CN115805076A - Catalyst and preparation method thereof, array carbon nanotube and preparation method thereof - Google Patents
Catalyst and preparation method thereof, array carbon nanotube and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of carbon material preparation, and discloses a catalyst and a preparation method thereof, an array carbon nanotube and a preparation method thereof. A catalyst is prepared by calcining a catalyst precursor solution, wherein the catalyst precursor solution is prepared by dissolving a soluble active component containing an active metal element, a soluble carrier component containing a carrier element and a soluble complexing agent in water, the concentration of the active metal element is 0.5-3mol/L, the concentration of the carrier element is 0.5-5.0mol/L, and the concentration of the complexing agent is 3.0-7.0mol/L. The catalyst is beneficial to preparing the array carbon nano tube with low specific surface area and short array length, thereby being beneficial to preparing the array carbon nano tube with high dispersibility, and further improving the application dispersibility of the array carbon nano tube.
Description
Technical Field
The invention relates to the technical field of carbon material preparation, in particular to a catalyst and a preparation method thereof, an array carbon nanotube and a preparation method thereof.
Background
The carbon nano tube is a one-dimensional quantum material with a unique nano hollow structure, has excellent conductivity, and can be dispersed in a solvent to form conductive slurry to be applied to a lithium ion battery.
The carbon nanotubes are classified into arrayed carbon nanotubes and clustered carbon nanotubes according to the aggregation state. The array carbon nano-tubes are orderly arranged and have good orientation, so that the electrical conductivity and the dispersibility of the array carbon nano-tubes are generally better than those of the clustered carbon nano-tubes. However, the length of the array of the carbon nanotubes on the market is long, a certain winding property still exists among the single carbon nanotubes in the tube bundle, and the specific surface area of the long array carbon nanotube is relatively high, so that the dispersibility of the long array carbon nanotube is not as good as that of the short array carbon nanotube with low specific surface area.
Based on this, the inventors believe that in order to improve the dispersibility of the arrayed carbon nanotubes, it is necessary to provide short arrayed carbon nanotubes with a low specific surface area, which are usually prepared by catalyzing a carbon source gas with a catalyst, so that the catalyst can significantly affect the physicochemical properties of the arrayed carbon nanotubes. At present, people usually adsorb and impregnate an active metal and a solid carrier, and then calcine the active metal after evaporating water to dryness to obtain a catalyst for preparing an array carbon nanotube, and the dispersibility of the array carbon nanotube prepared by the catalyst is still poor, so that a catalyst beneficial to preparing the array carbon nanotube with good dispersibility needs to be developed.
Disclosure of Invention
In order to prepare the array carbon nano tube with high dispersibility, the application provides a catalyst and a preparation method thereof, and the array carbon nano tube and a preparation method thereof.
In a first aspect, the present application provides a catalyst, which adopts the following technical scheme:
a catalyst is prepared by calcining a catalyst precursor solution, wherein the catalyst precursor solution is prepared by dissolving a soluble active component containing an active metal element, a soluble carrier component containing a carrier element and a soluble complexing agent in water, the concentration of the active metal element is 0.5-3mol/L, the concentration of the carrier element is 0.5-5.0mol/L, and the concentration of the complexing agent is 3.0-7.0mol/L.
The active component, the carrier component and the complexing agent are dissolved in water together, the complexing agent is used as an organic ligand and can be simultaneously complexed with the active metal element and the carrier element to form a metal organic framework compound, the metal organic framework compound expands under the action of calcination and then cracks and burns, simultaneously, moisture and non-metal ions in a catalyst precursor solution are evaporated, decomposed and removed, and then the residual metal element and oxygen in the air are self-assembled to generate the metal oxide catalyst with a lamellar structure. By calcining the catalyst precursor solution, the active metal elements can be uniformly distributed in the carrier elements, and the catalyst has higher activity; and the catalyst with the lamellar structure can be easily grown into the high-dispersity array carbon nano tube with low specific surface area and short array, so that the preparation of the conductive slurry with high solid content is facilitated, and the enterprise cost is reduced.
Further, the soluble active component is one or more of soluble manganese salt, iron salt, cobalt salt, nickel salt and molybdate.
