CN114195125A - Preparation method and catalyst of catalyst for preparing nano-carbon material - Google Patents
Preparation method and catalyst of catalyst for preparing nano-carbon material Download PDFInfo
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Abstract
本发明提供一种用于制取纳米碳材料的催化剂的制备方法及催化剂，用于制取纳米碳材料的催化剂的制备方法，包括：将碳黑和金属的前驱体混合后，按预设方法使金属担载于碳黑上，并获得粉末状产物；将粉末状产物在还原性气体环境和第一预设温度的条件下进行还原处理，并在还原处理后得到催化剂。本发明提供的用于制取纳米碳材料的催化剂的制备方法及催化剂，采用碳黑作为载体并对金属进行担载，使最终获得的催化剂能够应用于微波处理制取纳米碳材料，该催化剂具有良好的吸波性能，在微波作用下催化剂温度不低于200℃，且具有优良的催化性能，制备工艺简单、低成本。
The invention provides a preparation method and a catalyst for preparing a catalyst for preparing nano-carbon materials, and the preparation method for preparing a catalyst for preparing nano-carbon materials, comprising: after mixing carbon black and a metal precursor, according to a preset method The metal is supported on the carbon black to obtain a powdery product; the powdery product is subjected to reduction treatment under the conditions of a reducing gas environment and a first preset temperature, and a catalyst is obtained after the reduction treatment. The preparation method and catalyst for preparing a catalyst for preparing nano-carbon materials provided by the present invention use carbon black as a carrier and support metals, so that the finally obtained catalyst can be applied to microwave treatment to prepare nano-carbon materials, and the catalyst has It has good wave-absorbing performance, the catalyst temperature is not lower than 200 DEG C under the action of microwave, and has excellent catalytic performance, and the preparation process is simple and low-cost.
Description
Technical Field
The invention relates to the technical field of carbon material preparation, in particular to a preparation method of a catalyst for preparing a nano carbon material and the catalyst.
Background
The nano carbon material mainly comprises graphene, a carbon nano tube, nano graphite, carbon fiber, fullerene and the like, wherein the carbon nano tube has a unique topological structure, excellent electric conduction, heat conduction and corrosion resistance, stable chemical property, strong thermal stability and good adsorption property, so that the carbon nano tube is an ideal electrode material, composite material, light guide material, magnetic material and the like, and can be widely applied to the fields of aerospace, electric vehicles, intelligent manufacturing and the like. At present, the preparation method of the nano carbon material is mainly a chemical vapor deposition method, wherein the used catalyst is generally a supported catalyst, including silica gel, molecular sieve, alumina and the like, and a metal compound or a composite oxide is also directly used as the catalyst.
However, unlike the conventional vapor deposition method, the microwave catalytic reaction requires a catalyst having good wave-absorbing ability and good catalytic ability. The catalyst used in the traditional vapor deposition method cannot meet the requirement of microwave catalysis.
Disclosure of Invention
In order to avoid the defects of the prior art, the invention designs a preparation method of a catalyst for preparing a nano carbon material, which can be used for preparing the catalyst of a nano carbon material and carbon black composite material by microwave catalysis, and the catalyst, so as to solve the problem that the catalyst in the prior art can not be applied to preparing the nano carbon material by microwave.
In order to achieve the above object, the present invention provides a method for preparing a catalyst for preparing a nanocarbon material, comprising:
mixing carbon black and a metal precursor, and loading metal on the carbon black according to a preset method to obtain a powdery product;
and reducing the powdery product in a reducing gas environment at a first preset temperature, and obtaining the catalyst after the reduction treatment.
As an example, after the mixing of the carbon black and the precursor of the metal, the metal is supported on the carbon black according to a preset method, and a powdery product is obtained, further comprising:
mixing carbon black and a metal precursor in distilled water to form a suspension;
stirring the suspension, drying, and grinding the dried product;
and calcining the ground product for a first preset time under the conditions of inert gas environment and a second preset temperature to obtain a powdery product.
As an embodiment, the calcining the ground product under the inert gas environment and the second preset temperature for the first preset time to obtain a powdered product, further includes:
the numerical range of the second preset temperature is 340 ℃ to 450 ℃;
and/or the first preset time has a value ranging from 1 hour to 8 hours.
