CN112320787A - Preparation method and application of nano carbon material - Google Patents
Preparation method and application of nano carbon material Download PDFInfo
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Abstract
The invention relates to the technical field of carbon material preparation, in particular to a preparation method and application of a nano carbon material. The invention provides a preparation method of a nano carbon material, which takes carbon chain polymer substances such as plastics and the like as raw materials and is prepared by three-stage microwave treatment under the action of a microwave catalyst; in the three-stage microwave treatment, the power of the first stage microwave treatment is more than or equal to 200W, the power of the second stage microwave treatment is improved by 20-40% compared with the power of the first stage microwave treatment, and the power of the third stage microwave treatment is improved by 45-65% compared with the power of the second stage microwave treatment. The preparation method has the advantages of low cost, high yield and high purity, is a safe, energy-saving, environment-friendly and efficient nano carbon material preparation process, and combustible gas rich in hydrogen, methane and other gases generated in the preparation process can be recycled, so that the resource utilization rate is greatly improved.
Description
Technical Field
The invention relates to the technical field of carbon material preparation, in particular to a method for preparing a nano carbon material by using carbon chain polymer substances such as plastics and the like and application thereof.
Background
The nano carbon material mainly includes graphene, carbon nanotube, nanographite, carbon fiber, fullerene, and the like, wherein the graphene and the carbon nanotube have excellent physicochemical properties such as: the material has electrical conductivity, thermal conductivity, corrosion resistance and the like, and is widely applied to the fields of aerospace, electric vehicles, intelligent manufacturing and the like as an electrode material, a composite material, a light guide material, a magnetic material and the like.
At present, the preparation method of graphene and carbon nanotubes is mainly a chemical vapor deposition method. The method has the advantages of complex process and high production cost, and the produced carbon materials such as the carbon nano tube and the like have low purity, so that the large-scale low-cost industrial production is difficult to realize. Therefore, the method which has simple development process and low cost and can prepare the graphene and the carbon nano tube in batches is the key point for the wide application of the nano carbon material.
Plastics are high molecular compounds produced by the polyaddition or polycondensation of petrochemical products. The plastic has good plasticity, and can be made into various daily articles without damaging the molecular constitution thereof, and can be widely applied to life. Worldwide, about one third of the plastic is used for packaging materials; meanwhile, plastics are also widely used in building materials, pipes, automobile manufacturing, furniture and toys. Due to the wide application of plastic products in life, white pollution (plastic garbage pollution) is a worldwide problem which cannot be ignored. There are now about 49 billion tons of plastic waste worldwide, and it is expected that about 120 billion plastic waste will be produced by 2050; more than 50% of the waste plastics are derived from fast-dissipating plastics such as polyethylene and polypropylene. If the plastic is used as a raw material with abundant carbon, and the plastic is used for preparing carbon nano-tubes, graphene and other nano-carbon materials, the difficulties of white pollution and shortage of carbon nano-materials can be solved, and considerable economic benefits are brought.
Biomass (bioglass) is a generic term for various organisms formed by photosynthesis, including all animals, plants and microorganisms, which are rich in carbon-containing organic matter in large quantities. Biomass can become an important energy source for human survival by virtue of the characteristics of pervasiveness, richness, renewability and the like. In addition, with the development of human society, the carbon chain polymer waste (such as plastic, chemical fiber, etc.) generated globally increases year by year, and brings about greater environmental pollution pressure. The biomass and carbon chain polymer waste is rich in carbon raw materials, and if the biomass and carbon chain polymer waste is used as a raw material to prepare carbon nano-tubes, graphene and other carbon nano-materials, the problem of environmental stress caused by the carbon nano-materials can be relieved, the waste can be recycled, the problem of shortage of the carbon nano-materials can be solved, and the biomass and carbon chain polymer waste has important social and economic values.
Patent CN104787747A discloses a method for preparing multi-walled carbon nanotubes by microwave-enhanced fast pyrolysis of biomass and/or carbon-containing organic waste, which specifically comprises: the biomass or the carbon-containing organic waste is mixed independently or is uniformly mixed with a microwave absorbent and then is placed in a reactor of a microwave cavity, inert gas is introduced into the reactor to an oxygen-free environment, the microwave input power is adjusted to be more than 500w, the reactor is heated to 400-1500 ℃ for pyrolysis reaction, and after the reaction is finished, the multi-walled carbon nano tube is obtained. Although the method can realize the preparation of the multi-wall carbon nano tube by using the biomass, the diameter of the prepared carbon nano tube is 50-100nm, the yield can only reach 20-30%, and the quality and the yield of the carbon nano tube are still to be improved.
