CN111704196A - Nano CuO/COF composite arsenic removal material and preparation method thereof - Google Patents
Nano CuO/COF composite arsenic removal material and preparation method thereof Download PDFInfo
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- CN111704196A CN111704196A CN202010757313.7A CN202010757313A CN111704196A CN 111704196 A CN111704196 A CN 111704196A CN 202010757313 A CN202010757313 A CN 202010757313A CN 111704196 A CN111704196 A CN 111704196A
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
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Abstract
The invention relates to the field of composite material preparation, in particular to a nano CuO/COF composite arsenic removal material and a preparation method thereof, wherein the preparation method comprises the following steps: adding 1,3, 5-trimethylbenzene phloroglucinol and 2, 5-diethoxy terephthaloyl hydrazine into a mixed solution of 1, 4-dioxane, mesitylene and glacial acetic acid, carrying out ice bath ultrasonic treatment, and then carrying out three cycles of quick freezing, vacuumizing, unfreezing and degassing on the solution; heating the circulated reactant in vacuum for 2-3 days, washing with acetone and methanol, and freeze-drying to obtain a COF material; secondly, dissolving copper nitrate in the ethanol-water mixed solution, and then stirring and adding NaOH solution and NH at room temperature3·H2O, adding COF into the solution after stirring again and carrying out ultrasonic stirring; then putting the solution into a reaction kettle for reaction for 6-10 h, centrifuging, washing with ethanol and water, and drying after washingAnd drying to obtain the nano CuO/COF composite arsenic removal material. The nano CuO/COF composite arsenic removal material prepared by the invention can effectively remove trivalent arsenic in water.
Description
Technical Field
The invention belongs to the field of composite material preparation, and particularly relates to a nano CuO/COF composite arsenic removal material and a preparation method thereof.
Background
The accumulation of arsenic in water environments is a great concern due to its high toxicity, threatening the health of humans. Most arsenic is derived from emissions from industrial processes such as nonferrous smelting, coal burning, glass making, and other industries. Of these industries, the nonferrous metallurgy industry emits over 40,000 tons of arsenic annually. In addition, in non-ferrous metallurgy processes, stable arsenic in the ore is volatilized into exhaust gas at high combustion temperatures and then scrubbed into fouling acids in a wet flue gas scrubbing unit. Stone (stone)After precipitation of the apatite and iron salts, the actual concentration of arsenic in the fouling acid is less than 10mg/L, and the fouling acid has weak acidity and various coexisting heavy metal ions. Unlike many other heavy metals, the chemical valence of arsenic varies with the redox state of the solution. Inorganic trivalent As and tetravalent As are more toxic than organic arsenic in all arsenic species. Under weakly acidic conditions, pentavalent arsenate is negatively charged and therefore easier to handle. However, removal of trivalent arsenic is relatively difficult, and trivalent arsenic can be present as H at pH below 9.23AsO3The form of (1) is preserved. It is difficult to remove uncharged H using conventional physicochemical treatment methods3AsO3. In non-ferrous metal smelters, flue gases contain a large amount of SO2The pH value of the wastewater is always lower; in addition, the coexistence of other heavy metals also increases the difficulty of removing trivalent As from acidic wastewater. Therefore, it is sought to develop an efficient method to achieve the elimination of trivalent arsenic.
CuO is a narrow-bandgap P-type semiconductor material, has low raw material cost, is environment-friendly, pollution-free and easy to recover, and is often used as a catalytic material. The principle is that when the energy is equal to or more than the band gap energy of the semiconductor, OH free radicals with strong oxidizing ability are generated to carry out oxidative decomposition reaction. The nano CuO has high catalytic activity due to the large specific surface area, no toxicity and low cost, and has bright application prospect in the field of environmental catalysis.
Covalent Organic Frameworks (COFs) are a class of crystalline porous organic polymers composed of light elements and are built up by strong covalent bonds. COFs have been widely used in gas adsorption separation, photoelectric field, catalytic field and other fields due to their unique physical and chemical properties. Compared with the traditional crystal material, the COF has the advantages of large specific surface area, good chemical and thermal stability, adjustable pore diameter, low density, functional modification and the like.
