CN114195126A

CN114195126A - Preparation method of composite nano-carbon material and composite nano-material

Info

Publication number: CN114195126A
Application number: CN202110972936.0A
Authority: CN
Inventors: 张兆熙; 介翔宇
Original assignee: Wuhan New Carbon Technology Co ltd
Current assignee: Wuhan New Carbon Technology Co ltd
Priority date: 2020-10-26
Filing date: 2021-08-24
Publication date: 2022-03-18
Also published as: WO2022089671A1; CN112320787A; WO2022089670A1; CN114195125A; CN114195127A

Abstract

The invention provides a preparation method of a composite nano-carbon material and the composite nano-material, comprising the following steps: preparing a catalyst; mixing the raw materials with a catalyst to prepare a material; and (3) carrying out n-section microwave treatment on the configured materials. The invention provides a preparation method of a composite nano carbon material and the composite nano material, which adopt carbon black as a substrate, realize the in-situ growth of a carbon nano tube by supported metal, finally prepare the composite nano carbon material of the carbon nano tube and the carbon black, effectively improve the self-dispersibility of carbon nano tube powder, improve the agglomeration phenomenon existing in the process of preparing the carbon nano tube, construct a good conductive network combined by point and line, adopt the microwave treatment of multi-section gradient power, well connect and cooperate the microwave treatment of each section, obviously improve the yield, the purity and the quality of the carbon nano tube and effectively disperse the carbon nano tube in carbon black particles.

Description

Preparation method of composite nano-carbon material and composite nano-material

Technical Field

The invention relates to the technical field of carbon material preparation, in particular to a preparation method of a composite nano carbon material and a composite nano material.

Background

The carbon nano composite material is an ideal electrode material, composite material, photoconductive material, magnetic material and adsorbing material; can be widely applied to the fields of aerospace, electric vehicles, intelligent manufacturing and the like. Both carbon nanotubes and carbon black are widely used as excellent conductive materials due to their unique morphology and chemical and physical properties. Carbon atoms on the carbon nano tube are hybridized by sp2 to form a C-C covalent bond and form a large-range delocalized pi bond, and the carbon nano tube has unique and excellent electric conduction, heat conduction and corrosion resistance, stable chemical property, strong thermal stability and good adsorption property due to obvious conjugation effect. Carbon black is composed of spherical small particles, has low manufacturing cost, and is a widely used conductive material. The characteristics of the two carbon nano materials are combined, the composite carbon nano material is designed to be more ideal, and the conductive network combined by the point line and the point line has extremely important value in the application process.

At present, the composite material of carbon nanotube and carbon black basically adopts a physical mixing method (application No. CN 200710048028). In order to improve the problem of difficult dispersion of carbon nanotubes, carbon nanotubes and carbon black are basically prepared into slurry respectively, and then simply mechanically mixed in the form of slurry (Composites Part B: Engineering,161, 169-182). However, it is difficult to achieve a sufficiently uniform mixing of the two carbon nanomaterials and to form a physical connection between the two carbon nanomaterials in the composite material of the carbon nanotubes and the carbon black. Thus, the dotted network character created by the synergistic effect of carbon nanotubes and carbon black is greatly diminished.

In addition, the current methods for preparing carbon nanotubes mainly use conventional vapor deposition (thermal cracking) methods to prepare carbon nanotubes from alkane gases (application nos. CN201510549461, CN00112788, CN202010315883, and CN 201010586433). The method takes metal as a catalyst and only alkane substances as a carbon source to prepare the single carbon nano tube. The carbon nano tube produced by the method is extremely easy to agglomerate, is hardly dissolved in any organic solvent, has poor wettability with other substances, and cannot be uniformly dispersed in the using process, so that the application of the carbon nano tube in various fields is severely limited. In addition, the traditional vapor deposition method has limited carbon source selection, basically uses alkane gas as a raw material, and easily generates uncertain byproducts by using solid and liquid alkanes as the carbon source, so that the effective preparation of the carbon nano tube cannot be realized. Patent CN104787747A discloses a method for preparing multi-walled carbon nanotubes by microwave pyrolysis of biomass and/or carbon-containing organic waste, but the multi-walled carbon nanotubes prepared by the pyrolysis method have a large tube diameter range and a low yield, and it is difficult to control the growth of the carbon nanotubes. The prepared carbon nano tube has limited performance and practical application space.

Disclosure of Invention

In order to avoid the defects of the prior art, the invention designs the preparation method of the composite nano-carbon material and the composite nano-material, which can improve the yield, purity and quality of the carbon nano-tube in the nano-carbon material and improve the split linearity of the carbon nano-tube, so as to solve the problems of low production efficiency and poor constructed conductive network of the nano-carbon material in the prior art.

In order to achieve the above object, the present invention provides a method for preparing a composite nanocarbon material, comprising:

preparing a catalyst;

mixing the raw materials with a catalyst to prepare a material;

performing n sections of microwave treatment on the configured materials, and adding a preset amount of raw materials before each section of microwave treatment from the second section of microwave treatment to the nth section of microwave treatment, wherein n is more than or equal to 3;

wherein the microwave power in each section of microwave treatment is more than or equal to the microwave power in the previous section of microwave treatment.

As an example, in the preparing the catalyst, further 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.

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:

the temperature of the alkaline solution ranges from 40 ℃ to 100 ℃.

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 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 embodiment, in the n-stage microwave treatment of the configured material, and in the second-stage microwave treatment to the nth-stage microwave treatment, a preset amount of raw materials is added before each stage of microwave treatment, where n is greater than or equal to 3, the method further includes:

purging with inert gas before each microwave treatment; or, each section of microwave treatment is in an inert gas environment; or, each microwave treatment is carried out in the environment with standard atmospheric pressure and oxygen content lower than 5000 ppm.

the microwave power of the microwave treatment is greater than or equal to 200W.