Disclosure of Invention
The invention aims to provide a preparation method and application of a nano carbon material. The invention also aims to provide the nano carbon material prepared by the method and application thereof.
The invention develops an efficient preparation method of the nano carbon material by taking carbon chain polymer substances such as plastics as raw materials and based on a microwave treatment technology. For carbon chain polymer substances such as plastics with complex structures and the like, the high-yield preparation of the nano carbon material is difficult to realize by simple one-step microwave treatment. Through continuous research and practice verification, the invention develops a three-section type microwave treatment process, adopts three-section type gradient power microwave to treat carbon chain polymer substances such as plastics and the like, and microwave treatment of each section can well link and cooperate, thereby obviously improving the yield, purity and quality of the nano carbon material.
Specifically, the invention provides the following technical scheme:
in a first aspect, the invention provides a preparation method of a nano carbon material, which is prepared by taking carbon chain polymer substances as raw materials and performing three-stage microwave treatment under the action of a microwave catalyst;
in the three-stage microwave treatment, the power of the first stage microwave treatment is more than or equal to 200W, the power of the second stage microwave treatment is improved by 20-40% compared with the power of the first stage microwave treatment, and the power of the third stage microwave treatment is improved by 45-65% compared with the power of the second stage microwave treatment;
in the first stage of microwave treatment, the mass ratio of the raw material to the microwave catalyst is (0.5-2): 1;
in the second stage of microwave treatment, mixing the product obtained by the first stage of microwave treatment with the raw materials with the mass of 1.5-10 times of that of the product, and then carrying out microwave treatment;
in the third stage of microwave treatment, the product obtained by the second stage of microwave treatment is mixed with the raw materials with the mass of 0.2-1 time of that of the product, and then the microwave treatment is carried out.
In the three-stage microwave treatment, under the mediation of a catalyst, the microwave carries out continuous and repeated catalytic carbonization and decomposition on carbon chain polymers such as plastics, wherein in the first stage microwave treatment, the catalyst is activated under the action of the microwave, and the raw materials are initially catalytically decomposed to form a substrate for growth of the nano carbon material; the second stage of microwave treatment mainly comprises the growth and accumulation process of the 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 nano carbon material; the third stage of microwave treatment mainly comprises a carbon nano-carbon material curing process, and under the action of high-power microwaves and high temperature, the nano-carbon material formed by the second stage of treatment is cured, and the amorphous carbon is converted into the 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 nano carbon material is promoted together.
The three-stage microwave treatment as described above may be carried out in a conventional microwave reactor (for example, a microwave treatment oven) respectively, and the volumes of the first stage, second stage and third stage microwave treatment reactors are gradually increased according to the amounts of the raw materials and the volumes of the reaction systems.
Preferably, in the three-stage microwave treatment, the power of the first stage microwave treatment is 200-.
Specifically, in the three-stage microwave treatment, the power of the first stage microwave treatment is 500-.
The invention discovers that the yield of the nano carbon material can be obviously improved by adopting the three-section type gradient power microwave treatment process, and higher purity and quality are ensured at the same time.
As an embodiment of the present invention, in the three-stage microwave treatment, the power of the first stage microwave treatment is 800W-.
Preferably, the time of the first stage microwave treatment is 5-25 minutes; the time of the second stage of microwave treatment is 10-30 minutes; the time of the third microwave treatment is 5-30 minutes.
In practice, the specific processing time 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, generally, high power can suitably shorten the reaction time, and low power can suitably prolong the reaction time.
Specifically, for multi-walled carbon nanotubes, the preferred microwave treatment process is: the power of the first stage of microwave treatment is 600-800W, the treatment time is 10-20 minutes, the power of the second stage of microwave treatment is 900-1100W, the treatment time is 10-25 minutes, the power of the third stage of microwave treatment is 1500-2000W, and the treatment time is 15-30 minutes. The microwave treatment process is more beneficial to improving the yield and the purity of the multi-wall carbon nano tube.
The three-stage microwave treatment according to the invention is preferably carried out under standard atmospheric pressure in an environment with an oxygen content of less than 5000 ppm.
In particular, the three-stage microwave treatment may be carried out in an inert environment, for example: inert gases such as nitrogen and argon are used as carrier gases; alternatively, the reactor may be purged with an inert gas such as nitrogen or argon before the reaction.
The frequency of the three-stage microwave treatment according to the invention is preferably 2.45GHz or 915 MHz.