Disclosure of Invention
From the above technical background, it is known that trivalent arsenic ions have high toxicity, but generate uncharged H due to the environment of acidic industrial wastewater3AsO3It is very difficult to remove. The present invention providesA nano CuO/COF composite arsenic removal material can effectively remove trivalent arsenic in wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nano CuO/COF composite arsenic removal material comprises the following steps:
the method comprises the following steps: mixing 1, 4-dioxane, mesitylene and glacial acetic acid according to a certain proportion to obtain a mixed solution A, carrying out ultrasonic treatment for 20 minutes in ice bath, and adding a certain amount of 1,3, 5-trimethylbenzenetriol and a proper amount of 2, 5-diethoxy terephthaloyl hydrazine into the mixed solution A to obtain a mixed solution B; then the mixed solution B is subjected to three cycles of quick freezing, vacuumizing, unfreezing and degassing to complete vacuum extraction. And (3) heating the extracted reactant in a vacuum drying oven for 2-3 days in vacuum, washing the reactant for 3 times by using acetone and methanol respectively, and freeze-drying the washed reactant to obtain the COF material.
Step two: dissolving a certain mass of copper nitrate in an ethanol-water mixed solution, then continuously stirring at room temperature while dropping a proper amount of NaOH solution, adding COF into the solution after dropping and stirring for 15-30 min, and ultrasonically stirring for 40-60 min to obtain a mixed solution C; and then putting the mixed solution C into a reaction kettle with a polytetrafluoroethylene lining for reaction for 6-10 h, centrifuging the solution after the reaction, washing the obtained precipitate ethanol and water for 3 times, and drying after washing to obtain the nano CuO/COF composite arsenic removal material.
Preferably, in the first step, the volume ratio of the 1, 4-dioxane to the mesitylene is 1: 1-1: 1.5, the volume ratio of the 1, 4-dioxane to the glacial acetic acid is 10: 3-10: 1, the mass ratio of the 1,3, 5-trimethylisophthaloyl phloroglucinol to the 2, 5-diethoxy terephthaloyl hydrazine is 1: 1-1: 2, the mass ratio of the 2, 5-diethoxy terephthaloyl hydrazine to the mixed solution A is 1: 15-1: 30, and the temperature of the vacuum drying oven is 90-110 ℃.
Preferably, the vacuum extraction in the step one is to place the mixed solution B in liquid nitrogen for 5min to be frozen rapidly, then move the mixed solution B into a vacuum freezer to be frozen for 2-4 h, then unfreeze and degas, and repeat the cycle for 3 times.
Preferably, in the second step, the volume ratio of ethanol to water in the ethanol-water mixed solution is 1: 5-1: 10, the addition amount of COF is 10-15 g, the molar ratio of copper nitrate to NaOH is 1: 2-1: 3, and the temperature of the reaction kettle is 130-160 ℃.
The other technical scheme of the invention is to provide the composite arsenic removal material prepared by the preparation method.
Has the advantages that: the invention discloses a nano CuO/COF composite arsenic removal material, which overcomes the defect that the traditional material cannot effectively remove trivalent arsenic in sewage, and achieves high removal speed and high removal rate of arsenic ions. COF provides more opportunities for capturing arsenic ions for the matrix, improves the local arsenic ion concentration near the nano CuO, and can oxidize trivalent arsenic more effectively. Compared with other materials, the COF material prepared from the 1,3, 5-trimethylbenzene tri-phenol and the 2, 5-diethoxy terephthaloyl hydrazine has more dense holes, uniform distribution and excellent water/acid stability, so that the agglomeration of nano CuO can be reduced, the nano CuO is uniformly loaded on the surface of the COF, and the dispersibility of active adsorption sites is further improved; can also contain a large amount of SO2The composite material has strong stability in waste water, and the service life of the composite material is prolonged. The COF prepared by the invention can also provide lone pair electrons by utilizing heteroatoms in the skeleton, so that the stability of the nano CuO is ensured, and the oxidation capability of the nano CuO can be continuously maintained after the nano CuO is oxidized by trivalent arsenic ions. In addition, due to the strong covalent force of elements such as C, N, O between COF backbones, the nano CuO is firmly fixed on the frame, and the problem that the nano CuO is remained in water after arsenic removal is not worried about.
Drawings
FIG. 1 is a scanning electron microscope photograph of example 1 of the present invention;
FIG. 2 is a graph showing the removal rate of arsenic ions in wastewater according to examples 1 to 5 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The method comprises the following steps: mixing 10ml of 1, 4-dioxane, 10ml of mesitylene and 2.3ml of glacial acetic acid to obtain a mixed solution A, carrying out ultrasonic treatment for 20 minutes in ice bath, and adding 0.82g of 1,3, 5-trimethylbenzenetriol and 0.82g of 2, 5-diethoxy terephthaloyl hydrazine to the mixed solution A to obtain a mixed solution B; then circulating the mixed solution B for three times, placing the mixed solution B in liquid nitrogen for 5min, moving the mixed solution B into a vacuum freezer, continuously freezing the mixed solution for 2h, and then thawing and degassing the mixed solution; the reaction after the three reactions was heated in vacuum at 90 ℃ for 3 days in a vacuum oven, followed by washing 3 times each with acetone and methanol, and freeze-drying after washing to obtain a COF material.