As an embodiment, n is 3, and includes a first stage microwave treatment, a second stage microwave treatment and a third stage microwave treatment;

the microwave power of the second stage microwave treatment is 120 to 140 percent of that of the first stage microwave treatment;

the microwave power of the third stage microwave treatment is 145% to 165% of the microwave power of the second stage microwave treatment.

As an example, the microwave power of the first stage microwave treatment ranges from 200W to 8000W;

the microwave power of the second stage microwave treatment is 125-135% of that of the first stage microwave treatment;

the microwave power of the third stage microwave treatment is 145% to 155% of the microwave power of the second stage microwave treatment.

In one embodiment, the microwave power of the first stage microwave treatment is in the range of 500W to 2000W, the microwave power of the second stage microwave treatment is in the range of 1000W to 3000W, and the microwave power of the third stage microwave treatment is in the range of 1500W to 4500W.

As an example, in the mixing and preparing the raw material and the catalyst to form the material, the method further comprises the following steps:

the mass ratio of the feedstock to the catalyst ranges from 1:1 to 5: 1.

in the second to nth microwave treatments, the ratio of the mass of the raw material added before each microwave treatment to the mass of the product of the previous microwave treatment is in the range of 0.2:1 to 10: 1.

in the second stage of microwave treatment, the ratio of the mass of the added raw materials to the mass of the product after the first stage of microwave treatment is in the range of 0.5:1 to 2: 1;

in the third stage of microwave treatment, the ratio of the mass of the added raw material to the mass of the product after the second stage of microwave treatment is in the range of 0.2:1 to 1: 1.

the duration of each microwave treatment is in the range of 5min to 30 min.

n is more than 3, and the n sections of microwave treatment at least comprise a first section of microwave treatment, a second section of microwave treatment and a third section of microwave treatment;

the duration of the first stage of microwave treatment is 5min to 20 min;

the duration time of the second stage of microwave treatment is 10min to 20 min;

the duration time of the third microwave treatment is 5min to 15 min;

in the fourth microwave treatment to the nth microwave treatment, the duration of each microwave treatment is 5min to 10 min.

the n-stage microwave treatment at least comprises a first stage microwave treatment, a second stage microwave treatment and a third stage microwave treatment;

the third stage of microwave treatment is repeated at least once.

the microwave power of the first stage of microwave treatment is 500W to 2000W, and the duration is 5min to 20 min;

the microwave power of the second stage of microwave treatment is 1000W to 3000W, and the duration is 10min to 20 min;

the microwave power of the third microwave treatment stage is 1500W to 4500W, and the duration is 5min to 15 min.

each section of microwave treatment comprises at least one stage of microwave treatment process, and when the microwave treatment process is at least two stages, the microwave power in each stage of microwave treatment process is greater than or equal to the microwave power in the previous stage of microwave treatment process.

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.

As an example, the starting material comprises a carbon chain polymer.

As an example, the raw material includes one or more of plastic, chemical fiber, tire, medical waste, biomass, and household garbage.

As an example, the microwave power in each microwave treatment is 2.45GHz or 915 MHz.

As an embodiment, in the n-stage microwave treatment of the configured material, and in the second-stage microwave treatment to the nth-stage microwave treatment, a preset amount of raw materials is added before each stage of microwave treatment, and after n is greater than or equal to 3, the method further comprises:

and purifying the product of the last microwave treatment.

As an embodiment, in the purifying the product of the last microwave treatment, the method further comprises:

acid washing the product of the last microwave treatment for many times by using acid liquid;

washing the product obtained after acid washing for many times by using distilled water;

and drying and washing the obtained product.

As an example, in the multiple acid washing of the product of the last stage of microwave treatment with the acidic liquid, the method further comprises:

the acidic liquid comprises one of nitric acid, sulfuric acid or hydrochloric acid;

and/or the concentration of the acidic liquid is greater than or equal to 5.0M;

and/or the number of acid washes ranges from 5 to 20.

As an example, in the product obtained after the dry cleaning, the method further includes:

drying the washed product in microwave for a preset period of time.

and (3) carrying out high-temperature melting treatment on the product of the last microwave treatment for 30-60 min in an oxygen-free environment at a temperature of 1800 ℃ or higher.

The invention also provides a composite nano-carbon material which is obtained by applying the preparation method of the composite nano-material.

As an example, the composite type nanocarbon material includes carbon black and carbon nanotubes, and a ratio of a content of the carbon nanotubes to a content of the carbon black ranges from 1:1 to 60: 1.

As an example, the composite type nanocarbon material includes multi-walled carbon nanotubes having a diameter ranging from 5nm to 20 nm.

The invention provides a preparation method of a composite nano carbon material and the composite nano material, which adopts carbon black as a substrate, realizes the in-situ growth of a carbon nano tube by supported metal, finally prepares the composite nano carbon material of the carbon nano tube and the carbon black, effectively improves the self-dispersibility of carbon nano tube powder, improves the agglomeration phenomenon existing in the process of preparing the carbon nano tube, constructs a good conductive network combined by point and line, adopts the microwave treatment of multi-section gradient power, adopts the microwave treatment and the flow of the gradient power, adjusts the component proportion of each section of the microwave treatment according to the requirement, can well join and cooperate the microwave treatment of each section, obviously improves the yield, the purity and the quality of the carbon nano tube, effectively disperses the carbon nano tube in carbon black particles, and obtains the multi-wall carbon nano tube with the average diameter of 5nm to 30nm, the purity can reach more than 90%, the yield of the multi-walled carbon nano-tube can reach more than 70%, the preparation method has no secondary pollution and meets the requirement of pollution emission, combustible gas rich in hydrogen, methane and other gases is generated in the preparation process, the combustible gas can be used for combustion power generation to generate heat or can be recycled and supplied to a microwave reactor, and the combustible gas is treated by a flue gas treatment system (processes of cooling, dust removal, desulfurization and denitration and the like) and then is emitted, so that the resource utilization rate is greatly improved.

