CN111495380A - Preparation method of carbon nanotube catalyst and carbon nanotube - Google Patents
Preparation method of carbon nanotube catalyst and carbon nanotube Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B01J23/882—Molybdenum and cobalt
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
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Abstract
The invention discloses a preparation method of a carbon nano tube catalyst, which adopts the technical scheme that Mg is contained2+、Al3+、Co2+And the mixed solution of the catalyst auxiliary agent containing metal ions is added with a weak alkali solution, and then the catalyst with the spinel structure is prepared by high-temperature calcination, so that the yield of the carbon nano tube can be improved, and the prepared carbon nano tube has small tube diameter distribution, large specific surface area and good conductivity.
Description
Technical Field
The invention relates to the technical field of carbon nanotube preparation, in particular to a preparation method of a carbon nanotube catalyst and a carbon nanotube prepared by using the catalyst.
Background
The carbon nano tube is a one-dimensional tubular structure, has extremely high length-diameter ratio and excellent conductivity, can effectively form a conductive network by adding the carbon nano tube into an electrode material of the lithium ion battery, improves the conductivity of the electrode, enables the lithium ion battery to have excellent performance, particularly shows large battery capacity and long cycle life, and is suitable for high-end-number batteries and new energy automobile batteries.
At present, the industrial method for preparing the carbon nano tube is mainly a CVD method, and people do much work on a catalyst used for the CVD method. Metals playing a catalytic role in preparing the carbon nano tube are generally found to be iron, cobalt and nickel; the carrier is alumina, magnesia, etc.; the assistant is metal such as molybdenum, lanthanum, tungsten and the like. However, the catalyst structure and the catalytic performance obtained by different preparation processes are greatly different.
Patent CN 1718278 provides a catalyst for carbon nanotube growth and a preparation method thereof. The catalyst consists of metal oxide and spinel composite oxide; the preparation sequence is that metal ions are precipitated by mixed alkali liquor prepared by sodium hydroxide and inorganic sodium salt to prepare a hydrotalcite structure catalyst precursor, and then the catalyst is obtained by calcining. The concentration of metal ions in the process of precipitation is 0.4-1.2M, the diameter of a carbon rice tube grown by the catalyst is 20-40nm, the number of layers is more than 18, the conductivity is poor, and the yield is not more than 300%.
Patent CN107252682 provides a method for preparing carbon nanotube catalyst, which comprises preparing a mixture with a precipitant or a complexing agent or a dispersant, spray drying, and calcining to obtain the carbon nanotube catalyst. But the processes of filtering, washing and the like are not carried out, and the direct spray drying inevitably leaves impurity elements in the catalyst. Such as chloride or nitrate in the catalyst salt, sodium in the precipitant, etc., easily deactivate the catalyst. And the catalyst metal in the catalyst prepared by the method exists in the form of oxide.
Patent JP2016140781 also provides a catalyst for the preparation of a multi-wall tube and a preparation method. The catalyst consists of cobalt or iron and at least four elements of nickel, magnesium, aluminum and molybdenum. Firstly, adding salt containing catalyst into water, then adding organic acid, mixing, drying and calcining. However, the patent mentions that the calcination temperature of this method cannot exceed 650 ℃, otherwise the catalyst is easily deactivated by sintering. This necessarily results in a poor catalyst efficiency since the growth temperature range for carbon nanotubes is typically 670-1200 degrees.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a carbon nanotube catalyst, which has the advantages of high activity and improvement of the yield of carbon nanotubes.
The prepared carbon nano tube has the characteristics of small tube diameter distribution, large specific surface area and good conductivity.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of a carbon nanotube catalyst comprises the following steps:
a: preparing a salt solution: configured to contain Mg2+、Al3+、Co2+And a mixed solution of a catalyst promoter containing metal ions, wherein the molar ratio of Mg to Co to Al to the metal ions in the catalyst promoter is not= (1-3) to 1 (1-1.5) to (0.02-0.6), and the total molar concentration of the metal ions in the salt solution is 1.0-3.0 mol/L.
