CN109092245B - Diatomite-loaded carbon nanotube adsorbent and preparation method thereof - Google Patents
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Abstract
The invention discloses a preparation method of a diatomite-loaded carbon nanotube adsorbent, which comprises the following steps: (1) pretreating original diatomite; (2) adding diatomite into the catalyst solution, stirring, filtering, and drying to obtain solid powder; (3) heating the solid powder to 400-480 ℃ in a nitrogen atmosphere, introducing a mixed gas of nitrogen and hydrogen, preserving the heat for 1-2 h, then heating to 500-800 ℃, introducing a mixed gas mixed with nitrogen, hydrogen and a carbon source gas, preserving the heat for 15-90 min, closing the hydrogen and the carbon source gas, and cooling to room temperature in the nitrogen atmosphere; (4) and annealing the black solid powder, cooling, acidifying, washing, drying, grinding and sieving. The invention also discloses the diatomite-loaded carbon nanotube adsorbent prepared by the preparation method. The adsorbent has high adsorption performance and has a great application prospect in the aspect of adsorbing organic pollutants in wastewater.
Description
Technical Field
The invention relates to an adsorption material, in particular to a diatomite-loaded carbon nanotube adsorbent and a preparation method thereof.
Background
Phenolic compounds are widely used for manufacturing phenolic resin high molecular materials, ion exchange resins, synthetic fibers, dyes, medicines, explosives and the like. As the phenolic substances are wide in application and difficult to degrade, the phenolic compounds are easy to dissolve in water, the phenolic wastewater has the characteristics of carcinogenesis, mutagenesis and capability of causing cell protein denaturation and precipitation, the toxicity is high, and a small amount of phenolic organic matters in a water body can cause great harm to human bodies and aquatic organisms, so that a plurality of phenols are considered to be extremely toxic pollutants, and the phenolic wastewater is one of common harmful industrial wastewater. At present, the treatment methods of phenol-containing wastewater mainly comprise an adsorption method, an extraction method, a photocatalytic oxidation method, a biological method and other treatment methods. Among them, the adsorption method is widely favored because of its characteristics of simple equipment, low energy consumption, short process flow, etc.
Adsorption processes typically utilize high efficiency adsorbents having large specific surface areas and pore volumes to adsorb, concentrate, and further remove or recover the contaminants. Diatomite is used as a porous material, has unique surface structure, good adsorption performance, the advantages of large pore capacity, good physical and chemical stability and the like, is rich in resources and low in price, and is already used as an adsorbent in various industrial wastewater treatment processes. Diatomite is used as a porous material, has unique surface structure, good adsorption performance, the advantages of large pore capacity, good physical and chemical stability and the like, is rich in resources and low in price, and is already used as an adsorbent in various industrial wastewater treatment processes. The surface of the diatomite contains rich surface hydroxyl groups, so that a large amount of hydrogen bond acting force can be formed with phenolic hydroxyl groups of phenolic organic matters, the adsorption of the diatomite on most of the phenolic organic matters is improved, and the diatomite has inherent advantage on the treatment of phenolic wastewater. However, the diatomite has the defects of overlarge pore diameter, low adsorption efficiency and the like, and meanwhile, the diatomite has high hydrophilicity, and when phenolic organic matters are adsorbed, adsorption sites of the diatomite are always occupied by water molecules, so that the adsorption capacity of organic pollutants is low, and the use effect is reduced.
The carbon nano tube has larger specific surface area and strong adsorption capacity to organic matters. The adsorption action force of the carbon nano tube on the organic matters mainly comprises the following steps: van der waals interactions (e.g., hydrophobic interactions, electrostatic interactions, etc.), hydrogen bonding, and pi-pi interactions. However, the carbon nanotubes have strong van der waals force effect, and have high length-diameter ratio and large specific surface area, so that the carbon nanotubes are very easy to form aggregates, and the carbon nanotubes are independently used as an adsorbent, so that the cost is high, and the exertion of good performance of the carbon nanotubes is limited.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of a diatomite-loaded carbon nanotube adsorbent, the prepared diatomite-loaded carbon nanotube adsorbent has the advantages of large specific surface area and good thermal stability, and carbon nanotubes are uniformly dispersed on the surface of diatomite and have high adsorption capacity on phenolic organic matters.
The invention also aims to provide the diatomite-loaded carbon nanotube adsorbent prepared by the preparation method.
