CN113603204A - Preparation method of aluminum-carbon nanotube composite material and application of aluminum-carbon nanotube composite material in removing pollutants difficult to degrade in water - Google Patents
Preparation method of aluminum-carbon nanotube composite material and application of aluminum-carbon nanotube composite material in removing pollutants difficult to degrade in water Download PDFInfo
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Abstract
The invention discloses a preparation method of an aluminum-carbon nanotube composite material and application of the aluminum-carbon nanotube composite material in removing pollutants difficult to degrade in water. Simultaneously discloses the application of the material: the aluminum-carbon nanotube composite material can be directly added into a strong acid, near neutral or strong alkali solution to efficiently degrade pollutants in water. The material can reduce and degrade various pollutants under the conditions of near neutrality and the existence of dissolved oxygen. The aluminum-carbon nanotube composite material can be repeatedly utilized, is environment-friendly, does not cause secondary pollution, and has high activity and passivation resistance in various practical water bodies. The method is carried out at normal temperature and normal pressure, has mild and simple reaction conditions, wide and cheap material sources, less investment and low cost, and is easy to engineer.
Description
Technical Field
The invention belongs to the technical field of water pollution treatment, and particularly relates to a preparation method of an aluminum-carbon nanotube composite material and application of the aluminum-carbon nanotube composite material in removing pollutants difficult to degrade in water.
Background
Zero valent aluminum has a very low oxidation-reduction potential (E)0-1.662V), high reducing power, and is the most metal in the crust, rich in resources, and beneficial to large-scale application. The high-efficiency composite material can be used for removing various pollutants in water due to high reduction capability, but a dense oxide film (mainly alumina) is arranged on the surface of the micron zero-valent aluminum, and the oxide film is non-conductive, so that the release of electrons can be hindered, and particularly the removal efficiency of the pollutants under a near-neutral condition is extremely low; the fresh aluminum surface reacts with oxygen in the environment medium again after the film is broken, so that the material is passivated for the second time, and the continuous proceeding of the degradation reaction is prevented; in addition, because the oxide film on the surface of the zero-valent aluminum is hydrophilic, the hydrogen production content is high along with the degradation of pollutants, and the electron utilization efficiency is low.
The water contains high-concentration pollutants, which is common wastewater difficult to treat, and the conventional biological method cannot effectively remove the pollutants. The nitrophenol compounds and dyes with high concentration are difficult to remove, have high toxicity and are harmful to human health.
Disclosure of Invention
The invention aims to overcome the bottleneck of application of the zero-valent aluminum powder and treat pollutants which are difficult to degrade in water by using the zero-valent aluminum powder.
The novel material (aluminum-carbon nanotube) of the carbon nanotube modified micron aluminum is obtained by mechanical ball milling with the assistance of sodium chloride and multi-wall carbon nanotubes. The surface oxide film of the micron aluminum is damaged by the cutting action of the sodium chloride crystal, meanwhile, the carbon nano tube can cover the surface of the aluminum through local corrosion to prevent secondary passivation of the material, and in addition, the surface of the carbon nano tube is relatively hydrophobic, so that the electron utilization rate of the material is improved. Based on this, aluminum-carbon nanotubes can be used in near neutrality to remove high concentrations of p-nitrophenol in water while maintaining high electron utilization. In the aerobic state, can be used to reductively remove various contaminants without passivation. The invention has wide material source, low price and simple preparation process, and can remove various pollutants under the conditions of oxygen and wide pH.
The invention provides a preparation method of an aluminum-carbon nanotube composite material and application thereof in removing pollutants difficult to degrade in water, which comprises the following specific steps:
p1. preparation method of aluminum-carbon nanotube composite material: mixing zero-valent aluminum powder and carbon nanotubes, and ball milling in nitrogen atmosphere with grinding balls as grinding medium. Wherein, a certain amount of grinding aid is added in the grinding process, and then the aluminum-carbon nanotube composite material is obtained by ball milling on a ball mill;
p2, adding the aluminum-carbon nanotube composite material into the wastewater which is difficult to degrade, and stirring to fully mix the aluminum-carbon nanotube composite material and pollutants, thereby purifying the water quality.