B, preparing a weak base solution, namely preparing the weak base solution by using a weak base salt, wherein the total molar concentration of cations is 0.05-0.3 mol/L.
C: heating the salt solution, keeping the temperature of the salt solution at 40-100 ℃, slowly adding the weak base solution into the salt solution in a dropwise manner, controlling the dropwise adding time within 2-10 h, then preserving the temperature for 2-24h, filtering, washing, drying, and calcining at the temperature of 700-900 ℃ to obtain the catalyst;
the step a and the step B do not limit the sequence, that is, the step a and the step B may be configured separately or simultaneously.
The invention reduces the reaction speed by adding weak base, and ensures that the catalyst with spinel structure can be obtained under the condition of low-temperature calcination later.
Wherein the catalyst promoter is a compound containing at least one of Mo, Y and Mn and capable of ionizing metal ions.
Wherein the catalyst promoter is at least one of yttrium nitrate hexahydrate, ammonium molybdate and manganese nitrate.
Wherein, the weak alkali salt is a buffer solution prepared by carbonate and bicarbonate.
Wherein the weak base salt is at least one of ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, and the total molar concentration of cations in the weak base solution is 0.5-1.5 mol/L.
Wherein at least one of urea and hexamethylene tetramine is added as a precipitator in the salt solution in the step A, wherein the molar ratio of the total molar number of the urea or the hexamethylene tetramine or the urea and the hexamethylene tetramine to the molar number of the catalyst metal ions is (2-4): 1.
The uniform decomposition of urea and hexamethylene tetramine in the solution is used for providing hydroxide radicals, or the buffer solution prepared from carbonate and bicarbonate is used for reducing the reaction speed, so that the spinel structure catalyst with a large crystal form can be obtained under the condition of low-temperature calcination later.
Wherein, the salt solution is heated after the precipitant is added, the temperature of the salt solution is kept between 80 and 100 ℃, and the temperature is kept for 6 hours.
Wherein, Mg in the step A2+、Al3+、Co2+Is a nitrate compound.
Wherein, the temperature in the step C is increased to the calcining temperature at the speed of 10-15 ℃/min, and then the temperature is kept for 0.8-1.2 h.
And C, dropwise adding an alkali solution until the pH value of the solution system is 9-9.5.
The catalyst of the invention is prepared by preparing a precursor of multi-element metal hydrotalcite containing active components and then calcining. The catalyst has a multi-element composite structure and comprises a metal oxide and a spinel structure. Specifically brucite, cobalt oxide, molybdenum oxide and/or yttrium oxide and/or manganese oxide, magnesium aluminate and cobalt aluminate. The yield of the carbon nano tube grown by the catalyst reaches 1200-4000 percent, the tube diameter of the carbon nano tube is distributed between 3-14nm, and the specific surface area of the carbon nano tube is 270-450m2Has excellent conductive performance.
CoO and Co are contained in the catalyst2O3、Co3O4And CoAl2O4The four forms exist, and the carrier comprises brucite and magnesium aluminate. The carrier element aluminum is present as a spinel structure in the catalyst. Wherein Mo exists in three forms, MoO and MoO2And MoO3. Y is present in the form of Y2O3. Mn is present in the form of MnO and MnO2。
The carbon nano tube is prepared by the catalyst preparation method.
The specific method comprises the steps of putting a catalyst into a fluidized bed, introducing nitrogen, keeping the temperature of the furnace at 670-: the flow rate of propylene is not less than 0.8-1.2 and not more than 0.8-1.2, and the carbon nano tube can be collected when the temperature is reduced to the room temperature after the reaction is carried out for 30 min; wherein the specific surface area of the prepared carbon nano tube is in the range of 270-450m2The pipe diameter is distributed between 2 and 14 nm.
