CN110624496B - Preparation method of porous boron nitride-based composite material for purifying organic wastewater - Google Patents
Preparation method of porous boron nitride-based composite material for purifying organic wastewater Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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Abstract
A preparation method of a porous boron nitride-based composite material for purifying organic wastewater adopts two-step synthesis: firstly, preparing porous boron nitride by a thermal cracking method; and secondly, preparing the alpha-phase iron oxide/porous boron nitride-based composite water purification material by a microwave-assisted hydrothermal method. The invention utilizes microwave assistance, reduces the synthesis time, has simple process and little pollution, and is suitable for low-cost large-scale production. The regeneration efficiency of the alpha-phase iron oxide/porous boron nitride-based composite water purification material obtained by the invention is improved to 93.5 percent from 10.8 percent of pure porous boron nitride before compounding, and the regeneration and reutilization performance of the porous boron nitride-based water purification material is greatly improved. In addition, the conventional high-temperature calcination and acid washing processes are not used in the regeneration process of the obtained composite water purification material, and an ozone-assisted regeneration method is used, so that secondary pollution is avoided, and the regeneration cost is reduced.
Description
Technical Field
The technical scheme of the invention belongs to the technical field of water treatment environment treatment, and particularly relates to a preparation method of a porous boron nitride-based composite material for purifying organic wastewater.
Background
With the growth of the world population and the acceleration of the industrialization process, environmental problems, especially the problem of water pollution, increasingly become one of the key problems to be solved urgently. Untreated industrial and domestic wastewater is discharged directly, which poses a great threat to the natural ecological environment and the health of human bodies. The purification treatment of sewage by advanced technologies such as adsorption and the like has important significance for solving the problem of water body pollution.
Traditional adsorbing materials for water purification, such as activated carbon, carbon fiber membranes, aminated high molecular polymer fibers and the like, have good adsorption capacity for common pollutants. However, the sewage purification capacity and the recycling rate of the traditional adsorbing materials cannot completely meet the requirements of sewage with complex components (such as containing pesticides, antibiotics and the like) and stricter discharge standards.
Due to the unique physical and chemical characteristics of the porous boron nitride, such as high specific surface area, large pore volume, low density, excellent chemical stability and oxidation resistance, the porous boron nitride has wide application prospects in the field of water purification. However, the porous boron nitride water purification material has low recycling efficiency, which causes great waste of resources and is also not beneficial to environmental protection. The regeneration method for treating porous boron nitride with saturated adsorption on pollutants in water at present mainly comprises the following steps: acid washing and burning. However, these regeneration methods have the disadvantages of secondary environmental pollution, high cost, high energy consumption, etc., and the low-efficiency and high-pollution regeneration methods hinder the practical application of porous boron nitride in the field of water purification. Therefore, a composite water purification material which has low cost, simple preparation process, strong regeneration capacity, high efficient removal capacity for sewage containing complex components such as chemical pesticides, antibiotics and the like and high recycling efficiency is urgently needed.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a preparation method of a porous boron nitride-based composite material for purifying organic wastewater. Porous boron nitride and ferric chloride are used as raw materials, and the alpha-phase iron oxide/porous boron nitride-based composite water purification material is prepared through the steps of a microwave-assisted hydrothermal method, ball milling, ammoniation and the like. The obtained composite water purification material not only has excellent adsorption capacity, but also has enhanced regeneration capacity. In addition, the conventional high-temperature calcination and acid washing processes are not used in the regeneration process of the obtained composite water purification material, and an ozone-assisted regeneration method is used, so that secondary pollution is avoided, and the regeneration cost is reduced. Therefore, the method for producing the alpha-phase iron oxide/porous boron nitride-based composite water purification material in a large scale has wide application prospect in the field of environmental purification and restoration.