Still further, the soluble active components comprise nitrate, chloride, sulfate, organic acid salt and the like; the soluble manganese salt comprises manganese nitrate, manganese chloride, manganese sulfate, manganese acetate and the like; the soluble ferric salt comprises ferric nitrate, ferric chloride, ferric sulfate and the like; the soluble cobalt salt comprises cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate and the like; the soluble nickel salt comprises nickel nitrate, nickel chloride, nickel sulfate, nickel acetate and the like; the soluble molybdate comprises ammonium heptamolybdate.
Further, the soluble carrier component is one or more of soluble magnesium salt, aluminum salt, calcium salt and aluminosilicate.
Still further, the soluble carrier component comprises nitrate, chloride, sulfate, organic acid salt and the like, and the soluble magnesium salt comprises magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium acetate and the like; the soluble aluminum salt comprises aluminum nitrate, aluminum chloride, aluminum sulfate and the like; the soluble calcium salt includes calcium chloride, calcium acetate, calcium nitrate, etc.
Further, the molar ratio of the active metal element to the carrier element is 1: (0.6-3).
Furthermore, the mol ratio of the complexing agent to the sum of the active metal element and the carrier element is 1 (0.5-1.25).
The activity and the morphology of the catalyst can be controlled by adjusting the molar ratio of the active metal element, the carrier element and the complexing agent, so that the morphology, the specific surface area, the resistivity and the like of the carbon nano tube prepared by the catalyst are controlled, and finally the array carbon nano tube with high dispersibility is obtained.
Preferably, the complexing agent comprises one or more of citric acid, tartaric acid, sorbic acid, ethylene diamine tetraacetic acid, ethylene glycol, polyethylene glycol and glycerol.
In a second aspect, the present application provides a method for preparing a catalyst, which adopts the following technical scheme:
a method of preparing a catalyst comprising the steps of:
step S1, dissolving an active component containing an active metal element, a carrier component containing a carrier element and a complexing agent in water, and uniformly mixing to obtain a catalyst precursor solution;
and S2, calcining the catalyst precursor solution at the high temperature of 500-900 ℃ for 10min-4h to obtain the catalyst.
In the catalyst precursor solution, a complexing agent simultaneously complexes active metal elements and carrier elements to form a metal organic framework compound, and the metal organic framework compound is calcined at a high temperature of 500-900 ℃ for 10min-4h to be fully expanded, cracked and combusted, so that the catalyst with a lamellar structure is finally obtained. The preparation process of the catalyst is simple and easy to implement, has wide raw material sources, is beneficial to shortening the production period of the carbon nano tube, and is suitable for industrial mass production.
In a third aspect, the present application provides an array carbon nanotube, which adopts the following technical scheme:
the array carbon nanotube is prepared by the catalyst, the array length of the low specific surface area short array carbon nanotube is 10-50 mu m, and the specific surface area is 100-180m 2 (ii)/g, powder resistivity is 10 to 25 m.OMEGA.cm.
Most of the commercially available carbon nanotubes are 50 μm or more in array length and 200m in specific surface area 2 Because the carbon nano tube array is longer in length and relatively higher in specific surface area, the dispersion of the carbon nano tube array powder is poor.
The array carbon nanotube powder prepared by the method not only has better conductivity, but also has the array length of 10-50um and the specific surface area of 100-180m 2 The specific surface area is obviously lower than the array length and the specific surface area of the commercially available array carbon nano tube, so that the dispersity of the carbon nano tube is effectively improved.
In a fourth aspect, the present application provides a method for preparing an array carbon nanotube, which adopts the following technical scheme:
the preparation method of the array carbon nanotube comprises the following steps: introducing hydrogen into the catalyst at 650-720 ℃ for reduction for 0-60min, and introducing carbon source gas for catalytic reaction at 650-720 ℃ for 10-90min to obtain the array carbon nanotube powder.
The carbon source gas is generally a hydrocarbon compound, and as the carbon source gas is continuously cracked at a high temperature of 650-720 ℃, C-H bonds are broken, thereby gradually forming carbon and hydrogen. Therefore, the hydrogen gas generated by the cracking of the carbon source gas can reduce the active metal oxide on the surface of the catalyst to the simple active metal without introducing hydrogen gas. The active metal simple substance has a good catalytic effect on the carbon source deposited on the surface of the catalyst at 650-720 ℃, and the carbon source gas is subjected to catalytic reaction for 10-90min at 650-720 ℃, so that the carbon source gas is cracked and grown on the surface of the catalyst prepared by the method, and the array carbon nanotube powder with low specific surface area and short array length is obtained.