Preferably, the catalyst is put into a quartz blind tube furnace fluidized bed with the diameter of 60mm, nitrogen is introduced, and the flow rate is 1000 ml/min; the temperature of the furnace is raised to 700 ℃ at the speed of 10 ℃/min, then ethylene is introduced, the flow rate is 1000ml/min, and the carbon nano tube can be collected when the temperature is reduced to the room temperature after the reaction is carried out for 30 min; wherein the specific surface area of the prepared carbon nano tube is in the range of 270-450m2The pipe diameter is distributed between 2 and 14 nm. In summary, compared with the prior art, the beneficial effects of the invention are as follows: the catalyst containing the auxiliary agent prepared by adopting a weak base precipitation method or a weak base uniform precipitation method firstly and then a weak base precipitation method has high activity, the yield can reach 1200-5000 percent, the pipe diameter of the carbon nano tube is distributed between 2nm and 14nm, the specific surface area of the carbon nano tube reaches 270-450 m-2Has excellent conductivity per gram.
Drawings
FIG. 1 is an XRD pattern of a catalyst of the present invention;
FIG. 2 is a tube diameter distribution diagram of 100 carbon nanotubes prepared using the catalyst prepared in example 1;
FIG. 3 is a wall distribution diagram of 100 carbon nanotubes prepared using the catalyst prepared in example 1;
FIG. 4 is a tube diameter distribution diagram of 100 carbon nanotubes prepared using the catalyst prepared in example 3;
FIG. 5 is a wall distribution diagram of 100 carbon nanotubes prepared using the catalyst prepared in example 3.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
Step A, preparing a salt solution, namely weighing 9.60 g of cobalt nitrate hexahydrate, 25.38 g of magnesium nitrate hexahydrate, 24.76 g of aluminum nitrate nonahydrate and 1.26 g of yttrium nitrate hexahydrate, and adding the materials into 400 g of pure water, wherein the concentration of metal ions is 0.5 mol/L, and the molar ratio of metal elements is Mg, Co, Al and Y =3:1:2: 0.1.
And B: 20.73 g of potassium carbonate and 42 g of sodium bicarbonate were weighed and dissolved in 600 g of water to prepare a weak base solution.
And C: slowly dripping a weak base solution into the salt solution at the temperature of 100 ℃, finishing dripping for 10 hours until the final pH value is 9.5, continuously preserving the temperature at 95 ℃ for 10 hours, then carrying out suction filtration and washing until the pH value of a washing liquid is less than 8, and preparing the catalyst precursor. Drying the prepared catalyst precursor at 200 ℃, putting the dried catalyst precursor into a high-temperature furnace, raising the temperature to 900 ℃ at the speed of 15 ℃/min, and then preserving the temperature for 1 hour to obtain the catalyst, wherein the catalyst is in a spinel structure, and is shown in figure 1.
Example 2
Step A, preparing a salt solution, namely weighing 9.60 g of cobalt nitrate hexahydrate, 21.15 g of magnesium nitrate hexahydrate, 18.56 g of aluminum nitrate nonahydrate and 0.30 g of ammonium molybdate, and adding the materials into 600 g of pure water, wherein the concentration of metal ions is 0.33 mol/L, and the molar ratio of metal elements is Mg, Co, Al and Mo =2.5: 1.5: 0.05.
And B: 70.12 g of potassium bicarbonate and 18.02 g of potassium carbonate were weighed and dissolved in 400 g of water to prepare a weak base solution.
And C: slowly dripping a weak base solution into the salt solution at 65 ℃, finishing dripping for 10h until the pH value is 9.5, continuously preserving the temperature at 65 ℃ for 10h, carrying out suction filtration and washing until the pH value of washing liquor is less than 8, and preparing the catalyst precursor. And (3) drying the prepared catalyst precursor at 200 ℃, putting the dried catalyst precursor into a high-temperature furnace, raising the temperature to 700 ℃ at the speed of 15 ℃/min, and then preserving the temperature for 1 hour to obtain the catalyst.