As an example, after the mixing of the carbon black and the precursor of the metal, the metal is supported on the carbon black according to a preset method, and a powdery product is obtained, further comprising:
mixing carbon black and a metal precursor in distilled water to form a suspension;
and dripping the suspension into an alkaline solution, drying the precipitate, and grinding to obtain a powdery product.
As an example, in the dropping of the suspension into an alkaline solution, and then drying and grinding the precipitate to obtain a powdery product, the method further comprises:
and dissolving sodium hydroxide and sodium carbonate in distilled water according to a second preset proportion to prepare an alkaline solution.
As an example, the second predetermined ratio includes a molar ratio, and the ratio of the molar ratio ranges from 1:1 to 5: 1.
As an example, in the dropping of the suspension into an alkaline solution, and then drying and grinding the precipitate to obtain a powdery product, the method further comprises:
the temperature of the alkaline solution ranges from 40 ℃ to 100 ℃.
As an example, in the dropping of the suspension into an alkaline solution, and then drying and grinding the precipitate to obtain a powdery product, the method further comprises:
the precipitate was washed with distilled water at least three times and then dried.
As an example, after the mixing of the carbon black and the precursor of the metal, the metal is supported on the carbon black according to a preset method, and a powdery product is obtained, further comprising:
adding citric acid and distilled water into the mixed carbon black and metal precursor, and grinding to form viscous slurry;
and roasting the viscous slurry under the conditions of inert gas environment and third preset temperature to obtain a powdery product after roasting.
As an example, in the step of adding citric acid and distilled water to the mixed precursor of carbon black and metal and grinding to form viscous slurry, the method further comprises:
the ratio of the mass of the citric acid to the mass of the mixed carbon black and the metal precursor ranges from 0.1:1 to 0.5: 1.
As an embodiment, in the calcining the viscous slurry under the conditions of inert gas environment and third preset temperature, and obtaining a powdery product after calcining, the method further comprises:
the numerical range of the third preset temperature is 350 ℃ to 450 ℃;
and/or the duration of calcination ranges from 1 hour to 6 hours.
As an embodiment, in the reducing treatment of the powdered product under the conditions of reducing gas and first preset temperature, and obtaining the catalyst after the reducing treatment, the method further comprises:
the gas in the reducing gas environment comprises argon-hydrogen mixed gas.
As an example, the volume fraction of the hydrogen in the argon-hydrogen mixture gas ranges from 4% to 8%.
As an embodiment, in the reducing treatment of the powdered product under the conditions of reducing gas and first preset temperature, and obtaining the catalyst after the reducing treatment, the method further comprises:
the gas in the reducing gas environment comprises hydrogen;
and/or the first preset temperature has a value ranging from 550 ℃ to 850 ℃.
As an embodiment, in the reducing treatment of the powdered product under the conditions of the inert gas environment and the first preset temperature, and obtaining the catalyst after the reducing treatment, the method further comprises:
the duration of the reduction treatment ranges from 3 hours to 9 hours.
As an embodiment, the gas in the inert gas environment includes one or more of nitrogen, hydrogen, argon, and the like.
As an example, the carbon black includes one or more of acetylene black, SP conductive agent, or ketjen black.
As an example, the metal includes at least one or more of lithium, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, tungsten, gold, silver, platinum, ruthenium, and palladium.
As an embodiment, the precursor includes one or more of nitrate, chlorate and organic metal compound.
The catalyst is obtained by applying the preparation method of the catalyst for preparing the nano carbon material.
As an example, the ratio of the mass ratio of carbon black to metal in the catalyst ranges from 0.1:1 to 3: 1.
The preparation method of the catalyst for preparing the nano carbon material and the catalyst provided by the invention adopt the carbon black as a carrier and carry metals, so that the finally obtained catalyst can be applied to microwave treatment to prepare the nano carbon material, has good wave absorbing performance, has the catalyst temperature of not less than 200 ℃ under the action of microwaves, and has excellent catalytic performance, simple preparation process and low cost.
Drawings
The drawings herein illustrate embodiments consistent with the present invention and, together with the description, serve to explain the present disclosure. Other figures may also be derived from these figures to those of ordinary skill in the art.
FIG. 1 is a temperature rise curve of a catalyst prepared in the first example of the present invention under the action of microwaves.
Fig. 2 is a projection electron microscope image of the carbon nanotube prepared in the first embodiment of the present invention.
FIG. 3 is a temperature rise curve of the catalyst prepared in example two of the present invention under the action of microwaves.
Fig. 4 is a transmission electron microscope image of the carbon nanotube prepared in the second embodiment of the present invention.
