption and ease of handling. Generally, PMS is always more easily activated by transition metals than PDS due to its asymmetric structure. In addition, the PMS is solid at normal temperature, has stable property and is convenient to transport and store, thereby gradually arousing the attention of broad scholars. Iron oxychloride (FeOCl) by activating H₂O₂Has extremely high efficiency in decomposing OH and degrading persistent organic substances. Due to PMS and H₂O₂Having a similar peroxide structure, FeOCl is also considered to be an effective activator for PMS. Indeed, FeOCl has previously been reported as a functional material. Its structure is mainly characterized by its self-stacking crystal gaps, known as "van der waals layers". FeOCl has proven to be an excellent host of intercalation reactions due to the weak interlayer interactions. The chemical state of iron (Fe) will be changed by appropriate modification of the structure by strong oxidizing power by transferring charges between the intercalated organic compound and the inorganic matrix³⁺→Fe²⁺). About 25% Fe when the guest molecule is adsorbed or interacts with FeOCl³⁺Proved to be reduced to Fe in situ²⁺. However, because the iron element has limited catalytic efficiency on PMS, how to further modify materials and construct a more efficient and stable heterogeneous catalytic system is a key problem for further improving the removal rate of organic pollutants by a PMS-based advanced oxidation method and is also one of the main contents of the invention. The developed CoFeOCl material has more efficient catalytic activity on peroxymonosulfate, and is a brand new breakthrough in the research field of controlling organic matters which are difficult to degrade in water and protecting the safety of drinking water.

Disclosure of Invention

The technical problem is as follows: aiming at the problems, the invention aims to provide a preparation method and an application method of a CoFeOCl material, which improve the application of the FeOCl catalytic material in catalyzing peroxy monosulfurAcid potassium KHSO₅The method has the advantages that the catalytic efficiency is high, and in the application process of degrading antibiotics in water, CoFeOCl powder can be recycled and regenerated, so that the reaction speed is increased, and the cost is reduced.

The technical scheme is as follows: in order to achieve the above object, the present invention provides a method for preparing a coffeocl material, comprising the steps of:

1) putting ferric trichloride and anhydrous cobalt chloride into an aqueous solution, performing ultrasonic treatment, and drying;

2) sealing and heating the material dried in the step 1) in a nitrogen atmosphere, cooling, taking out, fully grinding, washing, vacuum drying and cooling to room temperature to obtain a black powdery CoFeOCl material.

Wherein:

the mass ratio of the ferric trichloride to the anhydrous cobalt chloride in the step 1) is 1: 1.5-1: 1.6.

In the drying after the ultrasonic treatment in the step 1), the drying refers to drying in an oven at the temperature of 40-60 ℃ for 10-10.5 h.

The step 2) of sealing and heating in the nitrogen atmosphere refers to sealing and heating in a muffle furnace in the nitrogen atmosphere, heating the muffle furnace to 250-270 ℃ for 80-90 min at a constant temperature, wherein the heating rate is 2-4 ℃/min.

The vacuum drying in the step 2) refers to drying for 10 to 10.5 hours in a vacuum drying oven at the temperature of between 60 and 70 ℃.

The invention also provides an application method of the CoFeOCl material prepared by the method, the CoFeOCl material is applied to degrading antibiotics in water, and the CoFeOCl material in the method can be regenerated and reused, and the specific steps are as follows:

1) dissolving acetanilide antibiotics in water, and then adding phosphate to adjust the pH value of the solution to 6.5-7.5 to obtain an aqueous solution containing the acetanilide antibiotics;

2) mixing powdery CoFeOCl with an aqueous solution containing acetanilide antibiotics to obtain a mixed solution;

3) adding potassium hydrogen peroxymonosulfate KHSO into the mixed solution₅Reacting, sucking a certain amount of liquid at regular intervalsThe sample was filtered, the filtrate was subjected to subsequent analysis, and the solid remaining after filtration was washed with distilled water and ethanol, and vacuum-dried to obtain regenerated CoFeOCl powder.

Wherein:

the acetanilide antibiotics comprise phenacetin or paracetamol.

The powdered CoFeOCl and the potassium hydrogen peroxymonosulfate KHSO₅The mass ratio of (A) to (B) is 1: 1.4-1: 1.6.

In the step 3) of absorbing a certain amount of sample for filtration, the filter membrane used for filtration is the filter membrane with the aperture less than or equal to 0.45 mu m.

And 3) in the regenerated CoFeOCl powder obtained by vacuum drying in the step 3), the vacuum drying refers to vacuum drying for 11 to 12 hours in an oven at the temperature of between 60 and 70 ℃.

Has the advantages that: compared with the prior art, the invention has the advantages that:

1. the CoFeOCl provided by the invention has the advantages of simple preparation process, easily purchased raw materials, safe and mild preparation conditions and capability of batch production;

2. in the application method for degrading antibiotics in water provided by the invention, CoFeOCl powder can be recycled and regenerated, the cost is reduced while the reaction speed is improved, and the CoFeOCl powder has good stability, is simple to operate and is easy to realize;

3. by adopting the application method of the CoFeOCl material in degrading the antibiotics in the water body, the CoFeOCl material is proved to be an excellent main body of intercalation reaction, has the physical sign of efficiently activating an oxidizer to generate a free group, can effectively remove the phenacetin and the paracetamol, has high removal efficiency, and can be used for the purification work of the water body polluted by the acetanilide antibiotics.

Drawings

FIG. 1 is a graph showing the relationship between the removal rate of potassium peroxymonosulfate to paracetamol and time under the condition of different catalyst CoFeOCl dosage in example 2, wherein the CoFeOCl catalyzes the removal rate of potassium peroxymonosulfate and the removal rate of paracetamol

The amounts of CoFeOCl added as the catalyst in example 2 were 0g/L,0.01g/L, 0.03g/L, 0.05g/L, 0.1 g/L;

FIG. 2 is a graph showing the relationship between the removal rate of paracetamol and time for different dosages of potassium hydrogen peroxymonosulfate in example 3

The adding amounts of the oxidizing agent potassium hydrogen peroxymonosulfate in example 3 are respectively 0g/L, 0.0075g/L, 0.015g/L, 0.045g/L and 0.075 g/L.

FIG. 3 shows the effect of different catalyst loadings on phenacetin removal rate from water.

FIG. 4 shows the effect of different amounts of potassium hydrogen peroxymonosulfate on the removal rate of phenacetin from water.

Detailed Description

The invention discusses the mechanism and the efficiency of a CoFeOCl material activated PMS system, tries to degrade typical acetanilide antibiotics, and has important academic research and application values on the development of an advanced oxidation method based on potassium hydrogen peroxymonosulfate and the efficient control of organic pollutants difficult to degrade in water. The invention is described in further detail below with reference to the following description of the drawings and the detailed description.