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 schematic process flow diagram of a preparation method according to an embodiment of the present invention, wherein (1) is a microwave reactor (reactor);

FIG. 2 is a thermogravimetric analysis diagram of the composite nanocarbon material prepared in the first embodiment of the present invention;

FIG. 3 is a scanning electron microscope image of the composite nano-carbon material prepared in the first embodiment of the present invention;

fig. 4 is a projection electron microscope image of carbon nanotubes contained in the composite nanocarbon material prepared in the first embodiment of the present invention;

FIG. 5 is a scanning electron microscope image of a composite nano-carbon material prepared in the second embodiment of the present invention;

FIG. 6 is a transmission electron microscope image of carbon nanotubes contained in the composite nanocarbon material prepared in the fifth embodiment of the present invention;

FIG. 7 is a thermogravimetric analysis chart of the composite type nanocarbon material prepared in the comparative example of the present invention;

FIG. 8 is a transmission electron microscope image of carbon nanotubes prepared in a comparative example of the present invention.

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 research of the inventor finds that the existing catalyst for preparing the nano-carbon material cannot be applied to microwave treatment, the microwave catalysis is increasingly applied to material preparation, for carbon chain polymer substances such as plastics with complex structures, the high-yield nano-carbon material preparation is difficult to realize by simple one-step microwave treatment, the microwave power has great influence on the yield, the purity and the quality of the nano-carbon material, the yield improvement of the nano-carbon material by adopting multi-step microwave treatment with equal power is very limited, and the high-power multi-step microwave treatment also easily causes the purity or the quality of the nano-carbon material to be adversely affected, so that the invention provides the preparation method of the composite nano-carbon material and the composite nano-material, which are shown in figures 1 to 6, and comprises the following steps: preparing a catalyst; mixing the raw materials with a catalyst to prepare a material; performing n sections of microwave treatment on the configured materials, and adding a preset amount of raw materials before each section of microwave treatment from the second section of microwave treatment to the nth section of microwave treatment, wherein n is more than or equal to 3; wherein the microwave power in each section of microwave treatment is more than or equal to the microwave power in the previous section of microwave treatment.

Through multi-stage microwave treatment, microwave treatment and flow with gradient power are adopted, the component proportion of each stage of microwave treatment is adjusted as required, each stage of microwave treatment can be well connected and matched, the yield, the purity and the quality of the carbon nano tube are obviously improved, the carbon nano tube is effectively dispersed in carbon black particles, the average diameter of the prepared multi-wall carbon nano tube is 5-30 nm, the purity can reach more than 90%, and the yield of the multi-wall carbon nano tube can reach more than 70%.

Wherein, when the raw materials and the catalyst are mixed, any suitable mechanical physical mixing mode can be adopted, such as stirring, grinding, crushing and the like. Preferably, the mixing time is 3mim to 15 minutes.

Preferably, the feedstock is comminuted prior to the first stage of microwave treatment. The particle size of the pulverized material is less than 5cm, preferably less than 1 cm.

Taking three-stage microwave treatment as an example, under the mediation of a catalyst, the microwave carries out continuous and repeated catalytic carbonization decomposition on raw materials such as carbon chain polymers and the like, wherein in the first-stage microwave treatment, the catalyst is activated under the action of the microwave, and the raw materials are primarily catalytically decomposed to form a substrate for growth of the composite nano carbon material; the second stage of microwave treatment mainly comprises the growth and accumulation process of the composite nano carbon material, wherein a large amount of raw materials are catalytically decomposed under the combined action of microwaves and a catalyst, and the raw materials continue to precipitate and grow on a carbon simple substance substrate formed by the first stage of treatment and loading to generate the composite nano carbon material; the third stage of microwave treatment mainly is a curing process of the carbon composite nano carbon material, and under the action of high-power microwaves and high temperature, the composite nano carbon material produced by the second stage of microwave treatment is cured, and amorphous carbon is converted into the composite nano carbon material. In the three-stage microwave treatment process, the treatment of each stage can be well linked and matched, and the generation of the composite nano carbon material is promoted together.

Specifically, the preparation of the catalyst further comprises: 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.

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.

Preferably, the method comprises the following steps of performing n-stage microwave treatment on the configured materials, adding a preset amount of raw materials before each stage of microwave treatment in the second-stage microwave treatment to the nth-stage microwave treatment, wherein n is more than or equal to 3: purging with inert gas before each microwave treatment; or, each section of microwave treatment is in an inert gas environment; or, each microwave treatment is carried out in the environment with standard atmospheric pressure and oxygen content lower than 5000 ppm. By adopting the three modes, inert gases such as nitrogen, argon and the like are used as carrier gases, so that the oxygen content of the semi-finished product to be subjected to microwave treatment is reduced, carbon elements are prevented from being oxidized in the microwave treatment process, and the cost reliability of the composite nano carbon material is ensured.

The inert gas includes nitrogen, argon, etc.

Further, n sections of microwave treatment are carried out on the configured materials, in the processes from the second section of microwave treatment to the nth section of microwave treatment, a preset amount of raw materials are added before each section of microwave treatment, and n is more than or equal to 3, the method further comprises the following steps: the microwave power of the microwave treatment is more than or equal to 200W, so that the microwave power can meet the requirement of each section of microwave treatment. Preferably, the microwave power of the microwave treatment is greater than or equal to 500W.