FIG. 5 is a temperature rise curve of the catalyst prepared in the third example of the present invention under the action of microwaves.
Fig. 6 is a transmission electron microscope image of the carbon nanotube prepared in the third embodiment of the present invention.
FIG. 7 is a temperature rise curve of the carbon black catalyst under the action of microwaves in comparative example one of the present invention.
FIG. 8 is a temperature rise curve of the iron metal catalyst prepared in comparative example II of the present invention under the action of microwaves.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The inventor researches to find that the existing catalyst for preparing the nano carbon material can not be applied to microwave treatment, and the microwave catalysis is increasingly applied to material preparation, therefore, the invention provides a preparation method of the catalyst for preparing the nano carbon material, which comprises the steps of mixing carbon black and a precursor of metal, then loading the metal on the carbon black according to a preset method, and obtaining a powdery product; and reducing the powdery product in a reducing gas environment at a first preset temperature, and obtaining the catalyst after the reduction treatment.
The catalyst which can be applied to microwave treatment is obtained by taking the carbon black as a carrier, loading metal on the carbon black by a preset method and carrying out reduction treatment on the obtained powdery product, so that the problem that the catalyst in the prior art cannot be applied to microwave treatment is solved, the catalyst obtained by applying the preparation method has good wave-absorbing performance, the temperature of the catalyst is not lower than 200 ℃ under the action of microwaves, the catalyst has excellent catalytic performance, and the preparation process is simple and low in cost.
Preferably, the ratio of the precursor of the metal to the carbon black is in the range of 0.1:1 to 9:1 by mass.
Wherein the particle size of the metal precursor is less than 50 μm.
As an example, the method for treating carbon black and a precursor of a metal by an impregnation method, specifically, after mixing the carbon black and the precursor of a metal, loading the metal on the carbon black according to a preset method, and obtaining a powdery product, further comprises: mixing carbon black and a metal precursor in distilled water to form a suspension; stirring the suspension, drying, and grinding the dried product; and calcining the ground product for a first preset time under the conditions of inert gas environment and a second preset temperature to obtain a powdery product.
Wherein, when the suspension is dried, an oven is adopted for drying.
Specifically, the calcining the ground product under the inert gas environment and the second preset temperature for the first preset time to obtain a powdered product, further comprises: the second predetermined temperature has a value in the range of 340 ℃ to 450 ℃, preferably 340 ℃ to 370 ℃, in particular 350 ℃ or 360 ℃.
In particular, the first predetermined time has a value ranging from 1 hour to 8 hours, preferably 3 hours or 6 hours.
As an embodiment, the method for treating carbon black and a metal precursor by using a coprecipitation method, specifically, after mixing the carbon black and the metal precursor, loading the metal on the carbon black according to a preset method, and obtaining a powdery product, further includes: mixing carbon black and a metal precursor in distilled water to form a suspension; and dripping the suspension into an alkaline solution, drying the precipitate, and grinding to obtain a powdery product.
Wherein, according to the state of the precipitate, the precipitate is optionally filtered, washed, dried, crushed and ground.
Specifically, the method comprises the steps of dropping the suspension into an alkaline solution, drying the precipitate, and grinding to obtain a powdery product, and further comprises the following steps: and dissolving sodium hydroxide and sodium carbonate in distilled water according to a second preset proportion to prepare an alkaline solution.
Specifically, the second preset ratio comprises a molar ratio, and the ratio of the molar ratio ranges from 1:1 to 5: 1. Preferably 3: 1. That is, sodium hydroxide and sodium carbonate were dissolved in 100ml of distilled water in a 3:1 mixture.
Specifically, the method comprises the steps of dropping the suspension into an alkaline solution, drying the precipitate, and grinding to obtain a powdery product, and further comprises the following steps: the temperature of the alkaline solution is in the range of 40 ℃ to 100 ℃, preferably 70 ℃.
Optionally, the dropping the suspension into an alkaline solution, drying the precipitate, and grinding to obtain a powdered product, further includes: the precipitate was washed with distilled water at least three times and then dried.
As an example, the method for treating carbon black and a metal precursor by a combustion method, specifically, after mixing the carbon black and the metal precursor, loading the metal on the carbon black according to a preset method, and obtaining a powdery product, further comprises: adding citric acid and distilled water into the mixed carbon black and metal precursor, and grinding to form viscous slurry; and roasting the viscous slurry under the conditions of inert gas environment and third preset temperature to obtain a powdery product after roasting.