As above, the mass ratio of the zero-valent aluminum powder to the carbon nanotubes in the step P1 is 5-200:1, and the particle size of the aluminum powder is 100-12500 meshes. The grinding ball is one or more of zirconia grinding ball, chromium alloy cast iron grinding ball, martensite ductile iron grinding ball, steel ball and agate ball. The carbon nanotube is a single-walled or multi-walled carbon nanotube. The inert gas is nitrogen, helium or argon.
As above, the grain diameter of the grinding ball in the step P1 is 5-10 mm, and the mass ratio of the zero-valent aluminum to the grinding ball is 1: 30-60.
As above, the grinding aid in step P1 is sodium chloride with a mass fraction of 2% -5% of zero-valent aluminum powder.
As above, the ball milling speed of the ball mill in the step P1 is 100-300 rpm, and the time is 1-9 h.
As above, the contaminants in the wastewater of step P2 include, but are not limited to, inorganic contaminants: cr (C)
) Nitrate radicals and the like; organic contaminants: p-nitrophenol, acid orange 7, reactive black 5, carbon tetrachloride and the like.
As above, the pH of the solution in step P2 is 3-11, the reaction temperature is 10-30 deg.C, and the pH is adjusted by sodium hydroxide or sulfuric acid.
As above, the mass ratio of the added amount of the aluminum-carbon nanotube composite material to the pollutants in the step P2 is 2-400: 1.
the invention can prepare the aluminum-carbon nanotube composite material by simple mechanical ball milling, the oxide film on the surface of the micrometer aluminum is damaged by the cutting action of the sodium chloride crystal, meanwhile, the carbon nanotube can cover the surface of the aluminum by local corrosion to inhibit the secondary formation of a passivation film, and in addition, the surface of the carbon nanotube is relatively hydrophobic, thereby improving the electronic utilization rate of the material.
The invention has the following advantages:
1) the carbon nano tube adopted by the invention is an industrial grade raw material, can be used in a large scale, has rich aluminum resource storage and low price of micron aluminum.
2) The preparation method of the aluminum-carbon nanotube composite material is carried out at normal temperature and normal pressure, has mild and simple reaction conditions, and is suitable for industrial production.
3) The invention solves the problem that the surface passivation film in the current zero-valent aluminum practical application hinders the electron release, the aluminum surface is hydrophilic, so that the aluminum material has low electron utilization rate, and the secondary passivation is easy to be carried out by the oxygen reaction of the environment medium after the film is broken.
4) The invention can effectively degrade pollutants in a wide pH range (3-11), the presence of dissolved oxygen, various ionic interferences and various real water environments without secondary passivation.
5) The invention can reduce and remove various pollutants in a near-neutral and aerobic state.
Drawings
FIG. 1 is a degradation diagram of an aluminum-carbon nanotube composite, with p-nitrophenol removed from aluminum alone and carbon nanotubes alone.
FIG. 2 shows the degradation of p-nitrophenol in the aluminum-carbon nanotube composite under different pH conditions.
FIG. 3 shows the degradation of p-nitrophenol in the presence of different dissolved oxygen for aluminum-carbon nanotube composites.
FIG. 4 shows the degradation of p-nitrophenol in the aluminum-carbon nanotube composite after exposure to air for various periods of time.
FIG. 5 shows that the Al-C nanotube composite degrades different pollutants (inorganic pollutant: Cr (C) (C))
) Nitrate, etc.; organic contaminants such as p-nitrophenol, acid orange 7, reactive black 5, carbon tetrachloride).
Fig. 6 is a graph showing the degradation of high concentrations of p-nitrophenol by different aluminum materials that have been currently published.
FIG. 7 shows that the aluminum-carbon nanotube composite material degrades p-nitrophenol in various real water environments.
FIG. 8 shows the cyclic degradation of p-nitrophenol by the aluminum-carbon nanotube composite.
FIG. 9 shows the degradation of p-nitrophenol in the aluminum-carbon nanotube composite material under the interference of ions of different concentrations.
FIG. 10 is a graph showing hydrogen production and electron utilization compared to other aluminum materials for degradation of p-nitrophenol.
FIG. 11 shows the hydrogen production and electron utilization rates of the aluminum-carbon nanotube composite material containing different amounts of carbon nanotubes for degrading p-nitrophenol.
FIG. 12 shows the hydrogen production and electron utilization rates of the aluminum-carbon nanotube composite material prepared at different rotation speeds and ball milling times for degrading p-nitrophenol.