Step two: dissolving 11.25g of copper nitrate in a mixed solution of 33ml of ethanol and 167ml of water, then dropping 60ml of NaOH solution with the concentration of 2mol/L while continuously stirring at room temperature, adding 10g of COF into the solution after stirring for 15min, and ultrasonically stirring for 40min to obtain a mixed solution C; and then the mixed solution C is put into a reaction kettle with a polytetrafluoroethylene lining to react for 10 hours at the temperature of 130 ℃, then the solution after the reaction is centrifuged, the obtained precipitate ethanol and water are washed for 3 times, and the nano CuO/COF composite arsenic removal material is obtained after washing and drying.
Example 2
The method comprises the following steps: mixing 9ml of 1, 4-dioxane, 13.5ml of mesitylene and 0.9ml of glacial acetic acid to obtain a mixed solution A, carrying out ultrasonic treatment on the mixed solution A for 20 minutes in ice bath, and adding 0.82g of 1,3, 5-trimethylbenzenetriol and 1.64g of 2, 5-diethoxy-terephthaloyl hydrazine to the mixed solution A to obtain a mixed solution B; then circulating the mixed solution B for three times, placing the mixed solution B in liquid nitrogen for 5min, moving the mixed solution B into a vacuum freezer, continuously freezing the mixed solution for 3h, and then thawing and degassing the mixed solution; the reaction after three reactions was heated under vacuum in a vacuum oven at 110 ℃ for 2 days, followed by washing with acetone and methanol each 3 times, and freeze-drying after washing to obtain a COF material.
Step two: dissolving 11.25g of copper nitrate in a mixed solution of 19ml of ethanol and 181ml of water, then dropping 90ml of NaOH solution with the concentration of 2mol/L while continuously stirring at room temperature, adding 14.5g of COF into the solution after stirring for 28min, and ultrasonically stirring for 40min to obtain a mixed solution C; and then the mixed solution C is put into a reaction kettle with a polytetrafluoroethylene lining to react for 10 hours at 160 ℃, then the solution after the reaction is centrifuged, the obtained precipitate ethanol and water are washed for 3 times, and the nano CuO/COF composite arsenic removal material is obtained after washing and drying.
Example 3
The method comprises the following steps: mixing 8ml of 1, 4-dioxane, 9ml of mesitylene and 1ml of glacial acetic acid to obtain a mixed solution A, carrying out ultrasonic treatment for 20 minutes in ice bath, and adding 1.1g of 1,3, 5-trimethylbenzenetriol and 1.2g of 2, 5-diethoxy terephthaloyl hydrazine to the mixed solution A to obtain a mixed solution B; then circulating the mixed solution B for three times, placing the mixed solution B in liquid nitrogen for 5min, moving the mixed solution B into a vacuum freezer, continuously freezing the mixed solution for 4h, and then thawing and degassing the mixed solution; the reaction after the three reactions was heated in a vacuum oven at 100 ℃ for 2 days under vacuum, followed by washing with acetone and methanol each 3 times, and freeze-drying after washing to obtain a COF material.
Step two: dissolving 11.25g of copper nitrate in a mixed solution of 25ml of ethanol and 175ml of water, then dropping 70ml of NaOH solution with the concentration of 2mol/L while continuously stirring at room temperature, adding 135g of COF into the solution after stirring for 20min, and ultrasonically stirring for 55min to obtain a mixed solution C; and then putting the mixed solution C into a reaction kettle with a polytetrafluoroethylene lining for reaction at 145 ℃ for 9 hours, centrifuging the solution after the reaction, washing the obtained precipitate ethanol and water for 3 times, and drying after washing to obtain the nano CuO/COF composite arsenic removal material.
Example 4
The method comprises the following steps: mixing 10ml of 1, 4-dioxane, 13.5ml of mesitylene and 1.5ml of glacial acetic acid to obtain a mixed solution A, carrying out ultrasonic treatment on the mixed solution A for 20 minutes in ice bath, and adding 0.82g of 1,3, 5-trimethylbenzenetriol and 1.4g of 2, 5-diethoxy-terephthaloyl hydrazine to the mixed solution A to obtain a mixed solution B; then circulating the mixed solution B for three times, placing the mixed solution B in liquid nitrogen for 5min, moving the mixed solution B into a vacuum freezer, continuously freezing the mixed solution for 3.5h, and then thawing and degassing the mixed solution; the reaction after the three reactions was heated in vacuum at 95 ℃ for 2 days in a vacuum oven, followed by washing 3 times each with acetone and methanol, and freeze-drying after washing to obtain a COF material.