Further, the carbon source gas is any one of methane, ethane, propane, ethylene and propylene.
Preferably, before introducing hydrogen, the catalyst is firstly introduced with nitrogen or inert gas to raise the temperature to 680-700 ℃, and after the temperature is stable, hydrogen is introduced; and further, after the carbon source gas is introduced, introducing nitrogen or inert gas, and naturally cooling to 20-30 ℃ to obtain the arrayed carbon nanotube powder.
Preferably, the catalyst is charged in an amount of 0.2 to 2g, and the flow rate of the carbon source gas is 1 to 3L/min.
In summary, the present application has the following beneficial effects:
1. the active component, the carrier component and the complexing agent are matched with a specific concentration to form a catalyst precursor solution, and then the catalyst precursor solution is calcined to form the lamellar catalyst, so that the lamellar catalyst is beneficial to catalyzing carbon source gas to obtain the array carbon nanotube with low specific surface area and short array length.
2. By adjusting the molar ratio of the active metal element to the carrier element and further adjusting the molar ratio of the sum of the active metal element and the carrier element to the complexing agent, the activity and the microscopic morphology of the catalyst can be further regulated and controlled, the catalyst can be used for better catalyzing a carbon source gas, and the array carbon nanotube with low specific surface area and short array length can be obtained.
3. The array carbon nano tube prepared by the method has the advantages of powder resistivity of 10-25m omega cm, better conductive performance, array length of 10-50 mu m and specific surface area of 100-180m 2 A/g, having a shorter array length and at the same time a lower specific surface area, the dispersibility of the array carbon nano tube prepared by the method is obviously improved compared with that of the array carbon nano tube in the prior art, and the dispersibility is also improved on the basis of keeping better conductivity.
Drawings
FIG. 1 is a scanning electron micrograph (upper panel) of a catalyst prepared in preparation example 1 of the present application and a scanning electron micrograph (lower panel) of a catalyst prepared in comparative preparation example 1.
Fig. 2 is a 500-fold scanning electron micrograph (upper view) and a 5000-fold scanning electron micrograph (lower view) of the arrayed carbon nanotubes prepared in example 1 of the present application.
Fig. 3 is a 500-fold scanning electron micrograph (upper panel) and a 5000-fold scanning electron micrograph (lower panel) of the arrayed carbon nanotubes prepared in example 3 of the present application.
Fig. 4 a raman spectrum of the carbon nanotube array prepared in example 3 of the present application.
FIG. 5 is a 500-fold scanning electron micrograph (upper panel) and a 5000-fold scanning electron micrograph (lower panel) of comparative sample 1, which is an example of the present application.
FIG. 6 is a 500-fold scanning electron micrograph (upper panel) and a 5000-fold scanning electron micrograph (lower panel) of comparative sample 2, which is an example of the present application.
Detailed Description
Preparation example 1
A catalyst is prepared by the following method:
step S1, stirring cobalt nitrate, aluminum nitrate and citric acid in 30mL of water until the cobalt nitrate, the aluminum nitrate and the citric acid are dissolved uniformly to obtain a catalyst precursor solution; wherein, cobalt nitrate is an active component, and the concentration of cobalt element is 0.85mol/L; aluminum nitrate is used as a carrier component, and the concentration of aluminum element is 1.6mol/L; citric acid is taken as a complexing agent, and the concentration of the citric acid is 4.9mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 into a crucible, and then placing the crucible in a muffle furnace to be calcined at a high temperature of 500 ℃ for 2h to obtain the catalyst (the structural morphology is shown in the upper diagram of FIG. 1).
Preparation example 2
A catalyst is prepared by the following method: step S1, stirring nickel acetate, ammonium heptamolybdate, magnesium acetate and tartaric acid in 30mL of water until the nickel acetate, the ammonium heptamolybdate, the magnesium acetate and the tartaric acid are dissolved uniformly to obtain a catalyst precursor solution; the nickel acetate and the ammonium heptamolybdate are used as active components, the concentration of nickel element is 3.0mol/L, the concentration of molybdenum element is 0.51mol/L, the magnesium acetate is used as a carrier component, the concentration of magnesium element is 4.98mol/L, the tartaric acid is a complexing agent, and the concentration of the tartaric acid is 6.79mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 to one third of the crucible, and then placing the crucible in a muffle furnace to be calcined at a high temperature of 500 ℃ for 4 hours to obtain the catalyst.