Optionally, n is 3, and the microwave processing includes a first stage microwave processing, a second stage microwave processing, and a third stage microwave processing; the microwave power of the second stage microwave treatment is 120 to 140 percent of that of the first stage microwave treatment; the microwave power of the third stage microwave treatment is 145% to 165% of the microwave power of the second stage microwave treatment. That is, the microwave power in the three-stage microwave treatment is gradually increased, so that the raw materials can be respectively subjected to microwave treatment under the condition of different microwave powers, the raw materials are sequentially subjected to primary catalytic decomposition to form a composite nano-carbon material growth substrate, a growth accumulation process of the composite nano-carbon material (the raw materials are subjected to a large amount of catalytic decomposition under the combined action of microwaves and a catalyst, and continue to precipitate and grow on a carbon simple substance substrate formed by the first stage treatment load to generate the composite nano-carbon material) and a curing process of the composite nano-carbon material (under the action of high-power microwaves and high temperature, the composite nano-carbon material generated by the second stage of microwave treatment is cured, and amorphous carbon is converted into the composite nano-carbon material), and finally the required composite nano-carbon material is formed.

Furthermore, the microwave power of the first stage microwave treatment ranges from 200W to 8000W; the microwave power of the second stage microwave treatment is 125-135% of that of the first stage microwave treatment; the microwave power of the third stage microwave treatment is 145% to 155% of the microwave power of the second stage microwave treatment.

As an example, in the mixing and preparing the raw material and the catalyst to form the material, the method further comprises the following steps: the mass ratio of the feedstock to the catalyst ranges from 1:1 to 5: 1.

Furthermore, the method comprises the following steps of performing n-stage microwave treatment on the configured materials, adding a preset amount of raw materials before each stage of microwave treatment from the second stage microwave treatment to the nth stage microwave treatment, wherein n is more than or equal to 3: in the second to nth microwave treatments, the ratio of the mass of the raw material added before each microwave treatment to the mass of the product of the previous microwave treatment is in the range of 0.2:1 to 10: 1.

preferably, n is 3, and comprises a first stage microwave treatment, a second stage microwave treatment and a third stage microwave treatment; in the second stage of microwave treatment, the ratio of the mass of the added raw materials to the mass of the product after the first stage of microwave treatment is in the range of 0.5:1 to 2: 1; in the third stage of microwave treatment, the ratio of the mass of the added raw material to the mass of the product after the second stage of microwave treatment is in the range of 0.2:1 to 1: 1.

As an embodiment, in the n-stage microwave treatment of the configured material, and in the second-stage microwave treatment to the nth-stage microwave treatment, a preset amount of raw materials is added before each stage of microwave treatment, where n is greater than or equal to 3, the method further includes: the duration of each microwave treatment is in the range of 5min to 30 min.

Preferably, the duration of the first stage of microwave treatment is from 5min to 25 min; the duration time of the second stage of microwave treatment is 10min to 30 min; the duration of the third microwave treatment stage is 5min to 30 min.

Optionally, the step of performing n-stage microwave treatment on the configured material, and in the second-stage microwave treatment to the nth-stage microwave treatment, adding a preset amount of raw materials before each stage of microwave treatment, wherein n is greater than or equal to 3, further includes: n is more than 3, and the n sections of microwave treatment at least comprise a first section of microwave treatment, a second section of microwave treatment and a third section of microwave treatment; the duration of the first stage of microwave treatment is 5min to 20 min; the duration time of the second stage of microwave treatment is 10min to 20 min; the duration time of the third microwave treatment is 5min to 15 min; in the fourth microwave treatment to the nth microwave treatment, the duration of each microwave treatment is 5min to 10 min.

In practice, the specific duration can be adjusted within the above range in accordance with the power setting of the microwave treatment and the volume mass of the raw material, and generally, the reaction time can be shortened when the microwave power of the microwave treatment is high, and the reaction time can be prolonged when the microwave power of the microwave treatment is low.

In the research process of the inventor, the optimization of the catalyst for microwave treatment shows that the yield and the purity of the composite nano carbon material can be obviously improved by adopting a single transition metal catalyst during the first-stage microwave treatment and adopting at least two transition metal catalysts for compounding during the subsequent microwave treatment. Furthermore, by adjusting the type of catalyst used in each stage of microwave treatment (especially the type of catalyst used in the microwave treatment at the later stage), the molecular arrangement structure of the product can be changed, and thus the type and content of the main carbon nanomaterial in the product can be changed, and it is known to those skilled in the art that the catalyst is rarely consumed in the microwave treatment process, so that the catalyst used in the first stage of microwave treatment can be added before the reaction starts, and the catalyst used in the later stage of microwave treatment can be supplemented before the corresponding microwave treatment starts. Therefore, the method comprises the following steps of performing n-stage microwave treatment on the configured materials, adding a preset amount of raw materials before each stage of microwave treatment in the second-stage microwave treatment to the nth-stage microwave treatment, wherein n is more than or equal to 3, and the method further comprises the following steps: and adding a second catalyst in at least one microwave treatment from the second microwave treatment to the nth microwave treatment.

Specifically, the second catalyst comprises an iron-nickel alloy or an iron-nickel compound. When the composite nano carbon material is a multi-walled carbon nanotube, the iron-based and nickel catalyst is used in cooperation in the second microwave treatment, so that the reaction direction can be guided to the synthesis of the multi-walled carbon nanotube, the high-purity multi-walled carbon nanotube can be obtained, and the high yield can be ensured.

Optionally, the ratio of the mass ratio of iron to nickel in the second catalyst ranges from 4:1 to 100: 1. Preferably, the ratio of the mass ratio of iron to nickel is in the range of 4:1 to 80: 1.