A preparation method of a porous boron nitride-based composite material for purifying organic wastewater comprises the following steps:
(1) the mass ratio of the components is 1: (0.01-100) weighing porous boron nitride and ferric chloride, placing the porous boron nitride and the ferric chloride in deionized water, stirring for 0.5-2 hours, and then carrying out ultrasonic treatment for 0.1-2 hours;
(2) adjusting the pH value of the mixed solution obtained in the step (1) to 9-11, and stirring for 0.5-5 hours;
(3) placing the mixed solution obtained in the step (2) into an autoclave, heating to 140-200 ℃ under the assistance of microwaves, and preserving heat for 0.1-0.3 hour;
(4) after the mixed solution obtained in the step (3) is cooled to room temperature, filtering to obtain solid powder, placing the obtained solid powder into a ball milling tank of a ball mill, and carrying out ball milling for 10-600 minutes at the rotating speed of 100-6000 revolutions per minute by the ball mill;
(5) and (4) carrying out heat treatment on the solid mixture obtained in the step (4) at 600-1000 ℃ in an ammonia atmosphere, wherein the heating rate is 1-20 ℃ per minute, and the heat preservation time is 3-6 hours. The obtained product is a porous boron nitride-based composite material for purifying organic wastewater.
The gas flow rate of the ammonia gas in the step (5) is 10-100 ml/min.
The invention has the beneficial effects that:
1. the porous boron nitride-based composite material for purifying organic wastewater, which is obtained by the method, overcomes the defect of low regeneration efficiency of the porous boron nitride adsorbing material, does not use the conventional high-temperature calcination and acid washing process in the regeneration process of the obtained composite water purifying material, and adopts an ozone-assisted regeneration method, so that secondary pollution is avoided, and the regeneration cost is reduced;
2. the main raw materials adopted by the invention are ferric chloride and boron nitride, which belong to common industrial raw materials, are easy to obtain and nontoxic, the preparation process is simple and easy to operate, the synthesis process is environment-friendly, and toxic and harmful byproducts are not generated;
3. the distance between the adsorbent and a target pollutant is reduced by utilizing the adsorption performance of the composite water purification material, the contact probability of the adsorbent and the target pollutant is improved, the synergistic effect of adsorption and catalytic degradation of porous boron nitride and alpha-phase iron oxide under the assistance of ozone is fully exerted, the regeneration efficiency of the obtained alpha-phase iron oxide/porous boron nitride-based composite water purification material under the assistance of ozone is improved to 93.5 percent from 10.8 percent of pure porous boron nitride before compounding, the regeneration reutilization performance of the porous boron nitride-based water purification material is greatly improved, and the composite water purification material has important significance for environmental management and green energy utilization.
4. The preparation process of the method is simple, does not use strong acid for activation, has little pollution and is suitable for large-scale industrial production.
Drawings
The invention is further illustrated with reference to the following figures and examples.
Fig. 1 is a scanning electron microscope image of the porous boron nitride-based composite material for organic wastewater purification in example 1.
Figure 2 is a low temperature nitrogen adsorption-desorption isotherm curve of the product of example 1.
FIG. 3 is a graph showing the removal rate of organic contaminants from an aqueous solution at ambient temperature for the product of example 1.
FIG. 4 shows the recycling efficiency of the product of example 1 at room temperature with the aid of ozone for organic pollutants in aqueous solution.
Detailed Description
Example 1
Referring to fig. 1 to 4, (1) the mass ratio of 1: 0.01 weighing porous boron nitride and ferric chloride, placing the porous boron nitride and the ferric chloride in deionized water, stirring for 0.5 hour, and then carrying out ultrasonic treatment for 0.1 hour;
(2) adjusting the pH value of the mixed solution obtained in the step (1) to 9, and stirring for 0.5 hour;
(3) placing the mixed solution obtained in the step (2) into an autoclave, heating to 140 ℃ under the assistance of microwaves, and preserving heat for 0.1 hour;
(4) after the mixed solution obtained in the step (3) is cooled to room temperature, solid powder is obtained through filtration, the obtained solid powder is placed in a ball milling tank of a ball mill, and the ball milling is carried out for 10 minutes at the rotating speed of 100 revolutions per minute;
(5) and (4) carrying out heat treatment on the solid mixture obtained in the step (4) at 600 ℃ in an ammonia gas atmosphere with the airflow rate of 10 ml/min, wherein the heating rate is 1 ℃ per minute, and the heat preservation time is 3 hours. The obtained product is a porous boron nitride-based composite material for purifying organic wastewater.