Example 3
Step A, preparing a salt solution, namely weighing 9.60 g of cobalt nitrate hexahydrate, 16.92 g of magnesium nitrate hexahydrate, 12.37 g of aluminum nitrate nonahydrate, 0.117 g of ammonium molybdate and 0.63 g of yttrium nitrate hexahydrate, and adding the weighed materials into 150 g of pure water, wherein the concentration of metal ions is 0.90 mol/L, and the molar ratio of metal elements is Mg, Co, Al, Mo, Y =2, 1, 0.02, 0.05.
And B: 7.81 g of ammonium bicarbonate and 8.93 g of ammonium carbonate were weighed out and dissolved in 400 g of water to prepare a weak base solution.
And C: slowly dripping a weak base solution into the salt solution at the temperature of 60 ℃, finishing dripping within 10h, keeping the pH value at 9.0, keeping the temperature at 60 ℃ for 3h, carrying out suction filtration and washing until the pH value of washing liquor is less than 8, and preparing the catalyst precursor. And (3) drying the prepared catalyst precursor at 200 ℃, putting the dried catalyst precursor into a high-temperature furnace, raising the temperature to 750 ℃ at the speed of 15 ℃/min, and then preserving the temperature for 1 hour to obtain the catalyst.
Example 4
Step A, preparing a salt solution, namely weighing 9.60 g of cobalt nitrate hexahydrate, 16.92 g of magnesium nitrate hexahydrate, 18.56 g of aluminum nitrate nonahydrate and 0.24 g of yttrium nitrate, and adding the materials into 1200 g of pure water, wherein the concentration of metal ions is 0.13 mol/L, and the molar ratio of metal elements is Mg, Co, Al, Y =2, 1, 1.5 and 0.04.
And B: 11.66 g of sodium carbonate and 37.04 g of potassium bicarbonate are weighed and dissolved in 400 g of water to prepare a weak base solution.
And C: slowly dripping a weak base solution into the salt solution at 70 ℃, finishing dripping within 5h, keeping the pH value at 70 ℃ for 10h, carrying out suction filtration and washing until the pH value of washing liquor is less than 8, and preparing the catalyst precursor. And (3) drying the prepared catalyst precursor at 200 ℃, putting the dried catalyst precursor into a high-temperature furnace, raising the temperature to 800 ℃ at the speed of 15 ℃/min, and then preserving the temperature for 1 hour to obtain the catalyst.
Example 5
Step A, preparing a salt solution, namely weighing 9.60 g of cobalt nitrate hexahydrate, 13.54 g of magnesium nitrate hexahydrate, 17.33 g of aluminum nitrate nonahydrate, 0.24 g of yttrium nitrate and 0.117 g of ammonium molybdate, and adding the weighed materials into 1300 g of pure water, wherein the concentration of metal ions is 0.1 mol/L, and the molar ratio of metal elements Mg to Co to Al to Y to Mo =1.6 to 1.4 to 0.04 to 0.02.
And B: 40.90 g of potassium bicarbonate and 8.68 g of sodium carbonate are weighed and dissolved in 400 g of water to prepare a weak base solution.
And C: slowly dripping a weak base solution into the salt solution at 85 ℃, finishing dripping for 6 hours until the pH value is 9.5, continuously preserving the temperature at 85 ℃ for 10 hours, carrying out suction filtration and washing until the pH value of washing liquor is less than 8, and preparing the catalyst precursor. And (3) drying the prepared catalyst precursor at 200 ℃, putting the dried catalyst precursor into a high-temperature furnace, raising the temperature to 720 ℃ at the speed of 15 ℃/min, and then preserving the temperature for 1 hour to obtain the catalyst.