The ratio of the mass ratio of iron to nickel in the second catalyst ranges from 10:1 to 100: 1. Preferably, the ratio of the mass ratio of iron to nickel is in the range of 10:1 to 80: 1. The catalyst with the proportion can better cooperate with various catalysts, and is more favorable for improving the yield and the purity of the multi-wall carbon nano tube.

In order to better ensure the yield of the composite nano carbon material, the method comprises the following steps of performing n-stage microwave treatment on the configured material, adding a preset amount of raw materials before each stage of microwave treatment from the second stage of microwave treatment to the nth stage of microwave treatment, wherein n is more than or equal to 3: the n-stage microwave treatment at least comprises a first stage microwave treatment, a second stage microwave treatment and a third stage microwave treatment; the third stage of microwave treatment is repeated at least once. Through the third stage of microwave treatment for multiple times, raw materials can be added for multiple times to increase the yield of the final composite nano carbon material.

As an embodiment, in the n-stage microwave treatment of the configured material, and in the second-stage microwave treatment to the nth-stage microwave treatment, a preset amount of raw materials is added before each stage of microwave treatment, where n is greater than or equal to 3, the method further includes: the n-stage microwave treatment at least comprises a first stage microwave treatment, a second stage microwave treatment and a third stage microwave treatment; the microwave power of the first stage of microwave treatment is 500W to 2000W, and the duration is 5min to 20 min; the microwave power of the second stage of microwave treatment is 1000W to 3000W, and the duration is 10min to 20 min; the microwave power of the third microwave treatment stage is 1500W to 4500W, and the duration is 5min to 30 min.

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.

As an example, the starting material comprises a carbon chain polymer.

Specifically, the raw materials comprise one or more of plastics, chemical fibers, tires, medical wastes, biomass and household garbage. The plastic may be any plastic containing a carbon chain polymer, including but not limited to polyethylene, polypropylene, polystyrene, and the like.

As an example, the second catalyst comprises a transition metal or a compound of a transition metal.

In particular, the catalyst comprises iron or an iron compound or iron carbide.

The composition of the catalyst is different from the composition of the second catalyst.

Optionally, the transition metal includes one or more of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, and tungsten.

The compound of nickel may be a nickel oxide compound; the compound of molybdenum can be molybdenum oxide or molybdenum carbide; the compound of chromium may be a chromium oxide compound or chromium carbide.

In order to better ensure the effect of absorbing microwaves by the catalyst, the particle size of the catalyst and/or the second catalyst is less than 0.5 mm. The preferred catalyst particle size is 50nm to 500 μm.

In order to further improve the purity of the product, the method comprises the following steps of performing n-stage microwave treatment on the configured materials, adding a preset amount of raw materials before each stage of microwave treatment in the second-stage microwave treatment to the nth-stage microwave treatment, and after n is more than or equal to 3: and purifying the product of the last microwave treatment.

As an alternative embodiment, in the purification of the product of the last microwave treatment, the method further comprises: acid washing the product of the last microwave treatment for many times by using acid liquid; washing the product obtained after acid washing for many times by using distilled water; and drying and washing the obtained product.

As an example, in the multiple acid washing of the product of the last stage of microwave treatment with the acidic liquid, the method further comprises: the acidic liquid comprises one of nitric acid, sulfuric acid or hydrochloric acid; and/or the concentration of the acidic liquid is greater than or equal to 5.0M; and/or the number of acid washes ranges from 5 to 20.

As an example, in the product obtained after the dry cleaning, the method further includes: the product obtained after washing is dried under microwave for a predetermined period of time, preferably 5min to 10 min.

As an embodiment, in the purifying the product of the last microwave treatment, the method further comprises: and (3) carrying out high-temperature melting treatment on the product of the last microwave treatment for 30-60 min in an oxygen-free environment at a temperature of 1800 ℃ or higher.

As an example, the composite type nanocarbon material includes multi-walled carbon nanotubes having a diameter ranging from 5nm to 20 nm. (As shown in FIG. 8, it is apparent that the carbon nanotubes have a significant agglomeration phenomenon)

The carbon content of the polyethylene and polypropylene plastics used in the examples below was about 86% and the carbon content of the biomass was about 40%.

Example 1

Preparing the multi-wall carbon nano tube by catalyzing and carbonizing polyethylene plastics by using an iron catalyst loaded by carbon black (Super P):

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.

in this embodiment, a schematic process flow diagram of the embodiment is shown in fig. 1, and the specific method is as follows:

(1) fully mixing carbon black (Super P) and iron precursor 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 a 5% H2/Ar atmosphere 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).

(2) The first stage of 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 first-stage microwave reactor, and purging under argon (100ml/min) for 10 minutes; the microwave power was set at 500W, the frequency was set at 2.45GHz, and the reaction was carried out for 10 minutes. 32.2g of solid product was collected.

(3) And (3) second-stage microwave treatment: mixing 32.2g of the solid product collected in the first stage of microwave treatment with 30g of comminuted polyethylene plastic; putting the fully mixed sample into a two-stage microwave reactor, and purging for 10 minutes under the argon condition (100 ml/min); setting the microwave power at 500W and the frequency at 2.45GHz, and reacting for 5 minutes (first-stage microwave treatment process); the microwave power was adjusted to 1000W, and the reaction was continued for 10 minutes (second microwave treatment step). 47.2g of solid product was collected.

(4) And (3) third-stage microwave treatment: mixing 47.2g of solid product collected from the second stage of microwave treatment with 20g of comminuted polyethylene plastic; putting the fully mixed sample into a three-section microwave reactor, and purging for 10 minutes under the argon condition (100 ml/min); setting the microwave power at 500W and the frequency at 2.45GHz, and reacting for 5 minutes (first-stage microwave treatment process); the microwave power was adjusted to 1500W, and the reaction was continued for 10 minutes (second microwave treatment step). 57g of solid product was collected.