Through observation of a scanning electron microscope (figure 1), the nano particles of the alpha-phase iron oxide are uniformly distributed on the surface of the porous boron nitride to form the composite water purification material; the alpha-phase iron oxide/porous boron nitride-based composite water purification material has a porous structure comprising micropores and mesopores, which can be obtained by calculation and analysis of a low-temperature nitrogen adsorption-desorption isotherm in fig. 2. The organic pollutant water purification capability and the regeneration reutilization rate of the obtained alpha-phase iron oxide/porous boron nitride-based composite water purification material are tested, and the results show that: under the conditions of normal temperature and ozone assistance, each gram of the product can remove 70 percent of organic pollutants in 10 liters of solution with the concentration of 20 mg/liter within 5 minutes, and remove 99 percent of the organic pollutants in the solution within 30 minutes (figure 3), which shows that the obtained alpha-phase iron oxide/porous boron nitride composite material has high water purification efficiency; fig. 4 shows that 93.5% of the removal efficiency of the product is still maintained after the product is reused for 60 times, which indicates that the obtained alpha-phase iron oxide/porous boron nitride-based composite water purification material has excellent recycling efficiency. The composite material has wide application prospect in the field of environmental purification.
Examples 2 and 3
The mass ratio of the porous boron nitride and the ferric chloride in the step (1) in the example 1 was changed to 1:1 and 1:100, and the other operations were the same as those in the example 1, to obtain the same product as in the example 1.
Examples 4 and 5
The stirring time in step (1) in example 1 was changed to 1 hour and 2 hours, and the other operations were the same as in example 1 to obtain the same product as in example 1.
Examples 6 and 7
The ultrasonic treatment time in the step (1) in example 1 was changed to 1 hour and 2 hours, and the other operations were the same as in example 1 to obtain the same product as in example 1.
Examples 8 and 9
The same procedure as in example 1 was repeated except that the pH in step (2) in example 1 was changed to 10 or 11, and the same procedure as in example 1 was repeated to obtain the same product as in example 1.
Examples 10 and 11
The stirring time in step (2) in example 1 was changed to 2.5 hours and 5 hours, and the other operations were the same as in example 1 to obtain the same product as in example 1.
Examples 12 and 13
The heating temperature in step (3) in example 1 was changed to 170 ℃ and 200 ℃, and the other operations were the same as in example 1 to obtain the same product as in example 1.
Examples 14 and 15
The holding time in step (3) in example 1 was changed to 0.2 hour and 0.3 hour, and the other operations were the same as in example 1 to obtain the same product as in example 1.
Examples 16 and 17
The same operations as in example 1 were carried out except that the rotation speed of the ball mill in step (4) in example 1 was changed to 3000 rpm and 6000 rpm, and the product was obtained as in example 1.
Examples 18 and 19
The ball milling time in the step (4) in example 1 was changed to 300 minutes and 600 minutes, and the other operations were the same as in example 1 to obtain the same product as in example 1.
Examples 20 and 21
The flow rate of ammonia gas in step (5) in example 1 was changed to 50 ml/min and 100 ml/min, and the other operations were the same as in example 1 to obtain the same product as in example 1.
Examples 22 and 23
The heating temperature in the step (5) in example 1 was changed to 800 ℃ and 1000 ℃, and the other operations were the same as in example 1 to obtain the same product as in example 1.
Examples 24 and 25
The same procedure as in example 1 was repeated except that the temperature increase rate in step (5) in example 1 was changed to 10 ℃ per minute and 20 ℃ per minute, to obtain the same product as in example 1.
Examples 26 and 27
The holding time in step (5) in example 1 was changed to 4.5 hours and 6 hours, and the other operations were the same as in example 1 to obtain the same product as in example 1.
The above are only some embodiments of the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are within the scope of the present invention.