When citric acid and distilled water are added, the carbon black and the precursor of the metal are fully mixed in a small amount of distilled water, and then the citric acid is added to fully mix and grind to form viscous slurry.
Specifically, the method for preparing the carbon black slurry comprises the following steps of adding citric acid and distilled water into the mixed carbon black and metal precursor, and grinding to form viscous slurry, and further comprises the following steps: the ratio of the mass of the citric acid to the mass of the mixed carbon black and the precursor of the metal is in the range of 0.1:1 to 0.5:1, preferably 0.3: 1.
In particular, in the step of calcining the viscous slurry under the inert gas environment and at the third preset temperature to obtain a powdery product after calcination, the method further comprises: the third predetermined temperature has a value ranging from 350 ℃ to 450 ℃, preferably 350 ℃.
In particular, the duration of the calcination ranges from 1 hour to 6 hours, preferably 3 hours.
As an embodiment, in the reducing treatment of the powdered product under the conditions of reducing gas and first preset temperature, and obtaining the catalyst after the reducing treatment, the method further comprises: the gas in the reducing gas environment comprises argon-hydrogen mixed gas.
Optionally, the volume fraction of hydrogen in the argon-hydrogen mixture is in the range of 4% to 8%, preferably 5%.
As an embodiment, in the reducing treatment of the powdered product under the conditions of reducing gas and first preset temperature, and obtaining the catalyst after the reducing treatment, the method further comprises: the gas in the reducing atmosphere comprises hydrogen.
In particular, the first preset temperature has a value ranging from 550 ℃ to 850 ℃, preferably 650 ℃.
As an embodiment, in the reducing treatment of the powdered product under the conditions of the inert gas environment and the first preset temperature, and obtaining the catalyst after the reducing treatment, the method further comprises: the duration of the reduction treatment ranges from 3 hours to 9 hours, preferably 6 hours.
The gas in the inert gas environment includes one or more of nitrogen, hydrogen, argon, and the like.
The carbon black includes one or more of acetylene black, SP conductive agent (Super P), and ketjen black.
The metal includes at least one or more of lithium, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, tungsten, gold, silver, platinum, ruthenium, and palladium.
The precursor includes one or more of nitrate, chlorate and organic metal compound.
The catalyst is obtained by applying the preparation method of the catalyst for preparing the nano carbon material.
Specifically, the ratio of the mass ratio of carbon black to metal in the catalyst ranges from 0.1:1 to 3: 1. Preferably, the ratio of the mass ratio of carbon black to metal is 1: 1.
The first embodiment is as follows:
an impregnation method is adopted to prepare a carbon black (Super P) supported iron catalyst, and the catalyst is used for microwave catalytic decomposition of polyethylene to prepare a multi-wall carbon nano tube:
in this example, carbon black (Super P) is used as a carrier, metal iron is loaded on the carbon black by an impregnation method, the loading amount of iron is 50%, and the mass ratio of iron to carbon in the finally obtained catalyst powder is 1: 1. the specific method comprises the following steps:
fully mixing carbon black (Super P) and ferric nitrate in distilled water according to the required proportion; calcining for 3 hours at 350 ℃ under the inert atmosphere of argon; after the calcination was completed, the catalyst was subjected to reduction treatment in an atmosphere of 5% H2/Ar under the reduction treatment conditions of 650 ℃ for 6 hours. Finally collecting black powder of the carbon black supported iron catalyst, wherein the mass ratio of iron to carbon of the finally obtained catalyst powder is 1:1 (hereinafter referred to as catalyst).
The catalyst prepared in example one was placed under microwave for testing:
the test conditions were: the heating rate and temperature of the catalyst under the action of 1000W microwaves were tested under an inert atmosphere of argon. The test results show that the heating rate of the catalyst under the action of microwaves is about 18 degrees/second; the stabilization temperature was about 360 deg.C (FIG. 1).
The nano carbon material is prepared by adopting the catalyst prepared in the embodiment to carry out microwave treatment:
20g of polyethylene plastic particles are crushed and fully physically and mechanically mixed with 20g of catalyst; putting the mixed sample into a microwave reactor, and purging under argon (100ml/min) for 10 minutes; the microwave power was set at 1000W, the frequency was set at 2.45GHz, and the reaction was carried out for 10 minutes. 32.2g of solid product was collected. The prepared carbon nano-tube is detected to be a multi-wall carbon nano-tube with the diameter of about 5nm to 20nm (figure 2).