(5) And (3) fourth-stage microwave treatment: mixing the solid product collected from the previous microwave treatment with 20g of crushed polyethylene plastic; putting the fully mixed sample into a microwave reactor, and purging under the argon condition (100ml/min) for 10 minutes; setting the microwave power at 500W and the frequency at 2.45GHz, and reacting for 3 minutes (first stage microwave treatment process); the microwave power was adjusted to 2000W, and the reaction was continued for 15 minutes (second microwave treatment step).

(6) And fifth stage of microwave treatment: the specific process is the same as the fourth microwave treatment process. 74g of solid product was finally collected.

Sampling and analyzing the solid product collected by microwave treatment; through detection, the content of the carbon nano material in the collected solid product is 97.2% (fig. 2), wherein the content of the carbon nano tube is calculated according to 2.8% of the metal oxide residues: 95.5 percent; the carbon black content is 1.7%; the ratio of carbon nanotubes to carbon black was about 56: 1. the prepared carbon nanotubes are multi-walled carbon nanotubes with a diameter of about 5-20nm (fig. 3 and 4).

Example 2:

in this example, carbon black (Super P) was used as a carrier, and metallic nickel was supported on the carbon black by an impregnation method.

In this embodiment, the carbon nanotube is prepared by using polyethylene as a raw material, and the specific method is as follows:

(1) 49.55g of nickel nitrate were dissolved in water, and 10g of carbon black (Super P) was dispersed in the nickel nitrate solution with stirring to form a suspension. After drying, calcining for 3 hours at 350 ℃ in an inert atmosphere; after the calcination was completed, the sample was subjected to a reduction treatment in a 5% H2/Ar atmosphere at 650 ℃ for 6 hours, and finally a black powder of the carbon black-supported nickel catalyst was collected.

(2) The first stage of microwave treatment: mixing 19.89g of the collected nickel-carbon black catalyst and 20g of polyethylene through a physical machine, putting the mixture into a microwave reactor, and purging the reactor with inert gas for 10 minutes; setting the microwave power to be 500W to perform catalytic decomposition reaction for 10 minutes;

(3) and (3) second-stage microwave treatment: mechanically and physically mixing 30.1g of the collected solid product with 30g of polyethylene particles again, putting the mixture into a microwave reactor, purging with inert gas for 10 minutes, setting the microwave power at 500W, and reacting for 5 minutes (first-stage microwave treatment process); adjusting the microwave power to 1000W, reacting for 10 minutes (second-stage microwave treatment process), and collecting 49.7g of solid product;

(4) and (3) third-stage microwave treatment: mixing the collected solid product with 25g of polyethylene again, putting the mixture into a microwave reactor, purging the reactor with inert gas for 10 minutes, setting the microwave power to be 500W, and reacting for 5 minutes (first-stage microwave treatment process); the microwave power was adjusted to 1500W, and the reaction was continued for 10 minutes (second microwave treatment step), whereby 62.7g of a solid product was collected.

(5) And repeatedly pickling the obtained product for 3 times by using a hydrochloric acid solution with the mass percentage of 15%, repeatedly washing the product for 10 times by using distilled water, and removing nickel catalyst particles to obtain the carbon nano tube and carbon black to obtain the composite carbon nano material (figure 5).

Example 3:

in this example, carbon black (Super P) was used as a carrier, and metallic cobalt was supported on the carbon black by an impregnation method.

(1) 49.38g of cobalt nitrate was dissolved in water, and 10g of carbon black (Super P) was dispersed in the cobalt nitrate solution with stirring to form a suspension. After drying, calcining for 3 hours at 350 ℃ in an inert atmosphere; after the calcination was completed, the sample was subjected to a reduction treatment in a 5% H2/Ar atmosphere at 650 ℃ for 6 hours. Finally, a black powder of carbon black-supported cobalt catalyst was collected

(2) The first stage of microwave treatment: mixing 20.5g of the collected cobalt-carbon black catalyst and 20g of polyethylene through a physical machine, putting the mixture into a microwave reactor, and purging the reactor with inert gas for 10 minutes; setting the microwave power to be 500W to perform catalytic decomposition reaction for 10 minutes;

(3) and (3) second-stage microwave treatment: mechanically and physically mixing 28.5g of the collected solid product with 30g of polyethylene particles again, putting the mixture into a microwave reactor, purging with inert gas for 10 minutes, setting the microwave power at 500W, and reacting for 5 minutes (first-stage microwave treatment process); adjusting the microwave power to 1000W, reacting for 10 minutes (second-stage microwave treatment process), and collecting 44.3g of solid product;

(4) and (3) third-stage microwave treatment: mixing the collected solid product with 20g of polyethylene again, putting the mixture into a microwave reactor, purging the reactor with inert gas for 10 minutes, setting the microwave power to be 500W, and reacting for 5 minutes (first-stage microwave treatment process); the microwave power was adjusted to 1500W, and the reaction was continued for 10 minutes (second microwave treatment step), whereby 56.1g of a solid product was collected.

(5) And repeatedly pickling the obtained product for 3 times by using a hydrochloric acid solution with the mass percentage of 15%, repeatedly washing the product for 10 times by using distilled water, and removing cobalt catalyst particles to obtain the carbon nano tube and the carbon black to obtain the composite carbon nano material.

Example 4:

in this example, carbon black (Super P) was used as a carrier, and metallic iron and metallic aluminum were supported on the carbon black by an impregnation method.