The microwave source used in the microwave treatment according to the invention may be a conventional microwave source, for example: a magnetron or a solid state source.
The microwave catalyst used in the three-stage microwave treatment of the invention can be transition metal or a compound of transition metal, wherein the transition metal is at least one selected from titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum and tungsten.
In the present invention, the iron compound may be an iron oxide compound or iron carbide; 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.
The invention further optimizes the catalyst used in the microwave treatment and finds that the yield and the purity of the nano carbon material can be obviously improved by adopting a single transition metal catalyst in the first stage of microwave treatment and adopting at least two transition metal catalysts for compounding in the second stage of microwave treatment. Moreover, by adjusting the type of the catalyst used in each stage of microwave treatment (especially the type of the catalyst used in the second stage of microwave treatment), the molecular arrangement structure of the product can be changed, and further, the type and content of the main carbon nano material in the product can be changed.
Specifically, when the nanocarbon material is a multi-walled carbon nanotube, in the three-stage microwave treatment, the microwave catalyst for the first-stage microwave treatment is iron or an iron compound, and the microwave catalysts for the second-stage and third-stage microwave treatments are the microwave catalyst for the first-stage microwave treatment and an iron-nickel alloy or an iron-nickel compound. The invention discovers that the iron-based catalyst is adopted in the first microwave treatment, the iron-based catalyst and the nickel catalyst are adopted in the second microwave treatment, the reaction direction can be guided to the synthesis of the multi-walled carbon nano-tube, the high-purity multi-walled carbon nano-tube can be obtained, and the higher yield can be ensured.
In order to better ensure the effect of the catalyst on absorbing microwaves, the particle size of the catalyst is less than 0.5 mm. The preferred catalyst particle size is 50nm to 500 μm.
For the above catalyst system, preferably, when the nano carbon material is a multi-wall carbon nanotube, the mass ratio of iron to nickel in the microwave catalyst of the second stage microwave treatment is (10-100): 1. preferably (10-80): 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.
It is known to those skilled in the art that the catalyst is rarely consumed during the microwave treatment, and therefore, the catalyst for the first stage of microwave treatment may be added before the start of the reaction, and the catalyst for the second and third stages of microwave treatment comprises the catalyst for the first stage of microwave treatment (present in the solid product obtained by the first stage of microwave treatment) and the catalyst for the second stage of microwave treatment which is added before the start of the reaction.
In order to better ensure the yield of the nano carbon material, the raw material supplement and the microwave treatment can be repeatedly carried out for a plurality of times in the second stage of microwave treatment.
Specifically, the second stage of microwave treatment comprises: (1) mixing the product obtained by the first stage of microwave treatment with iron-nickel alloy or iron-nickel compound with the mass of 0.05-0.2 time of that of the product, mixing the mixture with the raw material with the mass of 1.5-5 times of that of the product, and then carrying out microwave treatment; (2) mixing the product obtained in the step (1) with the raw materials with the mass of 0.5-5 times of that of the product, and then carrying out microwave treatment under the same conditions as the step (1);
preferably, the second stage microwave treatment further comprises (3): repeating the step (2) at least 1 time.
If the product purity is further improved, after the third stage of microwave treatment, a step of purifying the prepared nano carbon material can be provided, and specifically, the nano carbon material can be purified by an acid washing method or a high-temperature melting method.
The optional pickling conditions are as follows: and (3) repeatedly pickling the sample for 5-20 times by using concentrated nitric acid, concentrated sulfuric acid or concentrated hydrochloric acid with the concentration of not less than 5.0M, cleaning the sample for more than 10 times by using distilled water, and drying the cleaned sample under microwave for 5-10 minutes.
The optional high temperature melting conditions are: and carrying out high-temperature melting treatment for 30-60 minutes at the temperature of over 1800 ℃ in the absence of oxygen.
The carbon chain polymer substance is at least one selected from 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.
The optimal raw material of the preparation method provided by the invention is plastic, and the preparation method can be used for efficiently preparing the carbon nano tube with high purity and high yield by using the plastic as the raw material.
In the invention, when the first stage and the second stage of microwave treatment are carried out, the catalyst, the raw material and the solid product need to be mixed firstly, so that the raw material and the catalyst or the raw material and the solid product are in full contact and adhesion with each other. The mixing can be by any suitable mechanical physical mixing means, e.g., stirring, milling, pulverizing, and the like. The preferred mixing time is 3-15 minutes.