Example two:
preparing an iron catalyst supported by carbon black (Super P) by adopting a coprecipitation method, and preparing a multi-wall carbon nano tube by decomposing polyethylene through microwave catalysis:
in this embodiment, carbon black (Super P) is used as a carrier, metal iron is loaded on the carbon black by a coprecipitation method, the loading amount of iron is 50%, and the mass ratio of iron to carbon in the finally obtained catalyst powder is 1: 1. the specific method comprises the following steps:
carbon black (Super P) and ferric chloride are fully mixed in distilled water according to the required proportion and stirred to form a suspension. Sodium hydroxide and sodium carbonate are mixed according to a molar ratio of 3:1 is mixed and dissolved in 100ml of distilled water to prepare an alkaline solution. While stirring, the suspension was dropped into an alkaline solution heated to 70 ℃. Filtering the mixed precipitate, and repeatedly washing the precipitate with distilled water for at least 3 times; and drying, crushing and grinding the washed precipitate in sequence to obtain a powder sample. The powder samples were subjected to a reduction treatment in a 5% H2/Ar environment at 650 ℃ for 6 hours. Finally collecting black powder of the carbon black supported iron catalyst, wherein the mass ratio of iron to carbon of the finally obtained catalyst powder is 1:1 (hereinafter referred to as catalyst).
The catalyst prepared in example two was placed under microwave for testing:
the test conditions were: the heating rate and temperature of the catalyst under the action of 1000W microwaves were tested under an inert atmosphere of argon. The test result shows that the heating rate of the catalyst under the microwave action is about 13.3 degrees/second; the stabilization temperature was about 430 deg.C (FIG. 3).
The nano carbon material is prepared by adopting the catalyst prepared in the second embodiment to carry out microwave treatment:
20g of polyethylene plastic particles are crushed and fully physically and mechanically mixed with 20g of catalyst; putting the mixed sample into a microwave reactor, and purging under argon (100ml/min) for 10 minutes; the microwave power was set at 1000W, the frequency was set at 2.45GHz, and the reaction was carried out for 10 minutes. 30.8g of solid product was collected. The prepared carbon nano-tube is detected to be a multi-wall carbon nano-tube with the diameter of about 8nm to 30nm (figure 4).
Example three:
preparing an iron catalyst loaded by carbon black (Super P) by adopting a combustion method, and preparing a multi-wall carbon nano tube by decomposing polyethylene through microwave catalysis:
in this example, carbon black (Super P) is used as a carrier, and a combustion method is performed, citric acid is used as an auxiliary agent, metallic iron is loaded on the carbon black, the loading amount of iron is 50%, and the mass ratio of iron to carbon of the finally obtained catalyst powder is 1: 1. the specific method comprises the following steps:
fully mixing carbon black (Super P) and ferric nitrate in a small amount of distilled water according to the required proportion to form viscous slurry; citric acid in an amount of 30% by weight based on the sum of the carbon black and the ferric nitrate was added to the slurry to be sufficiently mixed and ground. Roasting the mixed slurry in an inert atmosphere of argon at 350 ℃ for 3 hours to obtain black powder; the obtained black powder was subjected to a reduction treatment in an atmosphere of 5% H2/Ar at 650 ℃ for 6 hours. Finally collecting black powder of the carbon black supported iron catalyst, wherein the mass ratio of iron to carbon of the finally obtained catalyst powder is 1:1 (hereinafter referred to as catalyst).
The catalyst prepared in example three was placed under microwave for testing: the test conditions were: the heating rate and temperature of the catalyst under the action of 1000W microwaves were tested under an inert atmosphere of argon. The test results show that the heating rate of the catalyst under the microwave action is about 12.5 degrees/second; the stabilization temperature was approximately 376 deg.C (FIG. 5).
The nano carbon material is prepared by adopting the three prepared catalysts in the embodiment to carry out microwave treatment:
20g of polyethylene plastic particles are crushed and fully physically and mechanically mixed with 20g of catalyst; putting the mixed sample into a microwave reactor, and purging under argon (100ml/min) for 10 minutes; the microwave power was set at 1000W, the frequency was set at 2.45GHz, and the reaction was carried out for 10 minutes. 34.3g of solid product was collected. The prepared carbon nano-tube is detected to be a multi-wall carbon nano-tube with the diameter of about 5-20nm (figure 6).