(1) 64.93g of iron nitrate and 13.9g of aluminum nitrate were dissolved in water, and 10g of carbon black (Super P) was dispersed in the metal salt solution with stirring to form a suspension. After drying, calcining for 3 hours at 350 ℃ in an inert atmosphere; after the calcination was complete, the sample was subjected to a reduction treatment in a 5% H2/Ar environment at 650 degrees Celsius for 6 hours, and finally a black powder of carbon black supported iron and aluminum catalyst was collected.

(2) The first stage of microwave treatment: mixing 19.5g of the collected iron-aluminum-carbon black catalyst and 20g of polyethylene through a physical machine, putting the mixture into a microwave reactor, and purging the reactor with inert gas for 10 minutes; setting the microwave power to be 500W to perform catalytic decomposition reaction for 10 minutes;

(3) and (3) second-stage microwave treatment: mechanically and physically mixing 33.6g of the collected solid product with 30g of polyethylene particles again, putting the mixture into a microwave reactor, purging with inert gas for 10 minutes, setting the microwave power at 500W, and reacting for 5 minutes (first-stage microwave treatment process); adjusting the microwave power to 1000W, reacting for 10 minutes (second-stage microwave treatment process), and collecting 51.2g of solid product;

(4) and (3) third-stage microwave treatment: mixing the collected solid product with 25g of polyethylene again, putting the mixture into a microwave reactor, purging the reactor with inert gas for 10 minutes, setting the microwave power to be 500W, and reacting for 5 minutes (first-stage microwave treatment process); the microwave power was adjusted to 1500W, and the reaction was continued for 10 minutes (second microwave treatment step), whereby 63.6g of a solid product was collected.

(5) And repeatedly pickling the obtained product for 3 times by using nitric acid solution with the mass percentage of 5%, repeatedly washing the product for 10 times by using distilled water, and removing catalyst particles of iron and aluminum to obtain the carbon nano tube and the carbon black to obtain the composite carbon nano material.

Example 5:

in this example, carbon black (Super P) was used as a carrier, and metallic iron and nickel were supported on the carbon black by an impregnation method.

(1) 36g of iron nitrate and 24.77g of nickel nitrate were dissolved in water, and 10g of carbon black (Super P) was dispersed in a metal salt solution with stirring to form a suspension. After drying, calcining for 3 hours at 350 ℃ in an inert atmosphere; after the calcination was complete, the sample was subjected to a reduction treatment in a 5% H2/Ar environment at 650 degrees Celsius for 6 hours, and finally a black powder of carbon black supported iron and nickel catalyst was collected.

(2) The first stage of microwave treatment: mixing 21.4g of the collected iron-nickel-carbon black catalyst and 20g of polyethylene through a physical machine, putting the mixture into a microwave reactor, and purging the reactor with inert gas for 10 minutes; setting the microwave power to 750W for catalytic decomposition reaction, wherein the reaction time is 10 minutes;

(3) and (3) second-stage microwave treatment: mechanically and physically mixing 29.9g of the collected solid product with 30g of polyethylene particles again, putting the mixture into a microwave reactor, purging with inert gas for 10 minutes, setting the microwave power to be 1000W, reacting for 10 minutes, and collecting 47.5g of the solid product;

(4) and (3) third-stage microwave treatment: the collected solid product was mixed with 25g of polyethylene again, and then charged into a microwave reactor, and after purging with an inert gas for 10 minutes, the reaction was carried out at 1500W for 15 minutes to collect 59.5g of a solid product.

(5) And repeatedly pickling the obtained product for 3 times by using nitric acid solution with the mass percentage of 5%, repeatedly washing the product for 10 times by using distilled water, and removing catalyst particles of iron and nickel to prepare the carbon nano tube and the carbon black to obtain the composite carbon nano material. The carbon nanotubes contained therein are multi-walled carbon nanotubes having a diameter of about 5 to 20nm (FIG. 6).

Comparative example

The comparative example provides a method for preparing a carbon nanotube and carbon black composite carbon nanomaterial by using polyethylene plastic as a raw material by using a traditional pyrolysis method, which comprises the following specific steps:

20g of polyethylene plastic particles were crushed and fully physically and mechanically mixed with 20g of iron catalyst powder supported on carbon black (mass ratio of iron to carbon is 1: 1); putting the mixed sample into an electric heating reactor, and carrying out cracking reaction under the condition of argon (100 ml/min); setting the temperature to 800 ℃, and setting the heating rate to 20 ℃ per minute; the reaction time was 60 minutes. After cooling, 12.3g of liquid product and 23.8g of solid product were collected. The solid product was again subjected to thorough physical mechanical mixing with 20g of plastic, and the above pyrolysis reaction was repeated; after repeating the procedure 5 times, 39.9g of solid product was collected.

Sampling and analyzing the collected solid product; through detection, the carbon content in the solid product is 68.2% (fig. 7), wherein, calculated according to the metal oxide residue of 31.8%, the carbon nanotube content is: 45.9 percent; the carbon black content was 22.3%. The carbon nanotube to carbon black ratio is about 2: 1. in addition, the prepared carbon nanotubes have obvious agglomeration phenomenon as seen from a projection electron microscope (fig. 8).

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

1. A preparation method of a composite nano carbon material is characterized by comprising the following steps: the method comprises the following steps:

preparing a catalyst;

mixing the raw materials with a catalyst to prepare a material;

2. The method of claim 1, wherein: in the preparing the catalyst, further comprising:

3. The method of claim 2, 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:

stirring the suspension, drying, and grinding the dried product;

4. The method of claim 2, 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:

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:

the temperature of the alkaline solution ranges from 40 ℃ to 100 ℃.