In order to better promote the reaction, before the microwave treatment, the raw materials are preferably crushed, and the particle size of the raw materials is controlled to be less than 5 cm; more preferably less than 1 cm.
In a second aspect, the invention also provides a nano carbon material prepared by the preparation method.
Preferably, when the nano carbon material is a multi-wall carbon nanotube, the average diameter of the multi-wall carbon nanotube is 2-100 nm; more preferably 5-80 nm.
In a third aspect, the invention also provides the preparation method or the application of the nano carbon material in the preparation of electrode materials, semiconductors, catalysts or composite materials.
The invention has the beneficial effects that: the invention provides a preparation method of a high-purity nano carbon material with low cost and high yield by taking carbon chain polymer substances such as plastics as raw materials. The average diameter of the multi-wall carbon nano tube prepared by using plastics as raw materials by the method is 5 nm-30 nm, the purity can reach more than 90%, and the yield of the multi-wall carbon nano tube can reach more than 70%.
In addition, the preparation method of the invention has no secondary pollution, meets the requirement of pollutant discharge, and is a safe, energy-saving, environment-friendly and efficient nano carbon material preparation process. And combustible gas rich in hydrogen, methane and other gases is generated in the preparation process, can be used for combustion power generation heat generation or recycling and supplying to the microwave reactor, and is discharged after being treated by a flue gas treatment system (processes of cooling, dust removal, desulfurization and denitration and the like), so that the resource utilization rate is greatly improved.
Drawings
FIG. 1 is a schematic view showing a process flow of a production method of examples 1 to 3 of the present invention, wherein (1) is a mixing and pulverizing apparatus; (2) a microwave reactor (reaction furnace).
FIG. 2 is a thermogravimetric analysis diagram of a multi-walled carbon nanotube prepared from polyethylene plastic as a raw material in example 1 of the present invention.
Fig. 3 is a TPO comparison graph of multi-walled carbon nanotubes prepared from polyethylene plastic as a raw material and commercial multi-walled carbon nanotubes in example 1 of the present invention.
Fig. 4 is a scanning electron microscope image of a multi-walled carbon nanotube prepared from polyethylene plastic as a raw material in example 1 of the present invention.
Fig. 5 is a transmission electron microscope image of a multi-walled carbon nanotube prepared from polyethylene plastic as a raw material in example 1 of the present invention.
FIG. 6 is a thermogravimetric analysis diagram of a multi-walled carbon nanotube prepared from polypropylene plastic as a raw material in example 2 of the present invention.
FIG. 7 is a TPO comparison graph of multi-walled carbon nanotubes prepared from polypropylene plastic as a raw material and commercial multi-walled carbon nanotubes in example 2 of the present invention.
Fig. 8 is a scanning electron microscope image of a multi-walled carbon nanotube prepared from polypropylene plastic as a raw material in example 2 of the present invention.
Fig. 9 is a transmission electron microscope image of a multi-walled carbon nanotube prepared from polypropylene plastic as a raw material in example 2 of the present invention.
FIG. 10 is a thermogravimetric analysis chart of a multi-walled carbon nanotube prepared from a polyethylene and polypropylene mixed plastic as a raw material in example 3 of the present invention.
FIG. 11 is a TPO comparison graph of multi-walled carbon nanotubes prepared from polyethylene and polypropylene mixed plastics as raw materials and commercial multi-walled carbon nanotubes in example 3 of the present invention.
FIG. 12 is a transmission electron microscope image of a multi-walled carbon nanotube prepared from a polyethylene-polypropylene mixed plastic as a raw material in example 3 of the present invention.
Fig. 13 is a thermogravimetric analysis diagram of a multi-walled carbon nanotube prepared from straw (biomass) as a raw material in example 4 of the present invention.
FIG. 14 is a transmission electron microscope image of a multi-walled carbon nanotube prepared from straw (biomass) as a raw material in example 4 of the present invention
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
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 preparation of multi-walled carbon nanotubes from polyethylene Plastic
In this embodiment, a schematic process flow diagram of a process for preparing a multi-walled carbon nanotube from polyethylene plastic is shown in fig. 1, and the specific method is as follows:
(1) the first stage of microwave treatment: 10g of polyethylene plastic particles are crushed and fully physically and mechanically mixed with 10g of iron powder; 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 750W and the frequency at 2.45GHz, and the reaction was carried out for 15 minutes. 15.6g of solid product was collected.