The invention further aims to provide application of the diatomite-loaded carbon nanotube adsorbent.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a diatomite-loaded carbon nanotube adsorbent comprises the following steps:
(1) pretreating original diatomite to remove impurities in pore passages and surfaces of the original diatomite material;
(2) adding the diatomite treated in the step (1) into a catalyst solution, stirring for 2-4 hours at the temperature of 60-80 ℃, then performing suction filtration, and drying to obtain solid powder; the catalyst solution is Ni (NO)3)2、Fe(NO3)3And Co (NO)3)2One or two ofSeed growing;
(3) heating the solid powder obtained in the step (2) to 400-480 ℃ in a nitrogen atmosphere, then introducing a mixed gas of nitrogen and hydrogen, preserving the heat for 1-2 h, then heating to 800 ℃ plus 500 ℃, introducing a mixed gas mixed with nitrogen, hydrogen and a carbon source gas, preserving the heat for 15-90 min, closing the hydrogen and the carbon source gas, and cooling to room temperature in the nitrogen atmosphere to obtain black solid powder with the carbon nanotube content of 30-60%;
(4) and (3) annealing the black solid powder in the step (3), cooling, adding the solid powder into a 20-30% acid solution, carrying out acidification treatment at the temperature of 80-100 ℃, washing, drying, grinding and sieving to obtain the diatomite-loaded carbon nanotube adsorbent with uniform particle size.
The method for pretreating the original diatomite in the step (1) comprises the following steps:
calcining original diatomite in a high-temperature furnace at 300-500 ℃ for 1-3 hours, cooling, adding the obtained diatomite into a hydrochloric acid solution with the concentration of 5-10%, cleaning and purifying, wherein the solid-to-liquid ratio is 1: 2-1: 5, and drying the obtained diatomite after cleaning.
The concentration of the catalyst solution in the step (2) is 0.5-1.5 mol/L.
And (3) the solid-to-liquid ratio of the diatomite to the catalyst solution in the step (2) is 1: 5-1: 10.
And (3) the carbon source gas is acetylene, methane or carbon monoxide.
The flow rate of the gas introduced in the step (3) is as follows: the carbon source gas is 100-400 mL/min, the hydrogen gas is 200-600 mL/min, and the nitrogen gas is 400-1500 mL/min.
The annealing temperature in the step (4) is 300-400 ℃.
The acid solution in the step (4) is hydrochloric acid or nitric acid solution.
The diatomite-loaded carbon nanotube adsorbent prepared by the preparation method of the diatomite-loaded carbon nanotube adsorbent.
The diatomite-loaded carbon nanotube adsorbent is applied to adsorption of phenolic organic matters.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the adsorbent disclosed by the invention adopts diatomite raw ore as a main raw material, and the carbon nano tubes are loaded on the surface of the diatomite by using a chemical vapor deposition technology, so that the problem of dispersion uniformity of the carbon nano tubes is solved, wherein the carbon nano tubes account for 30% -60% of the total mass, and the specific surface area of the composite adsorbent material can reach 40-100 m2Has the advantages of large specific surface area and good thermal stability.
(2) In the raw materials, the diatomite raw ore has wide and easily-obtained sources and low cost, the chemical vapor deposition preparation method is simple, the preparation cost is low, and the diatomite raw ore can be synthesized in a large amount, so that the diatomite composite material has certain economic and environmental benefits.
(3) The diatomite-loaded carbon nanotube adsorbent prepared by the method is green and pollution-free, the adsorption time is short, and the adsorption capacity is improved by nearly 150% compared with that of a pure diatomite material.
Drawings
FIG. 1 is a scanning electron micrograph of pretreated diatomaceous earth prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the diatomite-loaded carbon nanotube adsorbent prepared in example 1 of the present invention.
Fig. 3 is a thermogravimetric plot of the diatomaceous earth-loaded carbon nanotube adsorbent of the present invention.
FIG. 4 is a graph comparing the adsorption capacity of diatomaceous earth and diatomaceous earth loaded carbon nanotube adsorbents on phenol obtained from pretreatment in accordance with an embodiment of the present invention.
Fig. 5 is a scanning electron microscope image of the diatomite-loaded carbon nanotube adsorbent prepared in example 2 according to the present invention.
Fig. 6 is a scanning electron microscope image of the diatomite-loaded carbon nanotube adsorbent prepared in example 3 according to the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Preparation of diatomite-loaded carbon nano tube adsorbent composite adsorbent
1. Raw materials and reagents
1) The ignition loss of the original diatomite is less than 0.05 percent;
2)Ni(NO3)2is chemically pure.
2. Preparation procedure
Step 1: pretreatment of diatomite: calcining original diatomite in a high-temperature furnace at 500 ℃ for 2 hours, cooling, adding the obtained diatomite into a 10% hydrochloric acid solution, cleaning and purifying, wherein the solid-to-liquid ratio is 1:3, drying the obtained diatomite after cleaning, and scanning electron microscopy of the pretreated diatomite is shown in figure 1.