Example four:
the method adopts an impregnation method to prepare a plurality of catalysts of different metal systems supported by carbon black (Super P) and is used for preparing multi-wall carbon nano-tubes by microwave catalytic decomposition of polyethylene
In this example, carbon black (Super P) is used as a carrier, different metals including iron, nickel, cobalt and copper are loaded on the carbon black by an impregnation method, the loading amount of the metals is 40%, and the mass ratio of the metals to the carbon of the finally obtained catalyst powder is 2: 3. in addition, a bimetallic catalyst with carbon black (Super P) as a carrier was prepared, wherein the bimetallic included iron-aluminum, nickel-aluminum and cobalt-aluminum, the loading of metal was 40% and the loading of aluminum was 10%. The mass ratio of the finally obtained catalyst powder metal to aluminum to carbon was 4: 1: 4. the specific method comprises the following steps:
fully mixing carbon black (Super P) and a precursor of metal in distilled water according to a required proportion; calcining for 3 hours at 350 ℃ under the inert atmosphere of argon; after the calcination was completed, the catalyst was subjected to reduction treatment in an atmosphere of 5% H2/Ar at 650 ℃ for 6 hours. Finally collecting black powder of the carbon black supported iron catalyst, wherein the mass ratio of iron to carbon of the finally obtained catalyst powder is 1:1 (hereinafter referred to as catalyst).
The various catalysts prepared in example four were each tested in a microwave:
the test conditions were: the heating rate and temperature of the catalyst under the action of 1000W microwaves were tested under an inert atmosphere of argon.
The test result shows that:
the heating rates of Fe/C, Ni/C, Co/C and Cu/C catalysts under the action of microwaves are respectively 15.3 degrees/second, 11.2 degrees/second, 8.9 degrees/second and 7.3 degrees/second; the stabilization temperatures were 431, 376, 354 and 298 ℃ respectively.
The heating rates of the Fe-Al/C, Ni-Al/C and Co-Al/C bimetallic catalysts under the action of microwaves are 18.9, 14.3 and 12.5 degrees/second respectively; the stabilization temperatures were 422, 389 and 364 deg.C (Table 1), respectively.
Table 1 statistics of temperature rise test results of different catalysts prepared in example four under microwave action
The nano carbon material is prepared by adopting a plurality of catalysts prepared in the four embodiments to carry out microwave treatment:
20g of polyethylene plastic particles are crushed and fully physically and mechanically mixed with 20g of catalyst; putting the mixed sample into a microwave reactor, and purging under argon (100ml/min) for 10 minutes; the microwave power was set at 1000W, the frequency was set at 2.45GHz, and the reaction was carried out for 10 minutes. The solid product was collected and analyzed.
Wherein, the Fe/C, Ni/C, Co/C and Cu/C catalysts are used for catalytically decomposing polyethylene under the action of microwaves, and the collected solid products are respectively 32.5 g, 33.1 g, 28.3 g and 30.2 g.
The bimetallic catalysts of Fe-Al/C, Ni-Al/C and Co-Al/C are used for catalytically decomposing polyethylene under the action of microwaves, and solid products of 32.8 g, 32.1 g and 30.4g are collected. (Table 2)
Through detection, the multi-wall carbon nano-tubes with the diameter of about 5-50nm are detected in the solid samples.
TABLE 2 calculation of conservation of materials for preparing carbon nanotubes by microwave catalytic decomposition of polyethylene with different catalysts in example four
Comparative example one:
carbon black (Super P) is used as a catalyst, and polyethylene is decomposed by microwave catalysis to prepare the multi-walled carbon nano-tube
In the comparative example, carbon black (Super P) is used as a catalyst, and is mixed with polyethylene particles, and then the mixture is decomposed by microwave under microwave to prepare the multi-wall carbon nano tube. The specific method comprises the following steps:
first, a temperature rise test was performed with carbon black (Super P) placed under a microwave: the test conditions were: the heating rate and temperature of the catalyst under the action of 1000W microwaves were tested under an inert atmosphere of argon. The test result shows that the heating rate of the catalyst under the microwave action is about 4 degrees/second; the stabilization temperature was about 373 deg.C (FIG. 7).