Preparation example 3
A catalyst is prepared by the following method: step S1, stirring cobalt nitrate, manganese nitrate, aluminum nitrate and citric acid in 30mL of water until the cobalt nitrate and the manganese nitrate are uniformly dissolved to obtain a catalyst precursor solution, wherein the cobalt nitrate and the manganese nitrate are used as active components, the concentration of a cobalt element is 0.73mol/L, the concentration of a manganese element is 0.5mol/L, the aluminum nitrate is used as a carrier component, the concentration of an aluminum element is 2.9mol/L, the citric acid is used as a complexing agent, and the concentration of the citric acid is 7.0mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 into a crucible, and then placing the crucible in a muffle furnace for high-temperature calcination at 650 ℃ for 30min to obtain the catalyst.
Preparation example 4
A catalyst is prepared by the following method: step S1, stirring and uniformly dissolving ferric nitrate, ammonium heptamolybdate, aluminum nitrate, calcium nitrate and ethylene diamine tetraacetic acid in 30mL of water to obtain a catalyst precursor solution, wherein the ferric nitrate and the ammonium heptamolybdate are active components, the concentration of an iron element is 2.45mol/L, the concentration of a molybdenum element is 1.0mol/L, the calcium nitrate and the aluminum nitrate are carrier components, the concentration of a calcium element is 0.5mol/L, the concentration of an aluminum element is 1.57mol/L, the ethylene diamine tetraacetic acid is a complexing agent, and the concentration of the ethylene diamine tetraacetic acid is 4.83mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 into a crucible, and then placing the crucible into a muffle furnace to calcine at the high temperature of 900 ℃ for 10min to obtain the catalyst.
Preparation example 5
A catalyst is prepared by the following method: step S1, stirring and uniformly dissolving ferric nitrate, nickel nitrate, aluminum nitrate, magnesium nitrate and citric acid in 30mL of water to obtain a catalyst precursor solution, wherein the ferric nitrate and the nickel nitrate are active components, the concentration of an iron element is 1.56mol/L, the concentration of a nickel element is 0.5mol/L, the aluminum nitrate and the magnesium nitrate are carrier components, the concentration of an aluminum element is 1mol/L, the concentration of a magnesium element is 4.58mol/L, the citric acid is a complexing agent, and the concentration of the citric acid is 6.11mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 into a crucible, and then placing the crucible in a muffle furnace to calcine at a high temperature of 500 ℃ for 1h to obtain the catalyst.
Preparation example 6
A catalyst is prepared by the following method: step S1, stirring cobalt acetate, manganese nitrate, aluminum nitrate, magnesium acetate and ethylene glycol in 30mL of water until the cobalt acetate, the manganese nitrate and the manganese nitrate are uniformly dissolved to obtain a catalyst precursor solution, wherein the cobalt acetate and the manganese nitrate are used as active components, the concentration of a cobalt element is 0.73mol/L, the concentration of a manganese element is 0.93mol/L, the aluminum nitrate and the magnesium acetate are used as carrier components, the concentration of an aluminum element is 3.32mol/L, the concentration of a magnesium element is 1.66mol/L, the ethylene glycol is a complexing agent, and the concentration of the ethylene glycol is 6.3mol/L.
And S2, adding the catalyst precursor solution prepared in the step S1 into a crucible, and then placing the crucible into a muffle furnace to calcine at the high temperature of 750 ℃ for 30min to obtain the catalyst.
Preparation of comparative example 1
A comparative sample 1 was prepared by the following method: the difference from preparation example 1 is that: and (3) carrying out spray drying on the catalyst precursor solution prepared in the step (S1) to obtain catalyst precursor powder. The catalyst precursor powder was then calcined in a muffle furnace at 500 ℃ for 2h to obtain a preparation comparative sample 1 (see the lower diagram of fig. 1 for specific structural morphology).
