阅读说明：本技术 一种硅基杂多酸掺杂的磁性复合膜材料的制备方法 (Preparation method of magnetic composite membrane material doped with silicon-based heteropoly acid ) 是由 曾庆铭 张迪 窦国梁 王凯 张建 董志超 于 2020-04-10 设计创作，主要内容包括：本发明属于无机材料制备技术领域,具体涉及一种硅基杂多酸掺杂的磁性复合膜材料的制备方法,包括以下步骤：(1)将金属盐A、金属盐B和氧化石墨烯加入到溶剂C中,搅拌,加入硅基杂多酸,继续搅拌均匀得混合液；(2)将碱溶解在上述混合液中,并进行溶剂热反应；(3)将溶剂热反应制得的产物抽滤,并用乙醇和水分别洗涤干燥成膜。本发明所述的硅基杂多酸掺杂的磁性复合膜材料的制备方法简单,组成和结构均可控,膜层厚度可控,具有磁性,便于回收和使用,解决了复合膜材料制备工艺复杂的问题；工艺流程简便,环境友好,适于大规模工业化生产,应用前景广泛；所制备的硅基杂多酸掺杂的磁性复合膜材料芬顿性能优异,可回收,结构稳定性高。(The invention belongs to the technical field of inorganic material preparation, and particularly relates to a preparation method of a magnetic composite membrane material doped with a silicon-based heteropoly acid, which comprises the following steps: (1) adding the metal salt A, the metal salt B and the graphene oxide into the solvent C, stirring, adding the silicon-based heteropoly acid, and continuously stirring uniformly to obtain a mixed solution; (2) dissolving alkali in the mixed solution, and carrying out solvent thermal reaction; (3) and (3) filtering a product obtained by the solvent thermal reaction, and washing and drying the product with ethanol and water respectively to form a film. The preparation method of the magnetic composite film material doped with the silicon-based heteropoly acid is simple, the composition and the structure are controllable, the thickness of the film layer is controllable, the film layer is magnetic, the recovery and the use are convenient, and the problem that the preparation process of the composite film material is complex is solved; the process flow is simple and convenient, the environment is friendly, the method is suitable for large-scale industrial production, and the application prospect is wide; the prepared magnetic composite membrane material doped with the silicon-based heteropoly acid has excellent Fenton performance, can be recycled and has high structural stability.)

1. A preparation method of a magnetic composite membrane material doped with a silicon-based heteropoly acid is characterized by comprising the following steps: the method comprises the following steps:

(1) adding the metal salt A, the metal salt B and the graphene oxide into the solvent C, stirring at normal temperature, then adding the silicon-based heteropoly acid, and continuously stirring uniformly to obtain a mixed solution;

(2) dissolving alkali in the prepared mixed solution, and carrying out solvothermal reaction;

(3) and (3) filtering a product obtained by the solvent thermal reaction, washing the product with ethanol and water in sequence, and drying the product to form a film to obtain a finished product.

2. The preparation method of the magnetic composite film material doped with the heteropoly acid silyl group according to claim 1, which is characterized in that: the metal salt A is one or more of ferric nitrate, ferric chloride and ferric sulfate.

3. The preparation method of the magnetic composite film material doped with the heteropoly acid silyl group according to claim 1, which is characterized in that: the metal salt B is one of nitrate, chloride and sulfate of cobalt, or one of nitrate, chloride and sulfate of nickel.

4. The method for preparing the magnetic composite film material doped with the heteropoly acid silyl group according to any one of claims 1 to 3, wherein the method comprises the following steps: the molar ratio of the metal salt A to the metal salt B is 1: (0.8-1.2).

5. The preparation method of the magnetic composite film material doped with the heteropoly acid silyl group according to claim 1, which is characterized in that: the solvent C is formamide or N, N-dimethylformamide.

6. The preparation method of the magnetic composite film material doped with the heteropoly acid silyl group according to claim 1, which is characterized in that: the silicon-based heteropoly acid is one or more of silicotungstic heteropoly acid and silicomolybdic heteropoly acid.

7. The preparation method of the magnetic composite film material doped with the heteropoly acid silyl group according to claim 1, which is characterized in that: the alkali is sodium hydroxide or potassium hydroxide.