20g of polyethylene plastic granules are comminuted and thoroughly physically and mechanically mixed with 20g of carbon black (Super P); putting the mixed sample into a microwave reactor, and purging under argon (100ml/min) for 10 minutes; the microwave power was set at 1000W, the frequency was set at 2.45GHz, and the reaction was carried out for 10 minutes. 19.5g of solid product was collected. And (3) detecting that no carbon nano tube is produced.
The comparative example shows that carbon black has no catalytic capability and cannot catalyze and decompose polyethylene to prepare the carbon nano tube under the action of microwaves although the carbon black has excellent wave-absorbing and temperature-raising capability.
Comparative example two:
preparation of multi-walled carbon nano-tube by taking iron powder as catalyst and decomposing polyethylene under microwave catalysis
The comparative example uses iron powder as catalyst, the iron powder used is commercial iron powder (Sigama-Aldrich) with size of 20mesh (0.841 cm); mixing with polyethylene particles, placing under microwave, and microwave decomposing to obtain multi-wall carbon nanotube. The specific method comprises the following steps:
firstly, placing iron powder under microwave for temperature rise test: the test conditions were: the heating rate and temperature of the catalyst under the action of 1000W microwaves were tested under an inert atmosphere of argon. The test result shows that the heating rate of the catalyst under the microwave action is about 1 degree/second; the stabilization temperature was about 126 deg.C (FIG. 8).
20g of polyethylene plastic particles are crushed and fully physically and mechanically mixed with 20g of metallic iron catalyst; putting the mixed sample into a microwave reactor, and purging under argon (100ml/min) for 10 minutes; the microwave power was set at 1000W, the frequency was set at 2.45GHz, and the reaction was carried out for 10 minutes. 39.7g of solid product was collected. The polyethylene is not decomposed and no carbon nano tube is generated through detection.
The comparison example shows that 20mesh iron powder does not have the capacity of absorbing waves and raising temperature under the action of microwaves and cannot reach the temperature required by catalytic reaction.
Other embodiments of the present disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the disclosure following, in general, the principles of the disclosure and including such departures from the present disclosure as come within known or customary practice within the art to which the disclosure pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.
Moreover, although the steps of the methods of the present disclosure are depicted in the drawings in a particular order, this does not require or imply that the steps must be performed in this particular order, or that all of the depicted steps must be performed, to achieve desirable results. Additionally or alternatively, certain steps may be omitted, multiple steps combined into one step execution, and/or one step broken down into multiple step executions, etc.
In the above description, numerous specific details are provided to give a thorough understanding of embodiments of the invention. It is to be understood that the invention is not limited in its application to the details of construction and the arrangement of components set forth in the description. The invention is capable of other embodiments and of being practiced and carried out in various ways.
Claims (21)
1. A preparation method of a catalyst for preparing a nano carbon material is characterized by comprising the following steps:
mixing carbon black and a metal precursor, and loading metal on the carbon black according to a preset method to obtain a powdery product;
and reducing the powdery product in a reducing gas environment at a first preset temperature, and obtaining the catalyst after the reduction treatment.
2. The method of claim 1, wherein: after the carbon black and the precursor of the metal are mixed, the metal is loaded on the carbon black according to a preset method, and a powdery product is obtained, and the method further comprises the following steps:
mixing carbon black and a metal precursor in distilled water to form a suspension;
stirring the suspension, drying, and grinding the dried product;
and calcining the ground product for a first preset time under the conditions of inert gas environment and a second preset temperature to obtain a powdery product.
3. The method of claim 2, wherein: in the step of calcining the ground product for a first preset time under the conditions of the inert gas environment and a second preset temperature to obtain a powdered product, the method further comprises:
the numerical range of the second preset temperature is 340 ℃ to 450 ℃;
and/or the first preset time has a value ranging from 1 hour to 8 hours.
4. The method of claim 1, wherein: after the carbon black and the precursor of the metal are mixed, the metal is loaded on the carbon black according to a preset method, and a powdery product is obtained, and the method further comprises the following steps:
mixing carbon black and a metal precursor in distilled water to form a suspension;
and dripping the suspension into an alkaline solution, drying the precipitate, and grinding to obtain a powdery product.
5. The method of claim 4, wherein: the method comprises the following steps of dripping the suspension into an alkaline solution, drying the precipitate, and grinding to obtain a powdery product, and further comprises the following steps:
and dissolving sodium hydroxide and sodium carbonate in distilled water according to a second preset proportion to prepare an alkaline solution.