Preparation of comparative example 2
A comparative sample 2 was prepared by the following method: the difference from preparation example 3 is that: in the step S1, cobalt nitrate, manganese nitrate and aluminum nitrate are stirred in 30mL of water until the cobalt nitrate, the manganese nitrate and the aluminum nitrate are uniformly dissolved to obtain a catalyst precursor solution, wherein the cobalt nitrate and the manganese nitrate are used as active components, the concentration of a cobalt element is 0.73mol/L, the concentration of a manganese element is 0.5mol/L, the aluminum nitrate is used as a carrier component, and the concentration of an aluminum element is 2.9mol/L.
Preparation of comparative example 3
A comparative sample 3 was prepared by the following method: the difference from preparation example 3 is that: in the step S1, the concentration of the cobalt element is 0.33mol/L, and the concentration of the manganese element is 0.37mol/L.
Preparation of comparative example 4
A comparative sample 4 was prepared by the following method: the difference from preparation example 3 is that: in the step S1, cobalt nitrate, manganese nitrate and diaspore are uniformly stirred in 30mL of water to obtain a catalyst precursor suspension, wherein the concentration of cobalt element is 0.73mol/L, the concentration of manganese element is 0.5mol/L, and the concentration of aluminum element is 2.9mol/L.
In each of the above examples and comparative preparation examples, specific components of the active component, the carrier component and the complexing agent, and the molar ratio x of the active metal element to the carrier element and the molar ratio y of the complexing agent to the sum of the active metal element and the carrier element are specified in table 1.
The molar ratio x of the active metal element to the support element is calculated as follows:
the molar ratio y of complexing agent to the sum of active metal element and carrier element is calculated as follows:
TABLE 1
Example 1
An array carbon nanotube is prepared by the following method: placing 0.2g of the catalyst prepared in preparation example 1 in a vertical fluidized bed reactor, introducing 2L/min of nitrogen gas, starting a heating furnace to heat to 700 ℃, introducing 1L/min of hydrogen gas to reduce for 30min after the temperature is stable, introducing 1L/min of propylene to react for 30min after the reduction is finished, and continuing to cool to room temperature under the protection of 2L/min of nitrogen gas after the reaction is finished to obtain the array carbon nanotube powder (the specific structural morphology is shown in figure 2).
Example 2
An array carbon nanotube is prepared by the following method: placing 2g of the catalyst prepared in preparation example 2 in a vertical fluidized bed reactor, introducing 3L/min of nitrogen gas, starting a heating furnace, heating to 700 ℃, directly introducing 2L/min of propylene for reaction for 10min after the temperature is stable, and continuously cooling to room temperature under the protection of 3L/min of nitrogen gas after the reaction is finished to obtain the array carbon nanotube powder.
Example 3
An array carbon nanotube is prepared by the following method: placing 0.5g of the catalyst prepared in preparation example 3 in a vertical fluidized bed reactor, introducing 1L/min of nitrogen protection gas, starting a heating furnace, heating to 680 ℃, introducing 1L/min of hydrogen to reduce for 10min after the temperature is stable, introducing 1L/min of propylene to react for 60min after the reduction is finished, and continuing cooling to room temperature under the protection of 1L/min of nitrogen after the reaction is finished to obtain the low-array carbon nanotube powder (the specific structural form is shown in figure 3).
Example 4
The array carbon nanotube is prepared by the following method: placing 2g of the catalyst prepared in preparation example 4 in a vertical fluidized bed reactor, introducing argon gas with the flow rate of 2L/min as protective gas, starting a heating furnace, heating to 700 ℃, introducing 1L/min of hydrogen gas for reduction for 60min after the temperature is stable, introducing 3L/min of propylene for reaction for 90min after the reduction is finished, and continuing cooling to room temperature under the protection of 2L/min of nitrogen gas after the reaction is finished to obtain the array carbon nanotube powder.
Example 5
An array carbon nanotube is prepared by the following method: placing 1.0g of the catalyst prepared in preparation example 5 in a horizontal fixed bed reactor, introducing 1L/min of nitrogen protection gas, starting a heating furnace, heating to 700 ℃, introducing 1.0L/min of hydrogen for reduction for 30min after the temperature is stable, introducing 1.0L/min of propylene for reaction for 60min after the reduction is finished, and continuing cooling to room temperature under the protection of 1L/min of nitrogen after the reaction is finished to obtain the array carbon nanotube powder.