6. The method of claim 2, 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:

7. The method of claim 6, wherein: adding citric acid and distilled water to the mixed carbon black and metal precursor, and grinding to form viscous slurry, and further comprising:

8. The method of claim 2, 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.

9. The method of claim 1, wherein: the method comprises the following steps of performing n sections of microwave treatment on the configured materials, adding a preset amount of raw materials before each section of microwave treatment from the second section of microwave treatment to the nth section of microwave treatment, wherein n is more than or equal to 3, and the method also comprises the following steps:

10. The method of claim 1, wherein: the method comprises the following steps of performing n sections of microwave treatment on the configured materials, adding a preset amount of raw materials before each section of microwave treatment from the second section of microwave treatment to the nth section of microwave treatment, wherein n is more than or equal to 3, and the method also comprises the following steps:

11. The method of manufacturing according to claim 10, wherein:

n is 3, and comprises a first stage microwave treatment, a second stage microwave treatment and a third stage microwave treatment;

12. The method of claim 11, wherein: the microwave power range of the first stage of microwave treatment is 200W to 8000W;

13. The method of claim 11, wherein: the microwave power range of the first stage microwave treatment is 500W to 2000W, the microwave power range of the second stage microwave treatment is 1000W to 3000W, and the microwave power range of the third stage microwave treatment is 1500W to 4500W.

14. The method of claim 1, wherein: in the material formed by mixing and configuring the raw materials and the catalyst, the method also comprises the following steps:

the mass ratio of the feedstock to the catalyst ranges from 1:1 to 5: 1.

15. The method of claim 1, wherein: the method comprises the following steps of performing n sections of microwave treatment on the configured materials, adding a preset amount of raw materials before each section of microwave treatment from the second section of microwave treatment to the nth section of microwave treatment, wherein n is more than or equal to 3, and the method also comprises the following steps:

16. the method of claim 15, wherein:

17. The method of claim 1, wherein: the method comprises the following steps of performing n sections of microwave treatment on the configured materials, adding a preset amount of raw materials before each section of microwave treatment from the second section of microwave treatment to the nth section of microwave treatment, wherein n is more than or equal to 3, and the method also comprises the following steps:

the duration of each microwave treatment is in the range of 5min to 30 min.

18. The method of claim 1, wherein: the method comprises the following steps of performing n sections of microwave treatment on the configured materials, adding a preset amount of raw materials before each section of microwave treatment from the second section of microwave treatment to the nth section of microwave treatment, wherein n is more than or equal to 3, and the method also comprises the following steps:

the duration of the first stage of microwave treatment is 5min to 20 min;

the duration time of the third microwave treatment is 5min to 15 min;

19. The method of claim 1, wherein: the method comprises the following steps of performing n sections of microwave treatment on the configured materials, adding a preset amount of raw materials before each section of microwave treatment from the second section of microwave treatment to the nth section of microwave treatment, wherein n is more than or equal to 3, and the method also comprises the following steps:

the third stage of microwave treatment is repeated at least once.

20. The method of claim 1, wherein: the method comprises the following steps of performing n sections of microwave treatment on the configured materials, adding a preset amount of raw materials before each section of microwave treatment from the second section of microwave treatment to the nth section of microwave treatment, wherein n is more than or equal to 3, and the method also comprises the following steps:

21. The method of claim 1, wherein: the method comprises the following steps of performing n sections of microwave treatment on the configured materials, adding a preset amount of raw materials before each section of microwave treatment from the second section of microwave treatment to the nth section of microwave treatment, wherein n is more than or equal to 3, and the method also comprises the following steps:

22. The production method according to claim 3 or 6, characterized in that: the gas in the inert gas environment comprises one or more of nitrogen, hydrogen, argon and the like.

23. The method of claim 2, wherein: the carbon black comprises one or more of acetylene black, SP conductive agent or Ketjen black.

24. The method of claim 2, 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.

25. The method of claim 2, wherein: the precursor comprises one or more of nitrate, chlorate and organic metal compound.

26. The method of claim 1, wherein: the starting material comprises a carbon chain polymer.

27. The method of claim 1, wherein: the raw materials comprise one or more of plastics, chemical fibers, tires, medical wastes, biomass and household garbage.

28. The method of claim 1, wherein: the microwave power in each microwave treatment is 2.45GHz or 915 MHz.

29. The method of claim 1, wherein: the method comprises the following steps of performing n sections of microwave treatment on the configured materials, adding a preset amount of raw materials before each section of microwave treatment in the second-section microwave treatment to the nth-section microwave treatment, and after n is more than or equal to 3:

and purifying the product of the last microwave treatment.

30. The method of claim 29, wherein: in the purification of the product of the last microwave treatment, the method further comprises the following steps:

and drying and washing the obtained product.

31. The method of claim 30, wherein: in the multiple acid washing of the product of the last microwave treatment by using the acidic liquid, the method further comprises the following steps:

and/or the concentration of the acidic liquid is greater than or equal to 5.0M;

and/or the number of acid washes ranges from 5 to 20.

32. The method of claim 30, wherein: the product obtained after the drying and washing further comprises:

drying the washed product in microwave for a preset period of time.

33. The method of claim 29, wherein: in the purification of the product of the last microwave treatment, the method further comprises the following steps:

34. A composite nanocarbon material is characterized in that: obtained by applying the preparation method of the composite nano-material of any one of claims 1 to 33.

35. A composite nanocarbon material according to claim 34, wherein: the composite nano carbon material comprises carbon black and carbon nano tubes, and the ratio of the content of the carbon nano tubes to the content of the carbon black is 1: 1-60: 1.

36. A composite nanocarbon material according to claim 34, wherein: the composite nano carbon material comprises a multi-wall carbon nano tube, and the diameter range of the multi-wall carbon nano tube is 5nm to 20 nm.