(2) And (3) second-stage microwave treatment: mixing 15.6g of solid product collected in the first stage of microwave treatment with 1.5g of iron-nickel alloy particles (the mass ratio of iron to nickel is 9: 1); then mixing with 30g of crushed 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 to 1000W and the frequency to 2.45GHz, and reacting for 15 minutes; repeatedly mixing the collected solid product with 30g of crushed polyethylene plastic, and then carrying out the catalytic decomposition; repeating for 2 times; after the second treatment, 80.1g of a solid product was obtained.
(3) And (3) third-stage microwave treatment: mixing 80.1g of the solid product collected from the second stage of microwave treatment with 40g 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); the microwave power was set at 1500W and the frequency at 2.45GHz, and the reaction was carried out for 30 minutes. 107.9g of solid product was collected.
Sampling and analyzing the solid product collected by the third microwave treatment; through detection, the content of the multi-walled Carbon nanotubes in the collected solid product is 92.1% (fig. 2), and the comparison graph of the prepared multi-walled Carbon nanotubes and the TPO of the commercial multi-walled Carbon nanotubes (Sigma Aldrich, 698849Carbon nanotubes, Multi-walled, > 98% Carbon bases, O.D.6-13nm) is shown in fig. 3, and the prepared multi-walled Carbon nanotubes reach the commercial Carbon nanotube grade and have similar physicochemical properties. The diameter of the prepared multi-wall carbon nano-tube is about 8-20nm (figures 4 and 5), and the yield of the multi-wall carbon nano-tube is 70.2%.
Example 2 preparation of multiwall carbon nanotubes from Polypropylene Plastic
In this embodiment, a schematic process flow diagram of a process for preparing a multi-walled carbon nanotube from polypropylene plastic is shown in fig. 1, and the specific method is as follows:
(1) the first stage of microwave treatment: 10g of polypropylene plasticThe granules were crushed and admixed with 10g of Fe3O4Fully mixing the powder physically and mechanically; putting the mixed sample into a first-stage microwave reactor, and purging under argon (100ml/min) for 10 minutes; setting the microwave power at 800W and the frequency at 2.45GHz, and reacting for 10 minutes. 14.3g of solid product was collected.
(2) And (3) second-stage microwave treatment: mixing 14.3g of solid product collected in the first stage of microwave treatment with 1.4g of iron-nickel alloy particles (iron-nickel mass ratio is 8: 2); 30g of crushed polypropylene plastic; putting the fully mixed sample into a two-stage microwave reactor, and purging for 10 minutes under the argon condition (100 ml/min); the microwave power was set at 1100W, the frequency was set at 2.45GHz, and the reaction was carried out for 10 minutes. Repeatedly mixing the collected solid product with 30g of crushed polypropylene plastic, and then carrying out catalytic decomposition; repeating for 2 times; after the second treatment, 79.9g of a solid product was obtained.
(3) And (3) third-stage microwave treatment: 79.9g of the solid product collected in the second stage of microwave treatment was mixed with 40g of comminuted polypropylene plastic; putting the fully mixed sample into a three-section microwave reactor, and purging for 10 minutes under the argon condition (100 ml/min); the microwave power was 1800W, the frequency was 2.45GHz, and the reaction time was 20 minutes. 107.7g of solid product was collected.
Sampling and analyzing the solid product collected by the third microwave treatment; through detection, the content of the multi-walled Carbon nanotubes in the collected solid product is 93.4% (fig. 6), and the comparison graph of the prepared multi-walled Carbon nanotubes and the TPO of the commercial multi-walled Carbon nanotubes (Sigma Aldrich, 698849Carbon nanotubes, Multi-walled, > 98% Carbon bases, O.D.6-13nm) is shown in fig. 7, and the prepared multi-walled Carbon nanotubes reach the commercial Carbon nanotube grade and have similar physicochemical properties. The diameter of the prepared multi-wall carbon nano-tube is about 5-18nm (figures 8 and 9), and the yield of the multi-wall carbon nano-tube is 71.3%.
Example 3 preparation of multi-walled carbon nanotubes from mixed polyethylene and polypropylene plastics
In this embodiment, a schematic process flow diagram of a process for preparing a multi-walled carbon nanotube from mixed polyethylene and polypropylene plastic is shown in fig. 1, and the specific method is as follows:
(1) the first stage of microwave treatment: mixing 5g of polyethylene and 5g of polypropylene plastic particles and crushing; and then with 10g Fe3O4Fully mixing the powder physically and mechanically; putting the mixed sample into a first-stage microwave reactor, and purging under argon (100ml/min) for 10 minutes; setting the microwave power to 700W and the frequency to 2.45GHz, and reacting for 20 minutes; 15.1g of solid product was collected.