Example 6
An array carbon nanotube is prepared by the following method: placing 1.0g of the catalyst prepared in preparation example 6 in a horizontal fixed bed reactor, introducing 1.0L/min nitrogen protection gas, starting a heating furnace, heating to 680 ℃, introducing 1.0L/min hydrogen for reduction for 30min after the temperature is stable, introducing 1.0L/min propylene for reaction for 60min after the reduction is finished, and continuing cooling to room temperature under the protection of 1L/min nitrogen after the reaction is finished to obtain the array carbon nanotube powder.
Comparative example 1 was carried out
An example comparative sample 1 was prepared by the following method: the difference from example 1 is that: the catalyst of example 1 was replaced by an equal amount of the preparation of comparative sample 1 (see figure 5 for specific structural features).
Comparative example 2 was carried out
An example comparative sample 2 was prepared by the following method: the difference from example 3 is that: the catalyst of example 3 was replaced by the same amount as that of comparative sample 2 (see fig. 6 for specific structural morphology).
Comparative example 3 was conducted
An example comparative sample 3 was prepared by the following method: the difference from example 3 is that: the catalyst of example 3 was replaced by an equal amount of preparation comparative sample 3.
Comparative example 4 was carried out
A comparative sample 4 was prepared by the following method: the difference from example 3 is that: the catalyst of example 3 was replaced by an equal amount of preparation comparative sample 4.
Specific surface area, multiplying power and powder resistivity data of the short array carbon nanotubes prepared in the examples and the comparative samples are shown in table 2.
The formula for calculating the multiplying power is as follows:
multiplying factor = (carbon nanotube powder weight-catalyst weight)/catalyst weight
TABLE 2
The graphitization degree of the array carbon nanotube powder prepared in example 3 is measured by raman spectroscopy, and the raman spectrogram in fig. 4 proves that the array carbon nanotube powder prepared in example 3 has high graphitization degree and few defects.
The data of examples 1-6 in table 2 show that the rate of the carbon nanotubes array prepared in examples 1-6 is between 14-31, which proves that the method for preparing carbon nanotubes array in the present application has better yield. The resistivity of the carbon nanotubes of the arrays prepared in examples 1-6 is between 12.32 and 24.96, which shows that the carbon nanotubes of the arrays prepared in examples 1-6 have better conductivity. The specific surface area of the array carbon nano tube prepared by the method is 103-179m 2 The specific surface area of the commercial array carbon nano-tube is mostly 200m between/g 2 The specific surface area of the array carbon nano tube prepared by the method is proved to be obviously lower than that of the array carbon nano tube sold in the market. In combination with fig. 2-3 of the present application, the carbon nanotubes of the arrays prepared in examples 1 and 3 have the advantages of ordered arrangement, good orientation, obvious array morphology and short array length, and to sum up, the method for preparing the carbon nanotubes of the arrays in the present application not only obtains the carbon nanotubes with better conductivity in a higher rate manner, but also has the characteristics of low specific surface area and short array length, and is beneficial to disperse pulping and obtain conductive slurry with high solid content, or has better dispersibility in plastics, thereby improving the dispersion effect of the carbon nanotubes of the arrays when applied.
As can be seen from the data of example 1 and comparative example 1 in table 2, and by comparing fig. 1, fig. 2 and fig. 5, in the catalyst preparation process of example 1, the catalyst having a lamellar structure is obtained by calcining the catalyst precursor solution (see the upper diagram of fig. 1), and the arrayed carbon nanotubes having a distinct array morphology, a low specific surface area and a short array length can be obtained by the catalyst (see fig. 2), and in the catalyst preparation process of comparative example 1, the catalyst precursor solution is dried into powder and then calcined to obtain a powdery catalyst (see the lower diagram of fig. 1), so that the catalyst of comparative example 1 cannot form a catalyst having a lamellar structure as shown in the upper diagram of fig. 1 by self-assembly, and a comparative sample 1 (see fig. 5) having a high specific surface area, a lump and a distinct array morphology is obtained by directly calcining the catalyst precursor solution without drying, which is advantageous for preparing the arrayed carbon nanotubes having high dispersibility.