Example 6
Step A, preparing a salt solution, namely weighing 9.60 g of cobalt nitrate hexahydrate, 16.92 g of magnesium nitrate hexahydrate, 12.37 g of aluminum nitrate nonahydrate and 0.59 g of manganese nitrate, adding the weighed materials into 550 g of pure water, wherein the metal ion concentration is 0.25 mol/L, the molar ratio of metal elements is Mg: Co: Al: Mn =2:1:1: 0.1, weighing 4.52 g of urea and 11.07 g of hexamethylenetetramine, dissolving the weighed materials in the prepared solution, heating the solution to 85 ℃, and preserving the heat for 5 hours.
And B: 5.18 g of sodium carbonate and 16.46 g of potassium bicarbonate are weighed and dissolved in 200 g of water to prepare a weak base solution.
And C: and (3) dropwise adding the weak base solution into the solution obtained in the step (A), after dropwise adding for 5 hours, keeping the pH value at 9.0, keeping the temperature at 85 ℃ for 3 hours, carrying out suction filtration and washing until the pH value of washing liquor is less than 8, and preparing the catalyst precursor. And (3) drying the prepared catalyst precursor at 200 ℃, putting the dried catalyst precursor into a high-temperature furnace, raising the temperature to 900 ℃ at the speed of 15 ℃/min, and then preserving the temperature for 6 hours to obtain the catalyst.
Example 7
Step A, preparing a salt solution, namely weighing 9.60 g of cobalt nitrate hexahydrate, 16.92 g of magnesium nitrate hexahydrate, 12.37 g of aluminum nitrate nonahydrate and 0.59 g of manganese nitrate, adding the weighed materials into 550 g of pure water, wherein the metal ion concentration is 0.25 mol/L, the molar ratio of metal elements is Mg: Co: Al: Mn =2:1:1: 0.1, weighing 4.52 g of urea and 11.07 g of hexamethylenetetramine, dissolving the materials in the prepared solution, heating the solution to 85 ℃, and preserving the heat for 5 hours.
And B: 12.44 g of sodium carbonate are weighed out and dissolved in 200 g of water, and an alkaline solution is prepared.
And C: and (3) dropwise adding an alkali solution into the solution obtained in the step (A), after dropwise adding is completed within 5h, keeping the pH value at the final value of 9.0, keeping the temperature at 85 ℃ for 3h, carrying out suction filtration and washing until the pH value of a washing liquid is less than 8, and preparing the catalyst precursor. And (3) putting the prepared catalyst precursor into a high-temperature furnace, raising the temperature to 900 ℃ at the speed of 15 ℃/min, and then preserving the temperature for 6 hours to obtain the catalyst.
Comparative example 1:
9.60 g of cobalt nitrate hexahydrate, 16.92 g of magnesium nitrate hexahydrate, 12.37 g of aluminum nitrate nonahydrate and 0.117 g of ammonium molybdate were weighed and added into 600 g of pure water, wherein the metal ion concentration is 0.22 mol/L, the molar ratio of metal elements is Mg: Co: Al: Mo =2:1:1:0.02, 80.30 g of potassium bicarbonate was weighed and dissolved in 400 g of water to prepare an alkali solution.
Slowly dripping the alkali solution into the salt solution at the temperature of 60 ℃, finishing dripping for 10 hours until the final pH value is 9.0, and directly spray-drying to obtain the catalyst precursor.
The catalyst precursor prepared above was placed in a high temperature furnace, raised to 750 ℃ at a rate of 15 ℃/min, and then held for 1 hour to obtain comparative catalyst 1.
Comparative example 2:
9.60 g of cobalt nitrate hexahydrate, 21.15 g of magnesium nitrate hexahydrate, 18.56 g of aluminum nitrate nonahydrate and 0.30 g of ammonium molybdate are weighed and added into 600 g of pure water, wherein the concentration of metal ions is 0.33 mol/L, the molar ratio of metal elements is Mg: Co: Al: Mo =2.5:1:1.5:0.05, 13 g of sodium hydroxide is weighed and dissolved into 400 g of water to prepare an alkali solution.