Step 2: prefabrication of a diatomite carrier: adding the diatomite obtained in the step 1 into Ni (NO) with the concentration of 0.1mol/L3)2Stirring the solution at a solid-liquid ratio of 1:10 at 80 ℃ for 4 hours, then carrying out suction filtration, and drying to remove the solvent to obtain light green solid powder.
And step 3: loading of carbon nanotubes: placing 5g of the solid powder obtained in the step 2 into a porcelain boat, placing the porcelain boat into a tube furnace, heating to 480 ℃ under the nitrogen atmosphere, introducing mixed gas of nitrogen and hydrogen, preserving heat for 1 hour, heating to 500 ℃, introducing mixed gas mixed with nitrogen, hydrogen and carbon source gas, wherein the flow rate of the gas is as follows: the carbon source gas is 200mL/min, the hydrogen gas is 400mL/min, and the nitrogen gas is 800 mL/min; keeping the temperature for 60min, closing hydrogen and carbon source gas, and cooling to room temperature in a nitrogen atmosphere to obtain black solid powder.
And 4, step 4: and (3) placing the black solid powder obtained in the step (3) in a muffle furnace for annealing treatment at 350 ℃, cooling, adding the solid powder into 36% hydrochloric acid solution, carrying out acidification treatment at 100 ℃, washing, drying, slightly grinding and sieving to obtain the diatomite-loaded carbon nanotube adsorbent with uniform particle size, wherein a scanning electron microscope picture of the adsorbent is shown in figure 2.
(II) thermogravimetric analysis
The thermogravimetric graph of the diatomite-loaded carbon nanotube adsorbent composite adsorbent prepared in this example is shown in fig. 3, and it can be seen from the thermogravimetric graph that the carbon nanotubes in the synthesized composite material account for 39.23%.
(III) measurement of phenol adsorption Performance
1. Samples and reagents
1) Diatomaceous earth was obtained by diatomaceous earth pretreatment in step 1 of this example.
2) A diatomaceous earth-supported carbon nanotube adsorbent was prepared in this example.
3) Phenol standard solution: respectively weighing a certain amount of phenol, dissolving in water, and fixing the volume in a volumetric flask until the concentration is respectively 50 mg/L.
2. Measurement of phenol adsorption Performance
Weighing 6 parts of 50mg of diatomite and 6 parts of a diatomite-loaded carbon nanotube adsorbent, respectively adding the weighed materials into a phenol solution (50mg/L) containing 25ml of the phenol solution, placing the mixture into a constant-temperature stirrer, stirring the mixture at the speed of 120 revolutions per minute, taking out one part of diatomite and one part of the diatomite-loaded carbon nanotube adsorbent every 10 minutes, carrying out suction filtration, measuring the mass concentration of phenol in clear liquid by an ultraviolet-visible spectrophotometer, and respectively calculating the adsorption capacity at each moment according to the change of the mass concentration at each moment. The test result is shown in FIG. 4, and the maximum adsorption value can reach 7.41 mg/g.
Example 2
Preparation of diatomite-loaded carbon nano tube adsorbent composite adsorbent
1. Raw materials and reagents
1) The ignition loss of the original diatomite is less than 0.05 percent;
2)Ni(NO3)2is chemically pure.
2. Preparation procedure
Step 1: pretreatment of diatomite: calcining original diatomite in a high-temperature furnace at 500 ℃ for 2 hours, cooling, adding the obtained diatomite into a 10% hydrochloric acid solution, cleaning and purifying, wherein the solid-to-liquid ratio is 1:3, drying the obtained diatomite after cleaning, and performing pretreatment on the obtained diatomite by a scanning electron microscope shown in figure 1.
Step 2: prefabrication of a diatomite carrier: adding the diatomite obtained in the step 1 into Ni (NO) with the concentration of 0.1mol/L3)2Stirring the solution at a solid-to-liquid ratio of 1:10 at 80 ℃ for 4 hours, then carrying out suction filtration,the solvent was removed by drying to give a pale green solid powder.
And step 3: loading of carbon nanotubes: placing 5g of the solid powder obtained in the step 2 into a porcelain boat, placing the porcelain boat into a tube furnace, heating to 480 ℃ under the nitrogen atmosphere, introducing mixed gas of nitrogen and hydrogen, preserving heat for 1 hour, heating to 600 ℃, introducing mixed gas mixed with nitrogen, hydrogen and carbon source gas, wherein the flow rate of the gas is as follows: the carbon source gas is 200mL/min, the hydrogen gas is 400mL/min, and the nitrogen gas is 800 mL/min; keeping the temperature for 60min, closing hydrogen and carbon source gas, and cooling to room temperature in a nitrogen atmosphere to obtain black solid powder.