Claims (8)
1. A preparation method of a porous boron nitride-based composite material for purifying organic wastewater is characterized by comprising the following steps: the method comprises the following steps:
(1) the mass ratio of the components is 1: (0.01-100) weighing porous boron nitride and ferric chloride, placing the porous boron nitride and the ferric chloride in deionized water, stirring for 0.5-2 hours, and then carrying out ultrasonic treatment for 0.1-2 hours;
(2) adjusting the pH value of the mixed solution obtained in the step (1) to 9-11, and stirring for 0.5-5 hours;
(3) placing the mixed solution obtained in the step (2) into an autoclave, heating to 140-200 ℃ under the assistance of microwaves, and preserving heat for 0.1-0.3 hour;
(4) after the mixed solution obtained in the step (3) is cooled to room temperature, filtering to obtain solid powder, placing the obtained solid powder into a ball milling tank of a ball mill, and carrying out ball milling for 10-600 minutes at the rotating speed of 100-6000 revolutions per minute by the ball mill;
(5) and (3) carrying out heat treatment on the solid mixture obtained in the step (4) at 600-1000 ℃ in an ammonia atmosphere, wherein the heating rate is 1-20 ℃ per minute, and the heat preservation time is 3-6 hours, so that the obtained product is the porous boron nitride composite material for purifying organic wastewater.
2. The method for preparing a porous boron nitride-based composite material for organic wastewater purification according to claim 1, wherein: and (3) the gas flow rate of the ammonia gas in the step (5) is 10-100 ml/min.
3. The method for preparing a porous boron nitride-based composite material for organic wastewater purification according to claim 1, wherein: the morphology of the porous boron nitride in the step (1) comprises fiber shape, sheet shape and spherical shape.
4. The composite material for organic wastewater purification prepared by the preparation method according to any one of claims 1 to 3, wherein: the composite material is formed by uniformly distributing alpha-phase iron oxide nanoparticles on the surface of porous boron nitride.
5. The composite material for organic wastewater purification according to claim 4, wherein: in the regeneration process of the composite material, the conventional high-temperature calcination and acid washing processes are not used, and an ozone-assisted regeneration method is used.
6. The composite material for organic wastewater purification according to claim 4, wherein: the composite material has high specific surface area and stable performance and can be recycled.
7. The composite material for organic wastewater purification according to claim 4, wherein: the composite material is a porous structure and comprises micropores and mesopores.
8. The composite material for organic wastewater purification according to claim 4, wherein: the adsorption performance of the composite material reduces the distance between the adsorbent and the target pollutant, improves the contact probability of the adsorbent and the target pollutant, and exerts the synergistic effect of adsorption and catalytic degradation of the porous boron nitride and the alpha-phase iron oxide.
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| CN109174151A (en) * | 2018-08-30 | 2019-01-11 | 湖北第二师范学院 | One kind is for three-dimensional porous boron nitride composite of air cleaning and preparation method thereof |
| CN111229281A (en) * | 2020-02-25 | 2020-06-05 | 江苏大学 | Magnetic Fe2O3/BN composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109174151A (en) * | 2018-08-30 | 2019-01-11 | 湖北第二师范学院 | One kind is for three-dimensional porous boron nitride composite of air cleaning and preparation method thereof |
| CN111229281A (en) * | 2020-02-25 | 2020-06-05 | 江苏大学 | Magnetic Fe2O3/BN composite material and preparation method and application thereof |
Non-Patent Citations (3)
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| Dwindling the re-stacking by simultaneous exfoliation of boron nitride and decoration of a-Fe2O3 nanoparticles using a solvothermal route;Pitchai Thangasamy，et.al.;《New J. Chem》;20180221;第42卷;摘要，第5091页Experimental section * |
| 城市污水处理厂环境激素类污染物控制技术研究;王杰;《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》;20151215(第12期);第36页第1段，第30页第2段 * |
| 多孔氮化硼的制备、表征、化学活化及其环境能源领域应用的研究;李杰;《中国优秀博硕士学位论文全文数据库(博士) 工程科技Ⅰ辑》;20190315(第03期);第2页第2段 * |
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