Slowly dripping the alkali solution into the salt solution at 65 ℃, finishing dripping for 10 hours until the pH value is 9.5, continuously preserving the temperature at 65 ℃ for 10 hours, and then performing suction filtration and washing until the pH value of the washing liquid is less than 8.
The catalyst precursor prepared above was placed in a high temperature furnace, raised to 700 ℃ at a rate of 15 ℃/min, and then held for 1 hour to obtain comparative catalyst 2.
Preparation of carbon nanotubes by catalyst
Taking 1.5 g of each of the catalysts prepared in examples 1, 2, 3, 4, 5, 6 and 7 and comparative examples 1 and 2, putting the catalyst into a quartz blind tube furnace fluidized bed with the diameter of 60mm, and introducing nitrogen at the flow rate of 1000 ml/min; the furnace is heated to 700 ℃ at the speed of 10 ℃/min, then ethylene is introduced, the flow rate is 1000ml/min, the carbon nano tube growth is carried out, and the temperature is reduced to the room temperature after the reaction is carried out for 30 min.
And collecting the product, weighing, and testing the pipe diameter and the layer number of the pipe wall of the carbon nano tube. And each carbon nanotube is prepared into carbon nanotube slurry, the slurry contains 98.5 percent of NCM, 0.4 percent of CNT, 0.1 percent of dispersant and 1 percent of PVDF, and the solid content of the slurry is 74 percent, so that the carbon nanotube slurry is used for slurry mixing, coating (PET film) and testing the bulk resistivity of the coated ternary material NCM 523 of the lithium battery. TEM analysis is carried out on the prepared carbon nano-tubes, and Gatan Digital Micrograph software is used for testing the tube diameters of 100 carbon nano-tubes and the tube wall thickness of the carbon nano-tubes, wherein the tube diameters refer to the outer diameters of the carbon nano-tubes. The data obtained are shown in table one below.
From the table one, it can be seen that the catalyst prepared according to the method for preparing the catalyst provided in chinese patent No. CN107252682 in comparative example 1 has lower yield, thicker tube diameter and poor electrical conductivity.
Carbon nanotubes of the present invention prepared by the same method as the catalysts prepared in examples 1 and 3 are shown in FIGS. 2 to 5.
The productivity of the catalyst prepared according to the preparation method in the example of the Chinese patent CN 1718278 is not more than 300%, while the productivity of the catalyst prepared in the example of the Japanese patent JP2016140781 is similar to that of the present invention, but the reaction time is as long as 4-8h, while the reaction time of the catalyst of the present invention is only 0.5 h.
The above description is intended to be illustrative of the present invention and not to limit the scope of the invention, which is defined by the claims appended hereto.
Claims (10)
1. A preparation method of a carbon nano tube catalyst is characterized by comprising the following steps: the method comprises the following steps:
a: preparing a salt solution: configured to contain Mg2+、Al3+、Co2+And a mixed solution of a catalyst promoter containing metal ions, wherein the molar ratio of Mg to Co to Al to the metal ions in the catalyst promoter is = (1-3) to 1 (1-1.5) to (0.02-0.6), and the total molar concentration of the metal ions is 1.0-3.0 mol/L;
preparing weak base solution by using weak base salt, wherein the total molar concentration of cations is 0.05-0.3 mol/L;
c: heating the salt solution, keeping the temperature of the salt solution at 40-100 ℃, slowly adding the weak base solution into the salt solution in a dropwise manner, controlling the dropwise adding time within 2-10 h, then preserving the temperature for 2-24h, filtering, washing, drying, and calcining at the temperature of 700-900 ℃ to obtain the catalyst;
the step A and the step B do not limit the sequence.