As can be seen from comparison of data of example 3 and comparative example 2 in table 2 with fig. 3 and fig. 6, adding a complexing agent during the preparation of the catalyst is beneficial to obtaining a catalyst with good morphology and activity, so as to prepare an array carbon nanotube (see fig. 3) with low specific surface area, obvious array morphology and short array length, thereby being beneficial to obtaining an array carbon nanotube with high dispersibility, and in the absence of the complexing agent, obtaining a non-array carbon nanotube (see fig. 6) with an unobvious array morphology.
By comparing the data of the example 3 and the comparative example 3 in the table 2, the active metal element, the carrier element and the complexing agent are matched at a certain concentration to form the catalyst precursor solution, so that the catalyst precursor solution forms a catalyst with a lamellar structure with better activity after being calcined, and the short-array carbon nanotube which can catalyze the carbon source gas to generate a low specific surface area, a high yield and an obvious array morphology is obtained.
As can be seen from comparison of data of example 3 and comparative example 4 in table 2, in the preparation process of the catalyst of comparative example 4, soluble aluminum nitrate is replaced by insoluble diaspore as a support component, and diaspore is dispersed in water in a suspended state, so diaspore as a support component and an active component cannot be combined by self-assembly, and thus the morphology structures of the catalyst of comparative example 4 and the catalyst of example 3 in the present application are significantly different, and thus the carbon nanotubes having an array morphology cannot be prepared by preparing the catalyst of comparative example 4 in comparative example 4.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (12)
1. A catalyst, characterized by: the catalyst is prepared by calcining a catalyst precursor solution, wherein the catalyst precursor solution is prepared by dissolving a soluble active component containing an active metal element, a soluble carrier component containing a carrier element and a soluble complexing agent in water, the concentration of the active metal element is 0.5-3mol/L, the concentration of the carrier element is 0.5-5.0mol/L, and the concentration of the complexing agent is 3.0-7.0mol/L.
2. A catalyst according to claim 1, wherein: the molar ratio of the active metal element to the carrier element is 1: (0.6-3).
3. A catalyst according to claim 1, wherein: the mol ratio of the complexing agent to the sum of the active metal element and the carrier element is 1 (0.5-1.25).
4. A catalyst as claimed in any one of claims 1 to 3, characterised in that: the soluble active component is one or more of soluble manganese salt, iron salt, cobalt salt, nickel salt and molybdate.
5. A catalyst as claimed in any one of claims 1 to 3, wherein: the soluble carrier component is one or a combination of soluble magnesium salt, aluminum salt, calcium salt and aluminosilicate.
6. A catalyst as claimed in any one of claims 1 to 3, wherein: the complexing agent comprises one or more of citric acid, tartaric acid, sorbic acid, ethylene diamine tetraacetic acid, ethylene glycol, polyethylene glycol and glycerol.
7. A method of preparing the catalyst of claim 1, wherein: the method comprises the following steps:
step S1, dissolving an active component containing an active metal element, a carrier component containing a carrier element and a complexing agent in water, and uniformly mixing to obtain a catalyst precursor solution;
and S2, calcining the catalyst precursor solution at the high temperature of 500-900 ℃ for 10min-4h to obtain the catalyst.
8. An arrayed carbon nanotube characterized by: the catalyst of claim 1, wherein the array carbon nanotube has an array length of 10-50 μm and a specific surface area of 100-180m 2 The specific resistance of the powder is 10-25m omega cm.
9. A method for preparing carbon nanotubes in an array according to claim 8, wherein: introducing hydrogen, reducing the catalyst for 0-60min at 650-720 ℃, and introducing carbon source gas for catalytic reaction for 10-90min at 650-720 ℃ to obtain the arrayed carbon nanotube powder.
10. The method of claim 9, wherein the step of preparing the carbon nanotubes comprises: the carbon source gas is any one of methane, ethane, propane, ethylene and propylene.
11. The method for preparing carbon nanotubes in array according to claim 9, wherein: before introducing hydrogen, nitrogen or inert gas is introduced into the catalyst, the temperature is raised to 650-720 ℃, and hydrogen is introduced after the temperature is stable.
12. The method for preparing carbon nanotubes in array according to claim 9, wherein: the input amount of the catalyst is 0.2-2g, and the flow rate of the carbon source gas is 1-3L/min.
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