Step two: dissolving 11.25g of copper nitrate in a mixed solution of 30ml of ethanol and 170ml of water, then dripping 80ml of NaOH solution with the concentration of 2mol/L while continuously stirring at room temperature, adding 15g of COF into the solution after stirring for 25min, and ultrasonically stirring for 60min to obtain a mixed solution C; and then putting the mixed solution C into a reaction kettle with a polytetrafluoroethylene lining for reacting for 6 hours at 139 ℃, centrifuging the solution after reaction, washing the obtained precipitate ethanol and water for 3 times, and drying after washing to obtain the nano CuO/COF composite arsenic removal material.
Example 5
The method comprises the following steps: mixing 11ml of 1, 4-dioxane, 11ml of mesitylene and 2.5ml of glacial acetic acid to obtain a mixed solution A, carrying out ultrasonic treatment for 20 minutes in ice bath, and adding 0.82g of 1,3, 5-trimethylbenzenetriol and 1.24g of 2, 5-diethoxy terephthaloyl hydrazine to the mixed solution A to obtain a mixed solution B; then circulating the mixed solution B for three times, placing the mixed solution B in liquid nitrogen for 5min, moving the mixed solution B into a vacuum freezer, continuously freezing the mixed solution for 2h, and then thawing and degassing the mixed solution; the reaction after three reactions was heated under vacuum in a vacuum oven at 106 ℃ for 2 days, followed by washing with acetone and methanol each 3 times, and freeze-drying after washing to obtain a COF material.
Step two: dissolving 11.25g of copper nitrate in a mixed solution of 28ml of ethanol and 172ml of water, then dropping 65ml of NaOH solution with the concentration of 2mol/L while continuously stirring at room temperature, adding 14.5g of COF into the solution after stirring for 30min, and ultrasonically stirring for 40min to obtain a mixed solution C; and then putting the mixed solution C into a reaction kettle with a polytetrafluoroethylene lining for reacting for 8 hours at the temperature of 152 ℃, centrifuging the solution after reaction, washing the obtained precipitate ethanol and water for 3 times, and drying after washing to obtain the nano CuO/COF composite arsenic removal material.
Comparative example 1
Pure nano CuO prepared according to the method of the present invention was used as comparative example 1.
Dissolving 11.25g of copper nitrate into a mixed solution of 28ml of ethanol and 172ml of water, then dripping 65ml of NaOH solution with the concentration of 2mol/L into the mixed solution while continuously stirring the mixed solution at room temperature, after stirring the mixed solution for 30min, putting the mixed solution into a reaction kettle with a polytetrafluoroethylene lining to react for 8h at 152 ℃, then centrifuging the reacted solution, washing the obtained precipitate ethanol and water for 3 times, and drying the washed precipitate to obtain the nano CuO.
The specific data was analyzed in comparison as follows:
fig. 1 is a scanning electron microscope picture of the composite material at 500nm, from which it can be seen that nano CuO has been successfully supported on COF material and is distributed more uniformly.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | |
| 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| 0.5 | 32.1 | 27.8 | 26 | 31.3 | 28.7 | 18.6 |
| 1 | 62.1 | 59.2 | 59.8 | 61.5 | 60.1 | 38.4 |
| 1.5 | 81 | 78.3 | 79.5 | 82.9 | 83.7 | 58.8 |
| 2 | 94.2 | 91.1 | 91.8 | 94.8 | 92.7 | 70 |
| 2.5 | 98.5 | 97.8 | 97.5 | 99.4 | 98.6 | 75.2 |
FIG. 2 and Table 1 show statistics of removal of trivalent arsenic for examples 1-5 and comparative example 1, and it can be very intuitively seen from FIG. 2 that the composite material prepared by the preparation scheme of the present invention has increased efficiency of removing trivalent arsenic with time, and the slope of the curve of examples 1-5 does not change much in the first 90min, which indicates that the material is stable in removing trivalent arsenic; table 1 lists the removal rate data of six materials at different time points in detail, and it can be seen that the efficiency of examples 1-5 reaches about 80% at 1.5h, the efficiency of examples 1-5 reaches more than 90% at 2h, the removal rate of trivalent arsenic reaches 98% and 99% at 2.5h, and the maximum removal rate can reach 99.4%, which shows that the nano CuO/COF composite arsenic removal material prepared by the preparation method of the present invention can effectively remove trivalent arsenic in wastewater. Comparative example 1 is the application of nano CuO in arsenic removal, and its performance is far from that of examples 1-5.