And 4, step 4: and (3) placing the black solid powder obtained in the step (3) in a muffle furnace for annealing treatment at 350 ℃, cooling, adding the solid powder into 36% hydrochloric acid solution, carrying out acidification treatment at 100 ℃, washing, drying, slightly grinding and sieving to obtain the diatomite-loaded carbon nanotube adsorbent with uniform particle size, wherein a scanning electron microscope image of the adsorbent is shown in FIG. 5.
(II) thermogravimetric analysis
The thermogravimetric graph of the diatomite-loaded carbon nanotube adsorbent composite adsorbent prepared in this example is shown in fig. 3, and it can be seen from the thermogravimetric graph that the carbon nanotubes in the synthesized composite material account for 44.28%.
(III) measurement of phenol adsorption Performance
1. Samples and reagents
1) Diatomaceous earth was obtained by diatomaceous earth pretreatment in step 1 of this example.
2) A diatomaceous earth-supported carbon nanotube adsorbent was prepared in this example.
3) Phenol standard solution: respectively weighing a certain amount of phenol, dissolving in water, and fixing the volume in a volumetric flask until the concentration is respectively 50 mg/L.
2. Measurement of phenol adsorption Performance
Weighing 6 parts of 50mg of diatomite and 6 parts of a diatomite-loaded carbon nanotube adsorbent, respectively adding the weighed materials into a phenol solution (50mg/L) containing 25ml of the phenol solution, placing the mixture into a constant-temperature stirrer, stirring the mixture at the speed of 120 revolutions per minute, taking out one part of diatomite and one part of the diatomite-loaded carbon nanotube adsorbent every 10 minutes, carrying out suction filtration, measuring the mass concentration of phenol in clear liquid by an ultraviolet-visible spectrophotometer, and respectively calculating the adsorption capacity at each moment according to the change of the mass concentration at each moment. The test result is shown in FIG. 4, and the maximum adsorption value can reach 7.95 mg/g.
Example 3
Preparation of diatomite-loaded carbon nano tube adsorbent composite adsorbent
1. Raw materials and reagents
1) The ignition loss of the original diatomite is less than 0.05 percent;
2)Ni(NO3)2is chemically pure.
2. Preparation procedure
Step 1: pretreatment of diatomite: calcining original diatomite in a high-temperature furnace at 500 ℃ for 2 hours, cooling, adding the obtained diatomite into a 10% hydrochloric acid solution, cleaning and purifying, wherein the solid-to-liquid ratio is 1:3, drying the obtained diatomite after cleaning, and scanning electron microscopy of the pretreated obtained diatomite is shown in figure 1.
Step 2: prefabrication of a diatomite carrier: adding the diatomite obtained in the step 1 into Ni (NO) with the concentration of 0.1mol/L3)2Stirring the solution at a solid-liquid ratio of 1:10 at 80 ℃ for 4 hours, then carrying out suction filtration, and drying to remove the solvent to obtain light green solid powder.
And step 3: loading of carbon nanotubes: placing 5g of the solid powder obtained in the step 2 into a porcelain boat, placing the porcelain boat into a tube furnace, heating to 480 ℃ under the nitrogen atmosphere, introducing mixed gas of nitrogen and hydrogen, preserving heat for 1 hour, heating to 700 ℃, introducing mixed gas mixed with nitrogen, hydrogen and carbon source gas, wherein the flow rate of the gas is as follows: the carbon source gas is 200mL/min, the hydrogen gas is 400mL/min, and the nitrogen gas is 800 mL/min; keeping the temperature for 60min, closing hydrogen and carbon source gas, and cooling to room temperature in a nitrogen atmosphere to obtain black solid powder.
And 4, step 4: and (3) placing the black solid powder obtained in the step (3) in a muffle furnace for annealing treatment at 350 ℃, cooling, adding the solid powder into 36% hydrochloric acid solution, carrying out acidification treatment at 100 ℃, washing, drying, slightly grinding and sieving to obtain the diatomite-loaded carbon nanotube adsorbent with uniform particle size, wherein a scanning electron microscope image of the adsorbent is shown in FIG. 6.
(II) thermogravimetric analysis
The thermogravimetric graph of the diatomite-loaded carbon nanotube adsorbent composite adsorbent prepared in this example is shown in fig. 3, and it can be seen from the thermogravimetric graph that the carbon nanotubes in the synthesized composite material account for 19.52%.