8. The preparation method of the magnetic composite film material doped with the heteropoly acid silyl group according to claim 1, which is characterized in that: the dosage of each component is as follows:

9. the method for preparing the magnetic composite film material doped with the heteropoly acid silyl group according to any one of claim 1, wherein the method comprises the following steps: in the step (1), the metal salt A, the metal salt B and the graphene oxide are stirred in the solvent C for 30-90min, and the mixture is continuously stirred for 30-60min after the silicon-based heteropoly acid is added.

10. The method for preparing the magnetic composite film material doped with the heteropoly acid silyl group according to any one of claims 1 to 3 and 5 to 9, wherein the method comprises the following steps: the process conditions of the solvothermal reaction are as follows: the temperature is 60-130 deg.C, and the time is 30-120 min; the drying temperature of the film is 80-120 ℃, and the drying time is 10-20 h.

Technical Field

The invention belongs to the technical field of inorganic material preparation, and particularly relates to a preparation method of a magnetic composite membrane material doped with a silicon-based heteropoly acid.

Background

The organic silicon compound is a compound with a silicon-carbon bond, has organic and inorganic structural characteristics, has a plurality of unique characteristics in performance, such as high temperature resistance, low temperature resistance, weather resistance, electric insulation, hydrophobicity and the like, and is widely applied to a plurality of fields of textiles, automobiles, aviation, machinery, electronics and the like. The productivity of the organosilicon products in China is continuously increased, the technology is continuously improved, the China benefits from the rapid development of national economy and the manufacturing industry of China, and the organosilicon market which grows fastest globally has become China. However, the wastewater generated in the organosilicon industry poses serious threat to human environment and is in need of treatment. Particularly, the treatment of organic wastewater containing chlorobenzene generated in the production process of siloxane is a difficult problem which is urgently needed to be solved by the current organic silicon industry due to the great treatment difficulty.

At present, the processing method of chlorobenzene organic wastewater generated in the organic silicon industry mainly comprises a physical adsorption method, a chemical oxidation method, micro-electrolysis treatment and biochemical treatment technology. Wherein the physical adsorption method is not complete in treatment, and the adsorbent is easy to cause the harm of solid waste. The micro-electrolysis process consumes a large amount of electric energy, resulting in a large energy consumption. The biochemical treatment technology has high requirements on organic wastewater, is suitable for treating low-concentration organic wastewater, and has high requirements on wastewater. The chemical oxidation technology can treat the organic chlorobenzene waste water under the conditions of normal temperature and normal pressure. The Fenton oxidation technology machine has extremely strong oxidation capacity and is the most main chemical oxidation method for treating the organic silicon wastewater at present. For example, the invention patent (201811511353.2) discloses a biochemical treatment method of organic silicon wastewater, which comprises pretreatment, iron-carbon micro-electrolysis and Fenton-like FENTON advanced catalytic oxidation; the invention patent (201820079061.5) discloses an organic silicon wastewater treatment system, which comprises a sedimentation tank, a regulating tank, a coagulation tank, a secondary sedimentation tank, a UASB upflow anaerobic sludge blanket reactor, an SBR reaction tank, a fenton reactor, a multi-media filter, an RO reverse osmosis device and a sludge concentration tank. The most important technology in Fenton oxidation is the development of a Fenton catalyst, but the catalyst has the defect that the catalyst is not easy to recycle. For this reason, they are magnetically modified for recycling. For example, the invention patent (201811360304.3) discloses a photo-Fenton-like catalyst with barium ferrite capable of being magnetically recycled; the invention patent (201610843498.7) discloses a ferroferric oxide-based magnetic Fenton-like catalyst; the invention patent (201910438840.9) discloses a copper ferrite based magnetic Fenton-like catalyst and the like. However, the dispersion of the nanoparticles in the solution is not easy to collect, and the preparation of the nanoparticles into bulk materials reduces the catalytic activity of the nanoparticles. Therefore, the magnetic Fenton catalytic material is used for preparing the film forming material, so that the contact area of the film forming material and the wastewater can be increased, the catalytic performance is improved, and the film forming material is convenient to recycle. However, no magnetic film for treating organic silicon wastewater has been developed at present.

Disclosure of Invention

The invention aims to provide a preparation method of a silicon-based heteropoly acid doped magnetic composite membrane material, which is simple in process and environment-friendly, and the prepared magnetic composite membrane material is excellent in Fenton catalytic performance.