FIG. 13 shows the hydrogen production and electron utilization rates of aluminum-carbon nanotube composites by degrading p-nitrophenol with different concentrations.
FIG. 14 shows the degradation of p-nitrophenol by different contents of aluminum-carbon nanotube composite.
Detailed Description
The present invention will be further described with reference to specific embodiments, which are provided for illustration only and are not intended to be limiting.
The preparation method of the aluminum-carbon nanotube composite material described below is as follows: mixing zero-valent aluminum powder and carbon nanotubes according to a mass ratio of 20:1, wherein the particle size of the zero-valent aluminum powder is 100-200 meshes. The zirconia grinding ball is a grinding medium, and the mass ratio of the zirconia grinding ball to the zero-valent aluminum is 60: 1. ball milling is carried out in the protective atmosphere of nitrogen. And adding a certain amount of grinding aid in the grinding process, wherein the grinding aid is sodium chloride accounting for 2% of zero-valent aluminum powder by mass fraction, maintaining the rotating speed of 200 revolutions on a ball mill, and performing ball milling for 6 hours to obtain the aluminum-carbon nanotube composite material.
Example 1 comparison of the removal of p-nitrophenol (PNP) from water with different materials.
Preparing 100mL of paranitrophenol simulated wastewater with the concentration of 500 mg/L, introducing nitrogen into a serum bottle for 15 minutes, removing dissolved oxygen in the solution by using the nitrogen, adding 4g/L of aluminum-carbon nanotube composite material into the reaction serum bottle, and sealing by using a rubber plug. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. The samples were taken periodically and filtered through a 0.45 micron acetate fiber membrane, and the content of PNP was measured with an ultraviolet spectrophotometer, while untreated zerovalent aluminum, carbon nanotubes alone were used as a control. As shown in FIG. 1, only a small amount of PNP can be removed by the single micron zero-valent aluminum (mZVAl) and the single carbon nanotube, but 500 mg/L of PNP can be completely removed by the aluminum-carbon nanotube composite material prepared by the invention within 8 hours, which proves that the high activity of the aluminum-carbon nanotube composite material can effectively remove the PNP in water.
Example 2 decomposition of p-nitrophenol in aluminum-carbon nanotube composites at different pH.
Preparing 100mL of PNP simulated wastewater with the concentration of 500 mg/L, adjusting the initial pH of the solution to 3, 5, 7, 9 and 11 by using sodium hydroxide and sulfuric acid, respectively, introducing nitrogen into a serum bottle for 15 minutes, removing dissolved oxygen in the solution by using the nitrogen, adding 4g/L of aluminum-carbon nanotube composite material into the reaction serum bottle, and sealing by using a rubber plug. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. The sample is taken at regular time and filtered by a 0.45 micron acetate fiber filter membrane, and the content of PNP is detected by an ultraviolet spectrophotometer. As shown in fig. 2, the aluminum-carbon nanotube composite can effectively remove PNP in different pH environments.
Example 3 aluminum-carbon nanotube composites degraded p-nitrophenol under different initial dissolved oxygen conditions.
Preparing 100mL of PNP simulated wastewater with the concentration of 500 mg/L, wherein the initial pH of the solution is 5.45, and respectively carrying out three treatments on the solution: introducing nitrogen, and bubbling for 15 min; no treatment is carried out; the oxygen bubbling treatment was carried out for 15 min to allow the initial dissolved oxygen content of the solution to be clearly distinguished. The DO content in the aqueous solution treated by the three pretreatment methods is 0.33 mg L, 9.40 mg/L and 60.86 mg/L respectively, and after 4g/L of aluminum-carbon nanotube composite material is added into a reaction serum bottle, the reaction serum bottle is sealed by a rubber plug. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. The sample is taken at regular time and filtered by a 0.45 micron acetate fiber filter membrane, and the content of PNP is detected by an ultraviolet spectrophotometer. As shown in fig. 3a, the aluminum-carbon nanotube composite material can effectively remove PNP in different dissolved oxygen environments, and is less interfered by oxygen. Based on this, to further verify the oxygen passivation resistance of the material, we changed to an open mouth experiment with a conical flask, so that the whole reaction process was always in an aerobic environment, and the dissolved oxygen in the whole process was monitored. As shown in FIGS. 3b and 3c, the aerobic and anaerobic environments have the same rate constant for the degradation of PNP by CNT @ mZVAl, and can effectively degrade PNP (more than 85%), demonstrating that CNT @ mZVAl is indeed resistant to passivation.