2. The method for preparing a carbon nanotube catalyst according to claim 1, wherein: the catalyst promoter is a compound containing at least one of Mo, Y and Mn and capable of ionizing metal ions.
3. The method of claim 1, further comprising: the catalyst auxiliary agent is at least one of yttrium nitrate hexahydrate, ammonium molybdate and manganese nitrate.
4. The method of claim 1, wherein the weak base salt is at least one of ammonium carbonate, ammonium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate, and the total molar concentration of cations in the weak base solution is 0.5-1.5 mol/L.
5. The method for preparing a carbon nanotube catalyst according to claim 1, wherein: and adding at least one of precipitator urea and hexamethylene tetramine into the prepared salt solution in the step A, wherein the molar ratio of the total molar number of the urea or the hexamethylene tetramine or the urea and the hexamethylene tetramine to the molar number of the catalyst metal ions is (2-4) to 1.
6. The method for preparing a carbon nanotube catalyst according to claim 5, wherein: after the precipitant is added, the salt solution is heated, the temperature of the salt solution is kept between 80 and 100 ℃, and the temperature is kept for 6 hours.
7. The method for preparing a carbon nanotube catalyst according to claim 1, wherein: mg in said step A2 +、Al3+、Co2+Is a nitrate compound.
8. The method for preparing a carbon nanotube catalyst according to claim 1, wherein: and C, raising the temperature in the step C to the calcining temperature at the speed of 10-15 ℃/min, and then preserving the temperature for 0.8-1.2 h.
9. The method for preparing a carbon nanotube catalyst according to claim 1, wherein: and C, dropwise adding a weak base solution until the pH value of the solution system is 9-9.5, and stopping.
10. A carbon nanotube, characterized by: the catalyst prepared by the method of any one of claims 1 to 9, wherein the method comprises the steps of placing the catalyst into a fluidized bed, introducing nitrogen, maintaining the temperature of the furnace at 670 ℃ and 850 ℃, and introducing one or more of ethylene, propylene, propane, butane, methane, ethanol, propanol, isopropanol and methanol at a flow rate of nitrogen: the flow rate of propylene is not less than 0.8-1.2 and not more than 0.8-1.2, and the carbon nano tube can be collected when the temperature is reduced to the room temperature after the reaction is carried out for 30 min; wherein the specific surface area of the prepared carbon nano tube is in the range of 270-450m2The pipe diameter is distributed between 2 and 14 nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114618544A (en) * | 2022-03-17 | 2022-06-14 | 无锡东恒新能源科技有限公司 | Synthetic method of lamellar structure catalyst |
| CN114950399A (en) * | 2022-05-16 | 2022-08-30 | 湖北冠毓新材料科技有限公司 | Method for manufacturing carbon nano tube catalyst carrier |
| CN115501879A (en) * | 2022-10-14 | 2022-12-23 | 湖北冠毓新材料科技有限公司 | Production method of high-conductivity carbon nanotube catalyst |
| CN115806287A (en) * | 2021-09-15 | 2023-03-17 | 江苏天奈科技股份有限公司 | Array carbon nanotube and method for preparing array carbon nanotube and lamellar catalyst |
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| CN115806287A (en) * | 2021-09-15 | 2023-03-17 | 江苏天奈科技股份有限公司 | Array carbon nanotube and method for preparing array carbon nanotube and lamellar catalyst |
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| CN114618544B (en) * | 2022-03-17 | 2023-10-03 | 无锡东恒新能源科技有限公司 | Method for synthesizing catalyst with lamellar structure |
| CN114950399A (en) * | 2022-05-16 | 2022-08-30 | 湖北冠毓新材料科技有限公司 | Method for manufacturing carbon nano tube catalyst carrier |
| CN115501879A (en) * | 2022-10-14 | 2022-12-23 | 湖北冠毓新材料科技有限公司 | Production method of high-conductivity carbon nanotube catalyst |
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