6. The method of claim 5, wherein: the second predetermined ratio comprises a molar ratio, and the ratio of the molar ratio ranges from 1:1 to 5: 1.
7. The method of claim 4, wherein: the method comprises the following steps of dripping the suspension into an alkaline solution, drying the precipitate, and grinding to obtain a powdery product, and further comprises the following steps:
the temperature of the alkaline solution ranges from 40 ℃ to 100 ℃.
8. The method of claim 4, wherein: the method comprises the following steps of dripping the suspension into an alkaline solution, drying the precipitate, and grinding to obtain a powdery product, and further comprises the following steps:
the precipitate was washed with distilled water at least three times and then dried.
9. The method of claim 1, wherein: after the carbon black and the precursor of the metal are mixed, the metal is loaded on the carbon black according to a preset method, and a powdery product is obtained, and the method further comprises the following steps:
adding citric acid and distilled water into the mixed carbon black and metal precursor, and grinding to form viscous slurry;
and roasting the viscous slurry under the conditions of inert gas environment and third preset temperature to obtain a powdery product after roasting.
10. The method of claim 9, wherein: adding citric acid and distilled water to the mixed carbon black and metal precursor, and grinding to form viscous slurry, and further comprising:
the ratio of the mass of the citric acid to the mass of the mixed carbon black and the metal precursor ranges from 0.1:1 to 0.5: 1.
11. The method of claim 9, wherein: in the step of roasting the viscous slurry under the conditions of inert gas environment and third preset temperature, and obtaining a powdery product after roasting, the method further comprises the following steps:
the numerical range of the third preset temperature is 350 ℃ to 450 ℃;
and/or the duration of calcination ranges from 1 hour to 6 hours.
12. The method of claim 1, wherein: in the step of reducing the powdery product under the conditions of reducing gas and a first preset temperature and obtaining the catalyst after the reduction, the method further comprises the following steps:
the gas in the reducing gas environment comprises argon-hydrogen mixed gas.
13. The method of manufacturing according to claim 12, wherein: the volume fraction of the hydrogen in the argon-hydrogen mixed gas ranges from 4% to 8%.
14. The method of claim 1, wherein: in the step of reducing the powdery product under the conditions of reducing gas and a first preset temperature and obtaining the catalyst after the reduction, the method further comprises the following steps:
the gas in the reducing gas environment comprises hydrogen;
and/or the first preset temperature has a value ranging from 550 ℃ to 850 ℃.
15. The method of claim 1, wherein: in the step of reducing the powdery product in an inert gas environment at a first preset temperature to obtain the catalyst, the method further comprises:
the duration of the reduction treatment ranges from 3 hours to 9 hours.
16. The method of claim 2, 9 or 11, wherein: the gas in the inert gas environment comprises one or more of nitrogen, hydrogen, argon and the like.
17. The method of claim 1, wherein: the carbon black comprises one or more of acetylene black, SP conductive agent or Ketjen black.
18. The method of claim 1, wherein: the metal comprises at least one or more of lithium, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, tungsten, gold, silver, platinum, ruthenium and palladium.
19. The method of claim 1, wherein: the precursor comprises one or more of nitrate, chlorate and organic metal compound.
20. A catalyst, characterized by: the catalyst for producing nanocarbon materials according to any one of claims 1 to 19, which is used in the production method.
21. The catalyst of claim 20, wherein: the ratio of the mass ratio of carbon black to metal in the catalyst ranges from 0.1:1 to 3: 1.
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| CN104671238B (en) * | 2015-02-06 | 2017-01-11 | 中国科学院山西煤炭化学研究所 | Method for quickly preparing high-performance graphene |
| CN104787747B (en) * | 2015-04-10 | 2017-04-26 | 宁波诺丁汉大学 | Method for preparing multiwalled carbon nanotube through microwave enhanced fast pyrolysis of biomass and/or carbonaceous organic waste |
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| CN1583273A (en) * | 2004-06-11 | 2005-02-23 | 中山大学 | Preparing method for loaded metal oxide catalyst |
| CN109759107A (en) * | 2019-03-22 | 2019-05-17 | 湘潭大学 | A kind of composite catalyst and preparation method thereof |
| CN112238122A (en) * | 2020-09-15 | 2021-01-19 | 介翔宇 | Treatment process for microwave catalytic decomposition of medical waste |
| CN112320787A (en) * | 2020-10-26 | 2021-02-05 | 介翔宇 | Preparation method and application of nano carbon material |
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