Example 4 is the degradation of PNP after exposure of aluminum-carbon nanotube composites to air for various periods of time.
Preparing 100mL of paranitrophenol simulated wastewater with the concentration of 500 mg/L, leading the initial pH of the solution to be 5.45, introducing nitrogen into a serum bottle for 15 minutes, removing dissolved oxygen in the solution by using the nitrogen, adding 4g/L of aluminum-carbon nanotube composite material exposed in the air into the reaction serum bottle for 0 day after 5 days and 10 days, and sealing by using a rubber plug. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. The sample is taken at regular time and filtered by a 0.45 micron acetate fiber filter membrane, and the content of PNP is detected by an ultraviolet spectrophotometer. As shown in fig. 4, the PNP can be effectively removed from the aluminum-carbon nanotube composite material exposed to air for different periods of time.
Example 5 aluminum-carbon nanotube composite Material degrades different contaminants (inorganic contaminant: Cr: (C.))
) Nitrate, etc.; organic contaminants such as p-nitrophenol, acid orange 7, reactive black 5, carbon tetrachloride).
100mL of Cr (at a concentration of 20 mg/L) are prepared respectively
) 14 mg/L nitrate radical, 500 mg/L p-nitrophenol, 500 mg/ L acid orange 7, 500 mg/L active black 5 and 0.1 mM carbon tetrachloride simulated wastewater, the initial dissolved oxygen environment of the solution is kept to be about 9.3 mg/L, and after 4g/L aluminum-carbon nanotube composite material is added into a reaction serum bottle, the reaction serum bottle is sealed by a rubber plug. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. Sampling at regular time, filtering with 0.45 μm acetate fiber membrane, and measuring p-nitrophenol, acid orange 7, reactive black 5, Cr (C/C)
) Detecting nitrate radical; detecting carbon tetrachloride by gas chromatography. As shown in fig. 5, the aluminum-carbon nanotube composite material can effectively remove various pollutants in water in an initial aerobic environment, and has universality for pollutant degradation.
Example 6 degradation of high concentrations of p-nitrophenol compared to different aluminum materials currently published.
Preparing 100mL of PNP simulated wastewater with the concentration of 500 mg/L, wherein the initial pH of the solution is 5.45, introducing nitrogen into a serum bottle for 15 minutes, removing dissolved oxygen in the solution by using the nitrogen, adding 4g/L of different aluminum materials (aluminum-carbon nanotube composite material, nano aluminum, ball-milled micron aluminum and sodium chloride, ball-milled micron aluminum and ethanol, acid-washed micron aluminum and alkali-washed micron aluminum) into different serum bottles with the same concentration, and sealing by using a rubber plug. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. The sample is taken at regular time and filtered by a 0.45 micron acetate fiber filter membrane, and the content of PNP is detected by an ultraviolet spectrophotometer. As shown in fig. 6, except for the aluminum-carbon nanotube composite, all the other different aluminum materials (nano aluminum, ball-milled micro aluminum and sodium chloride, ball-milled micro aluminum and ethanol, acid-washed micro aluminum, and alkali-washed micro aluminum) could not effectively remove the PNP, demonstrating the excellent performance of the aluminum-carbon nanotube composite.
Wherein the following were prepared for the different aluminum materials described in example 6: nano aluminum: commercially available 50nm aluminum powder; ball milling of micron aluminum and sodium chloride: mixing zero-valent aluminum powder and sodium chloride according to a mass ratio of 20:1, wherein the particle size of the zero-valent aluminum powder is 100-200 meshes. The zirconia grinding ball is a grinding medium, and the mass ratio of the zirconia grinding ball to the zero-valent aluminum is 60: 1. ball milling is carried out in the protective atmosphere of nitrogen, the ball milling time is 1 h, and the rotating speed is 300 rpm; ball milling of micron aluminum and ethanol: mixing zero-valent aluminum powder and sodium chloride according to the ratio of 100: 7.8, and the particle diameter of the zero-valent aluminum powder is 100-200 meshes. The zirconia grinding ball is a grinding medium, and the mass ratio of the zirconia grinding ball to the zero-valent aluminum is 60: 1. ball milling is carried out in the protective atmosphere of nitrogen, the ball milling time is 1 h, and the rotating speed is 300 rpm; acid washing the micron aluminum; the particle size of the zero-valent aluminum powder is 100-mesh and 200-mesh, the zero-valent aluminum powder is soaked in a solution with the pH =2 for 6h, and the solution is subjected to suction filtration and then is freeze-dried for 15 h; washing micron aluminum with alkali; the particle size of the zero-valent aluminum powder is 100-200 meshes, the zero-valent aluminum powder is soaked in a solution with the pH =2 for 6h, and the solution is subjected to suction filtration and freeze drying for 15 h.