(2) And (3) second-stage microwave treatment: mixing 15.1g of solid product collected in the first stage of microwave treatment with 1.5g of iron-nickel alloy particles (the mass ratio of iron to nickel is 9: 1); then mixing with 30g of the mixture with equal mass of crushed polyethylene and polypropylene plastic particles; putting the mixed sample into a two-stage microwave reactor, and purging under argon (100ml/min) for 10 minutes; setting the microwave power to 900W and the frequency to 2.45GHz, and reacting for 25 minutes; repeatedly mixing the collected solid product with 30g of the mixture of polyethylene and polypropylene plastic particles with equal mass after being crushed, and then carrying out catalytic decomposition; repeating for 2 times; after the second treatment, 79.9g of a solid product was obtained.
(3) And (3) third-stage microwave treatment: 79.9g of solid product collected by the second stage of microwave treatment is mixed with 40g of the equal mass mixture of the crushed polyethylene and polypropylene plastic particles; 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 to 1800W and the frequency to 2.45GHz, and reacting for 15 minutes; 107.9g of solid product was collected.
Sampling and analyzing the solid product collected by the third microwave treatment; the collected solid product was found to have a multi-walled Carbon nanotube content of 91.6% (fig. 10), and the comparison of the multi-walled Carbon nanotubes prepared with commercial multi-walled Carbon nanotubes (Sigma Aldrich, 698849Carbon nanotubes, multi-walled, > 98% Carbon basis, o.d.6-13nm) TPO as shown in fig. 11 resulted in multi-walled Carbon nanotubes with a diameter of about 8-25nm (fig. 12) and a yield of 70.6%.
Example 4 preparation of multiwalled carbon nanotubes from Biomass (straw)
In this embodiment, a method for preparing a multi-walled carbon nanotube using biomass as a raw material comprises the following steps:
(1) the first stage of microwave treatment: crushing 10g of dry straws and fully and physically and mechanically mixing the crushed dry straws with 10g of iron powder; 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 750W and the frequency at 2.45GHz, and the reaction was carried out for 15 minutes. 11.2g of solid product was collected.
(2) And (3) second-stage microwave treatment: mixing 11.2g of solid product collected in the first stage of microwave treatment with 1.5g of iron-nickel alloy particles (the mass ratio of iron to nickel is 9: 1); mixing with 20g of crushed straw; 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 to 1000W and the frequency to 2.45GHz, and reacting for 15 minutes; repeatedly mixing the collected solid product with 20g of crushed biomass, and then carrying out the catalytic decomposition; repeating for 2 times; after the second treatment, 32.4g of a solid product was obtained.
(3) And (3) third-stage microwave treatment: mixing 32.4g of solid product collected in the second stage of microwave treatment with 15g of crushed straw; putting the fully mixed sample into a three-section microwave reactor, and purging for 10 minutes under the argon condition (100 ml/min); the microwave power was set at 1500W and the frequency at 2.45GHz, and the reaction was carried out for 30 minutes. 37.3g of solid product was collected.
Sampling and analyzing the solid product collected by the third microwave treatment; the collected solid product was found to contain 80.4% multi-walled carbon nanotubes (fig. 13), and the diameter of the multi-walled carbon nanotubes was found to be about 35-80nm (fig. 14), and the yield of the multi-walled carbon nanotubes was found to be 35.3%.
Comparative example 1
The comparative example provides a method for preparing a multi-walled carbon nanotube by using polypropylene plastic as a raw material, which comprises the following specific steps:
10g of polypropylene plastic granules are comminuted and admixed with 10g of Fe3O4Fully mixing the powder physically and mechanically; putting the mixed sample into a first-stage microwave reactor, and purging under argon (100ml/min) for 10 minutes; setting the microwave power at 800W and the frequency at 2.45GHz, and reactingFor 10 minutes. 14.6g of solid product was collected.
Sampling and analyzing the collected solid product; through detection, the content of carbon in the collected solid product is 42.6%, and the content of the multi-wall carbon nano tube is 17.5%. The yield of multi-walled carbon nanotubes was 25.6%.
Comparative example 2
The comparative example provides a method for preparing a multi-walled carbon nanotube by using polypropylene plastic as a raw material, which comprises the following specific steps:
(1) the first stage of microwave treatment: 10g of polypropylene plastic granules are comminuted and admixed with 10g of Fe3O4Fully mixing the powder physically and mechanically; putting the mixed sample into a first-stage microwave reactor, and purging under argon (100ml/min) for 10 minutes; setting the microwave power at 800W and the frequency at 2.45GHz, and reacting for 10 minutes. 14.9g of solid product was collected.