(III) measurement of phenol adsorption Performance
1. Samples and reagents
1) Diatomaceous earth was obtained by diatomaceous earth pretreatment in step 1 of this example.
2) A diatomaceous earth-supported carbon nanotube adsorbent was prepared in this example.
3) Phenol standard solution: respectively weighing a certain amount of phenol, dissolving in water, and fixing the volume in a volumetric flask until the concentration is respectively 50 mg/L.
2. Measurement of phenol adsorption Performance
Weighing 6 parts of diatomite obtained by pretreatment of 50mg and 6 parts of diatomite-loaded carbon nanotube adsorbent, respectively adding the diatomite-loaded carbon nanotube adsorbent into a phenol solution (50mg/L) containing 25ml at room temperature, placing the solution into a constant-temperature stirrer, stirring at the speed of 120 revolutions per minute, taking out one part of diatomite and one part of diatomite-loaded carbon nanotube adsorbent every 10min, carrying out suction filtration, measuring the mass concentration of phenol in clear liquid by an ultraviolet-visible spectrophotometer, and respectively calculating the adsorption capacity at each moment according to the change of the mass concentration at each moment. The test result is shown in FIG. 4, and the maximum adsorption value can reach 5.82 mg/g.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. The preparation method of the diatomite-loaded carbon nanotube adsorbent is characterized by comprising the following steps of:
(1) pretreating original diatomite to remove impurities in pore passages and surfaces of the original diatomite material, and specifically comprises the following steps: calcining original diatomite in a high-temperature furnace at 300-500 ℃ for 1-3 hours, cooling, adding the obtained diatomite into a hydrochloric acid solution with the concentration of 5-10%, cleaning and purifying, and drying the obtained diatomite after cleaning;
(2) adding the diatomite treated in the step (1) into a catalyst solution, stirring for 2-4 hours at the temperature of 60-80 ℃, then performing suction filtration, and drying to obtain solid powder; the catalyst solution is Ni (NO)3)2、Fe(NO3)3And Co (NO)3)2One or two of them;
(3) heating the solid powder obtained in the step (2) to 400-480 ℃ in a nitrogen atmosphere, then introducing a mixed gas of nitrogen and hydrogen, preserving the heat for 1-2 h, then heating to 800 ℃ plus 500 ℃, introducing a mixed gas mixed with nitrogen, hydrogen and a carbon source gas, preserving the heat for 15-90 min, closing the hydrogen and the carbon source gas, and cooling to room temperature in the nitrogen atmosphere to obtain black solid powder with the carbon nanotube content of 30-60%;
(4) annealing the black solid powder in the step (3) at 300-400 ℃, cooling, adding the solid powder into 20-30% acid solution, acidizing at 80-100 ℃, washing, drying, grinding and sieving to obtain the black solid powder with uniform particle size and specific surface area of 40-100 m2The diatomite supports the carbon nano tube adsorbent.
2. The method for preparing the diatomite-loaded carbon nanotube adsorbent according to claim 1, wherein the solid-to-liquid ratio of the diatomite and the hydrochloric acid solution in the step (1) is 1:2 to 1: 5.
3. The method for preparing the diatomite-supported carbon nanotube adsorbent according to claim 1, wherein the concentration of the catalyst solution in the step (2) is 0.5mol/L to 1.5 mol/L.
4. The method for preparing the diatomite-supported carbon nanotube adsorbent according to claim 1 or 3, wherein the solid-to-liquid ratio of the diatomite to the catalyst solution in the step (2) is 1:5 to 1: 10.
5. The method for preparing the diatomite-supported carbon nanotube adsorbent according to claim 1, wherein the carbon source gas in the step (3) is acetylene, methane or carbon monoxide.
6. The method for preparing the diatomite-supported carbon nanotube adsorbent according to claim 1, wherein the flow rate of the gas introduced in the step (3) is as follows: the carbon source gas is 100-400 mL/min, the hydrogen gas is 200-600 mL/min, and the nitrogen gas is 400-1500 mL/min.
7. The method for preparing the diatomite-supported carbon nanotube adsorbent according to claim 1, wherein the acid solution in the step (4) is hydrochloric acid or nitric acid solution.
8. The diatomite-loaded carbon nanotube adsorbent prepared by the method for preparing the diatomite-loaded carbon nanotube adsorbent according to any one of claims 1 to 7.
9. The use of the diatomaceous earth-loaded carbon nanotube adsorbent of claim 8 for adsorbing phenolic organic compounds.
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