Example 7 is the degradation of p-nitrophenol in various real water environments by aluminum-carbon nanotube composites.
The method comprises the steps of respectively preparing 100mL of PNP simulated wastewater with the concentration of 500 mg/L by using ultrapure water, tap water, seawater, river water and secondary treatment effluent of a sewage treatment plant and advanced treatment effluent of the sewage treatment plant, wherein the initial pH of the solution is 5.45, introducing nitrogen into a serum bottle for 15 minutes, removing dissolved oxygen in the solution by using the nitrogen, and respectively adding 4g/L of aluminum-carbon nanotube composite materials into different serum bottles with the same concentration. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. The sample is taken at regular time and filtered by a 0.45 micron acetate fiber filter membrane, and the content of PNP is detected by an ultraviolet spectrophotometer. As shown in fig. 7, the aluminum-carbon nanotube composite material can effectively degrade PNP in different real water environments, and the material exhibits excellent activity and passivation resistance.
The aqueous solutions in example 7 were obtained as follows. Ultrapure water: preparing by using a water purifier on the market; tap water: water from the Qingdao water service (Laoshan mountain area) water supply company; sea water: taken from the sea bathing place of Qingdao city stone old people; river water: taking river water near the east of nine-water mountain in Laoshan area of Qingdao city; secondary treatment effluent of a sewage treatment plant: the effluent is obtained from a Qingdao city major water treatment plant after secondary treatment; advanced treatment effluent of a sewage treatment plant: the effluent is taken from advanced treatment of Qingdao city water treatment plant.
Example 8 is the cyclic degradation of p-nitrophenol for aluminum-carbon nanotube composites.
Preparing 100mL of PNP simulated wastewater with the concentration of 100 mg/L, introducing nitrogen into a serum bottle for 15 minutes, removing dissolved oxygen in the solution by using the nitrogen, adding 4g/L of aluminum-carbon nanotube composite material into the reaction serum bottle, and sealing by using a rubber plug. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. After the degradation of PNP is completed, 100 mg/L PNP is injected into the serum bottle again. The sample is taken at regular time and filtered by a 0.45 micron acetate fiber filter membrane, and the content of PNP is detected by an ultraviolet spectrophotometer. As shown in fig. 8, after four cycles, the aluminum-carbon nanotube composite material still degraded 90.5% of PNP, demonstrating that the material can function for a long time.
Example 9 is the decomposition of p-nitrophenol in the aluminum-carbon nanotube composite under the interference of ions of different concentrations.
Preparing 100mL of PNP simulated wastewater with the concentration of 500 mg/L, introducing nitrogen into a serum bottle for 15 minutes, removing dissolved oxygen in the solution by using the nitrogen, adding 4g/L of aluminum-carbon nanotube composite material into serum bottles with different concentrations, and sealing by using rubber plugs. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. The sample is taken at regular time and filtered by a 0.45 micron acetate fiber filter membrane, and the content of PNP is detected by an ultraviolet spectrophotometer. As shown in FIG. 9, the aluminum-carbon nanotube composite material can completely degrade PNP in sodium chloride and sodium sulfate solutions with different concentrations, and the reaction rate is hardly influenced, thus proving the ion interference resistance of the aluminum-carbon nanotube composite material
Example 10 is a comparison of other aluminum materials to degrade p-nitrophenol, hydrogen production and electron utilization.