(2) And (3) second-stage microwave treatment: mixing 14.9g of solid product collected in the first stage of microwave treatment with 1.5g of iron-nickel alloy particles (iron-nickel mass ratio is 8: 2); 30g of crushed polypropylene 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 800W and the frequency at 2.45GHz, and reacting for 10 minutes. Repeatedly mixing the collected solid product with 30g of crushed polypropylene plastic, and then carrying out catalytic decomposition; repeating for 2 times; after the second treatment, 83.8g of a solid product was obtained.
(3) And (3) third-stage microwave treatment: mixing 83.8g of solid product collected in the second stage microwave treatment with 40g of crushed polypropylene 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 800W and the frequency at 2.45GHz, and reacting for 10 minutes. 114.8g of solid product was collected.
Sampling and analyzing the solid product collected by the third microwave treatment; the detection shows that the carbon content of the collected solid product is 91.2 percent, and the content of the multi-wall carbon nano tube is 72.9 percent. The yield of multiwall carbon nanotubes was 59.7%.
Comparative example 3
The comparative example provides a method for preparing a multi-walled carbon nanotube by using polypropylene plastic as a raw material, which comprises the following specific steps:
(1) the first stage of microwave treatment: 10g of polypropylene plastic granules are comminuted and admixed with 10g of Fe3O4Fully mixing the powder physically and mechanically; 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 1200W, the frequency was set at 2.45GHz, and the reaction was carried out for 10 minutes. 15.5g of solid product was collected.
(2) And (3) second-stage microwave treatment: mixing 15.5g of solid product collected in the first stage of microwave treatment with 1.5g of iron-nickel alloy particles (iron-nickel mass ratio is 8: 2); 30g of crushed polypropylene plastic; putting the fully mixed sample into a two-stage microwave reactor, and purging for 10 minutes under the argon condition (100 ml/min); the microwave power was set at 500W, the frequency was set at 2.45GHz, and the reaction was carried out for 30 minutes. Repeatedly mixing the collected solid product with 30g of crushed polypropylene plastic, and then carrying out catalytic decomposition; repeating for 2 times; after the second treatment, 68.7g of a solid product was obtained.
(3) And (3) third-stage microwave treatment: mixing 68.7g of the solid product collected from the second stage of microwave treatment with 35g of the comminuted polypropylene plastic; putting the fully mixed sample into a three-section microwave reactor, and purging for 10 minutes under the argon condition (100 ml/min); the microwave power was set at 750W and the frequency at 2.45GHz, and the reaction was carried out for 30 minutes. 89.7g of solid product was collected.
Sampling and analyzing the solid product collected by the third microwave treatment; through detection, the content of carbon in the collected solid product is 88.1%, and the content of the multi-wall carbon nano tube is 61.7%. The yield of multi-walled carbon nanotubes was 40.9%.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a nano carbon material is characterized in that a carbon chain polymer substance is used as a raw material and is prepared by three-stage microwave treatment under the action of a microwave catalyst;
in the three-stage microwave treatment, the power of the first stage microwave treatment is more than or equal to 200W, the power of the second stage microwave treatment is improved by 20-40% compared with the power of the first stage microwave treatment, and the power of the third stage microwave treatment is improved by 45-65% compared with the power of the second stage microwave treatment;
in the first stage of microwave treatment, the mass ratio of the raw material to the microwave catalyst is (0.5-2): 1;
in the second stage of microwave treatment, mixing the product obtained by the first stage of microwave treatment with the raw materials with the mass of 1.5-10 times of that of the product, and then carrying out microwave treatment;
in the third stage of microwave treatment, the product obtained by the second stage of microwave treatment is mixed with the raw materials with the mass of 0.2-1 time of that of the product, and then the microwave treatment is carried out.
2. The method as claimed in claim 1, wherein in the three-stage microwave treatment, the power of the first stage microwave treatment is 200-;
preferably, the power of the first stage microwave treatment is 500-2000W, the power of the second stage microwave treatment is 800-3000W, and the power of the third stage microwave treatment is 1200-4500W.
3. The method of claim 1 or 2, wherein the first stage of microwave treatment is carried out for a period of 5 to 25 minutes; the time of the second stage of microwave treatment is 10-30 minutes; the time of the third microwave treatment is 5-30 minutes;
preferably, the three-stage microwave treatment is carried out in an environment with standard atmospheric pressure and oxygen content below 5000ppm, and/or the frequency of the three-stage microwave treatment is 2.45GHz or 915 MHz.