The preparation method of the magnetic composite membrane material doped with the silicon-based heteropoly acid comprises the following steps:

(1) adding the metal salt A, the metal salt B and the graphene oxide into the solvent C, stirring at normal temperature, then adding the silicon-based heteropoly acid, and continuously stirring uniformly to obtain a mixed solution;

(2) dissolving alkali in the prepared mixed solution, and carrying out solvothermal reaction;

(3) and (3) filtering a product obtained by the solvent thermal reaction, washing the product with ethanol and water respectively, and drying the product to form a film to obtain a finished product.

The metal salt A is one or more of ferric nitrate, ferric chloride and ferric sulfate, preferably ferric nitrate.

The metal salt B is one of nitrate, chloride and sulfate of cobalt, or one of nitrate, chloride and sulfate of nickel. The metal salt B is preferably a nitrate of cobalt or nickel.

The molar ratio of the metal salt A to the metal salt B is 1: (0.8-1.2), preferably in a molar ratio of 1: (0.9-1.1).

The solvent C is formamide or N, N-dimethylformamide, preferably formamide.

The silicon-based heteropoly acid is one or more of silicon-tungsten heteropoly acid and silicon-molybdenum heteropoly acid, and preferably silicon-tungsten heteropoly acid.

The base is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.

In the preparation method, the dosage of each component is as follows:

the preferred component contents are as follows: 100 parts of solvent C, 2-4 parts of metal salt A and metal salt B, 0.02-0.08 part of graphene oxide, 0.2-0.4 part of silicon-based heteropoly acid and 0.2-0.8 part of alkali.

In the step (1), the metal salt A, the metal salt B and the graphene oxide are stirred in the solvent C for 30-90min, preferably 45-80min, and the mixture is continuously stirred for 30-60min after the silicon-based heteropoly acid is added.

The process conditions of the solvothermal reaction are as follows: the temperature is 60-130 deg.C, preferably 70-120 deg.C, and the time is 30-120min, preferably 40-100 min; the drying temperature of the film is 80-120 ℃, preferably 90-110 ℃, and the drying time is 10-20h, preferably 12-18 h.

According to the invention, the metal ions are firstly adsorbed on the surface of the graphene oxide nanosheet by utilizing the electrostatic attraction effect between the metal ions dissolved in the amide solvent and the graphene oxide. After the silica-based heteropoly acid is added, metal ions on the surface of the graphene oxide and the silica-based heteropoly acid can form a stable coordination structure, and the contact between the silica-based heteropoly acid and magnetic particles is facilitated. To provide an alkaline environment, a certain base is added to the solution. In the process of solvothermal reaction, iron ions are combined with cobalt ions or nickel ions to form cobalt ferrite or nickel ferrite magnetic nanoparticles. And forming the magnetic nanoparticles doped with the silicon-based heteropoly acid due to the coordination of the silicon-based heteropoly acid and the magnetic metal ions. The magnetic particles doped with the silicon-based heteropoly acid can be uniformly dispersed on the surface of the graphene oxide nanosheet. During the suction filtration process, the graphene oxide may form a filter cake. In the subsequent drying process, the graphene oxide-supported silicon-based heteropoly acid doped magnetic nanoparticle filter cake can be further dried to form a film.

Compared with the prior art, the invention has the following beneficial effects:

(1) the preparation method of the magnetic composite film material doped with the silicon-based heteropoly acid is simple, the composition and the structure are controllable, the thickness of the film layer is controllable, the film layer is magnetic, the recovery and the use are convenient, and the problem that the preparation process of the composite film material is complex is solved;

(2) the method has simple and convenient process flow, is environment-friendly, is suitable for large-scale industrial production, and has wide application prospect;

(3) the magnetic composite membrane material doped with the silicon-based heteropoly acid prepared by the invention has excellent Fenton performance, recoverability and high structural stability.

Drawings

FIG. 1 is a scanning electron microscope image of a silica-based heteropoly acid doped magnetic composite film material prepared in example 1;

FIG. 2 is a diagram showing the degradation of chlorobenzene molecules in the membrane material prepared in example 1.

Detailed Description

The invention is further described with reference to the following examples and the accompanying drawings.