Preparing 100mL of PNP simulated wastewater with the concentration of 20 mg/L, wherein the initial pH of the solution is 5.45, introducing nitrogen into a serum bottle for 15 minutes, removing dissolved oxygen in the solution by using the nitrogen, adding 4g/L of different aluminum materials (aluminum-carbon nano tube composite material, nano aluminum, ball-milled micron aluminum and sodium chloride) into different serum bottles with the same concentration, and sealing by using rubber plugs. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. Sampling at fixed time, filtering with 0.45 micrometer acetate fiber membrane, detecting PNP content with ultraviolet spectrophotometer, and detecting hydrogen with gas phase-TCD detector. As shown in fig. 10a-10c, the aluminum-carbon nanotube composite can rapidly degrade PNP while generating a small amount of hydrogen (side reaction wastes electrons) compared to the nano aluminum and the ball-milled micro aluminum and sodium chloride, so the aluminum-carbon nanotube composite can improve the electron utilization of aluminum compared to other two aluminum materials.
Wherein the following were prepared for the different aluminum materials described in example 10: nano aluminum: commercially available 50nm aluminum powder; ball milling of micron aluminum and sodium chloride: mixing zero-valent aluminum powder and sodium chloride according to a mass ratio of 20:1, wherein the particle size of the zero-valent aluminum powder is 100-200 meshes. The zirconia grinding ball is a grinding medium, and the mass ratio of the zirconia grinding ball to the zero-valent aluminum is 60: 1. ball milling is carried out in the protective atmosphere of nitrogen, the ball milling time is 1 h, and the rotating speed is 300 rpm.
Example 11 is a method for degrading p-nitrophenol, producing hydrogen and utilizing electrons for aluminum-carbon nanotube composite materials containing different amounts of carbon nanotubes.
Preparing 100mL of PNP simulated wastewater with the concentration of 500 mg/L, introducing nitrogen into a serum bottle for 15 minutes, removing dissolved oxygen in the solution by using the nitrogen, adding 4g/L of aluminum-carbon nanotube composite materials with different carbon nanotube contents into different serum bottles with the same concentration, and sealing by using rubber plugs. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. Sampling at fixed time, filtering with 0.45 micrometer acetate fiber membrane, detecting PNP content with ultraviolet spectrophotometer, and detecting hydrogen with gas phase-TCD detector. As shown in fig. 11a-11c, a carbon nanotube loading of 0.5wt% failed to effectively degrade PNP primarily because the CNT amount was too small, at which point the aluminum micron did not break free of agglomeration and the activity was very low. The load of the carbon nano tube of 2wt% -20wt% has almost no influence on the degradation of the PNP, the PNP can be completely degraded, and the hydrogen production result also verifies the point, so the electron utilization rates of the PNP are close to the same and are all as high as about 69%.
Example 12 degradation of p-nitrophenol, hydrogen production and electron utilization for aluminum-carbon nanotube composites prepared at different rotational speeds and ball milling times.
Preparing 100mL of PNP simulated wastewater with the concentration of 500 mg/L, introducing nitrogen into a serum bottle for 15 minutes, removing dissolved oxygen in the solution by using the nitrogen, adding 4g/L of aluminum-carbon nanotube composite material into serum bottles with different concentrations, and sealing by using rubber plugs. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. Sampling at fixed time, filtering with 0.45 micrometer acetate fiber membrane, detecting PNP content with ultraviolet spectrophotometer, and detecting hydrogen with gas phase-TCD detector. As shown in fig. 12a-12d, prolonging the ball milling time can suitably improve the reaction rate constant when the aluminum-carbon nanotube composite material degrades PNP, mainly because increasing the milling time can make the carbon nanotubes more uniformly distributed and better release the activity of micron aluminum; the different ball milling rotating speeds have almost no influence on the reaction rate constant during degradation of the PNP; the hydrogen generated in the PNP degradation process of the aluminum-carbon nanotube composite material prepared by different ball milling time and rotating speed is also relatively close. According to the demonstration of the electron utilization efficiency in fig. 12e, the ball milling parameters have little influence on the preparation of the aluminum-carbon nanotube composite material at different ball milling times and rotation speeds when the PNP is degraded, and the high electron utilization rate is maintained among colleagues who completely degrade the PNP.
Example 13 is an aluminum-carbon nanotube composite that degrades p-nitrophenol at different concentrations, producing hydrogen and utilizing electrons.