In general, compared with data analysis on materials prepared in examples and comparative examples, the nano CuO/COF composite arsenic removal material provided by the invention can effectively remove trivalent arsenic in industrial wastewater, and has the advantages of high removal speed and high removal rate. The nano CuO is also firmly fixed on the frame, and the harm caused by the nano CuO remaining in the water after arsenic removal is avoided.
While the invention has been described with respect to a preferred embodiment, it will be understood by those skilled in the art that the foregoing and other changes, omissions and deviations in the form and detail thereof may be made without departing from the scope of this invention.
Claims (5)
1. A preparation method of a nano CuO/COF composite arsenic removal material is characterized by comprising the following steps:
the method comprises the following steps: mixing 1, 4-dioxane, mesitylene and glacial acetic acid to obtain a mixed solution A, carrying out ultrasonic treatment for 20 minutes, and adding 1,3, 5-trimethylphloroglucinol and 2, 5-diethoxy terephthaloyl hydrazine to the mixed solution A to obtain a mixed solution B; then the mixed solution B is subjected to three cycles of quick freezing, vacuumizing, unfreezing and degassing to finish vacuum extraction; heating the extracted reactant in a vacuum drying oven for 2-3 days in vacuum, washing the reactant for 3 times by using acetone and methanol respectively, and freeze-drying the washed reactant to obtain a COF material;
step two: dissolving a certain mass of copper nitrate in an ethanol-water mixed solution, then continuously stirring at room temperature while dropping a NaOH solution, adding COF into the solution after dropping and stirring for 15-30 min, and ultrasonically stirring for 40-60 min to obtain a mixed solution C; and then putting the mixed solution C into a reaction kettle with a polytetrafluoroethylene lining for reaction for 6-10 h, centrifuging the solution after the reaction, washing the obtained precipitate ethanol and water for 3 times, and drying after washing to obtain the nano CuO/COF composite arsenic removal material.
2. The preparation method of the nano CuO/COF composite arsenic removal material as claimed in claim 1, wherein in the first step, the volume ratio of 1, 4-dioxane to mesitylene is 1: 1-1: 1.5, the volume ratio of 1, 4-dioxane to glacial acetic acid is 10: 3-10: 1, the mass ratio of 1,3, 5-trimethylbenzene tri-phenol to 2, 5-diethoxy terephthaloyl hydrazine is 1: 1-1: 2, the mass ratio of 2, 5-diethoxy terephthaloyl hydrazine to the mixed solution A is 1: 15-1: 30, and the temperature of the vacuum drying oven is 90-110 ℃.
3. The method for preparing the nano CuO/COF composite arsenic removal material as claimed in claim 1, wherein the vacuum extraction in the first step is to put the mixed solution B into liquid nitrogen for 5min to rapidly freeze the mixed solution B, then to move the mixed solution B into a vacuum freezer to continue freezing for 2-4 h, then to thaw and degas, and to repeat the cycle for 3 times.
4. The preparation method of the nano CuO/COF composite arsenic removal material as claimed in claim 1, wherein in the second step, the volume ratio of ethanol to water in the ethanol-water mixed solution is 1: 5-1: 10, the addition amount of COF is 10-15 g, the molar ratio of copper nitrate to NaOH is 1: 2-1: 4, and the temperature of the reaction kettle is 130-160 ℃.
5. The composite material prepared by the preparation method of the nano CuO/COF composite arsenic removal material as claimed in any one of claims 1 to 4, wherein the composite material can effectively remove trivalent arsenic in wastewater.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113000027A (en) * | 2021-04-07 | 2021-06-22 | 昆明理工大学 | Method for removing arsenic in non-ferrous metal smelting wastewater through FeOOH @ COFs |
| CN115260423A (en) * | 2022-08-19 | 2022-11-01 | 南京理工大学 | Long alkyl chain modified covalent organic framework material, preparation method and application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113000027A (en) * | 2021-04-07 | 2021-06-22 | 昆明理工大学 | Method for removing arsenic in non-ferrous metal smelting wastewater through FeOOH @ COFs |
| CN115260423A (en) * | 2022-08-19 | 2022-11-01 | 南京理工大学 | Long alkyl chain modified covalent organic framework material, preparation method and application |
| CN115260423B (en) * | 2022-08-19 | 2023-08-18 | 南京理工大学 | Covalent organic framework material modified by long alkyl chain, preparation method and application |
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Application publication date: 20200925 |