Respectively preparing 100mL of PNP simulated wastewater with the concentrations of 20, 50, 100, 200, 500 and 1000mg/L, wherein the initial pH of the solution is 5.45, introducing nitrogen into a serum bottle for 15 minutes, removing dissolved oxygen in the solution by using the nitrogen, adding 4g/L of aluminum-carbon nanotube composite material into the serum bottles with different concentrations, and sealing by using rubber plugs. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. Sampling at fixed time, filtering with 0.45 micrometer acetate fiber membrane, detecting PNP content with ultraviolet spectrophotometer, and detecting hydrogen with gas phase-TCD detector. As shown in fig. 12a-12c, the aluminum-carbon nanotube composite material can completely degrade 20-1000 mg/L of PNP within a certain time, and meanwhile, the electron utilization rate of the aluminum-carbon nanotube composite material is higher along with the increase of the concentration of PNP in combination with the calculation of hydrogen production and electron utilization rate. When the concentration of PNP is 1000mg/L, the electron utilization efficiency of the aluminum-carbon nanotube composite material is as high as 77.47%.
Example 14 degradation of p-nitrophenol for different contents of aluminum-carbon nanotube composites.
Preparing 100mL of PNP simulated wastewater with the concentration of 500 mg/L, introducing nitrogen into a serum bottle for 15 minutes, removing dissolved oxygen in the solution by using the nitrogen, adding 1, 2, 4 and 8g/L of aluminum-carbon nanotube composite materials into different serum bottles with the same concentration respectively, and sealing by using rubber plugs. And putting the serum bottle into a constant-temperature water bath oscillator, wherein the temperature of the oscillator is set to be 25 +/-1 ℃, and the rotating speed is set to be 220 r/min. The sample is taken at regular time and filtered by a 0.45 micron acetate fiber filter membrane, and the content of PNP is detected by an ultraviolet spectrophotometer. As shown in fig. 14, increasing the amount of the aluminum-carbon nanotube composite material can increase the degradation rate of the PNP, mainly because the increase of the amount of the aluminum-carbon nanotube composite material can release more electrons and provide more reaction sites, thereby increasing the reaction speed and degrading the PNP more quickly.
Claims (9)
1. A preparation method of an aluminum-carbon nanotube composite material is characterized by comprising the following steps:
mixing zero-valent aluminum powder and carbon nanotubes according to the mass ratio of 5-200:1, taking grinding balls as grinding media, and carrying out ball milling in the protective atmosphere of inert gas; wherein, a certain amount of grinding aid is added in the grinding process, the grinding aid is sodium chloride with the mass fraction accounting for 2-5% of zero-valent aluminum powder, and then the aluminum-carbon nanotube composite material is obtained by ball milling on a ball mill.
2. The preparation method as claimed in claim 1, wherein the particle size of the zero-valent aluminum powder is 100-12500 meshes, the particle size of the grinding ball is 5-10 mm, and the mass ratio of the zero-valent aluminum to the grinding ball is 1: 30-60.
3. The preparation method according to claim 1, wherein the grinding balls are one or more of zirconia grinding balls, chrome alloy cast iron grinding balls, martensite ductile iron grinding balls, steel balls and agate balls, the carbon nanotubes are single-walled or multi-walled carbon nanotubes, and the inert gas is nitrogen, helium or argon.
4. The preparation method as claimed in claim 1, wherein the ball milling rotation speed of the ball mill is 100-300 rpm and the time is 1-9 h.
5. The application of the aluminum-carbon nanotube composite material prepared by the preparation method of claim 1 in removing pollutants difficult to degrade in water is characterized in that the prepared aluminum-carbon nanotube composite material is added into pollutant wastewater difficult to degrade, and the aluminum-carbon nanotube composite material and the pollutants are fully mixed through stirring to purify water.
6. Use according to claim 5, wherein the contaminants in the wastewater are inorganic contaminants or organic contaminants.
7. Use according to claim 5, wherein the inorganic contaminant is Cr(
) Or a nitrate radical; the organic pollutants are p-nitrophenol, acid orange 7, active black 5 or carbon tetrachloride.
8. Use according to claim 5, characterized in that the pH is adjusted to 3-11 with sodium hydroxide or sulphuric acid and the reaction temperature is 10-30 ℃.
9. The use of claim 5, wherein the mass ratio of the amount of aluminum-carbon nanotube composite added to the contaminants is 2-400: 1.
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