4. The method according to any one of claims 1 to 3, wherein the microwave catalyst is a transition metal or a compound thereof, and the transition metal is at least one selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, and tungsten.
5. The preparation method according to any one of claims 1 to 4, wherein the nano carbon material is a multi-walled carbon nanotube, and in the three-stage microwave treatment, the microwave catalyst of the first stage microwave treatment is iron or an iron compound, and the microwave catalysts of the second and third stages microwave treatment are the microwave catalyst of the first stage microwave treatment and an iron-nickel alloy or an iron-nickel compound;
preferably, the particle size of the catalyst is less than 0.5 mm.
6. The preparation method according to claim 5, wherein in the microwave catalyst for the second stage microwave treatment, the mass ratio of iron to nickel is (10-100): 1;
preferably, in the microwave catalyst of the second stage microwave treatment, the mass ratio of iron to nickel is (10-80): 1.
7. the method according to any one of claims 1 to 6, wherein the second stage of microwave treatment comprises: (1) mixing the product obtained by the first stage of microwave treatment with iron-nickel alloy or iron-nickel compound with the mass of 0.05-0.2 time of that of the product, mixing the mixture with the raw material with the mass of 1.5-5 times of that of the product, and then carrying out microwave treatment; (2) mixing the product obtained in the step (1) with the raw materials with the mass of 0.5-5 times of that of the product, and then carrying out microwave treatment under the same conditions as the step (1);
preferably, the second stage of microwave treatment further comprises: (3) repeating the step (2) at least 1 time.
8. The method according to any one of claims 1 to 7, wherein the carbon-based polymer is at least one selected from the group consisting of plastics, chemical fibers, tires, medical waste, biomass, and household garbage.
9. The nanocarbon material produced by the production method according to any one of claims 1 to 8;
preferably, the nano carbon material is a multi-wall carbon nanotube, and the average diameter of the multi-wall carbon nanotube is 2-100 nm; more preferably 5-80 nm.
10. Use of the method of any one of claims 1 to 8 or the nanocarbon material of claim 9 in the preparation of an electrode material, a semiconductor, a catalyst or a composite material.
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| CN202110972727.6A CN114195125A (en) | 2020-10-26 | 2021-08-24 | Preparation method of catalyst for preparing nano carbon material and catalyst |
| CN202110972936.0A CN114195126A (en) | 2020-10-26 | 2021-08-24 | Preparation method of composite nano-carbon material and composite nano-material |
| CN202110972953.4A CN114195127A (en) | 2020-10-26 | 2021-08-24 | Preparation method of nano carbon material |
| PCT/CN2021/141381 WO2022089671A1 (en) | 2020-10-26 | 2021-12-24 | Preparation method for composite nano-carbon material and composite nanomaterial |
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| CN113620277A (en) * | 2021-06-10 | 2021-11-09 | 北京化工大学 | Method for preparing carbon nano tube and hydrogen by high-valued utilization of waste medical masks |
| CN114195125A (en) * | 2020-10-26 | 2022-03-18 | 武汉新碳科技有限公司 | Preparation method of catalyst for preparing nano carbon material and catalyst |
| CN115432663A (en) * | 2021-06-04 | 2022-12-06 | 南京工程学院 | Method and device for preparing hydrogen and multi-walled carbon nanotubes by microwave pyrolysis of waste plastics |
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| CN1583273A (en) * | 2004-06-11 | 2005-02-23 | 中山大学 | Preparing method for loaded metal oxide catalyst |
| CN1750176A (en) * | 2004-09-17 | 2006-03-22 | 中国科学院成都有机化学有限公司 | Method for preparing carbon containing nano tube conductive powder |
| CA2823494C (en) * | 2011-01-19 | 2014-07-08 | Services Kengtek Inc. | Catalyst for distributed batch microwave pyrolysis, system and process thereof |
| 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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| CN107892293A (en) * | 2018-01-08 | 2018-04-10 | 韩笑峰 | A kind of method that graphene is prepared using coal as raw material |
| CN108516534A (en) * | 2018-06-09 | 2018-09-11 | 太原理工大学 | The method of catalyzed conversion solid carbon materials nano-carbon material |
| CN111100662B (en) * | 2018-10-29 | 2021-07-02 | 中国石油化工股份有限公司 | Continuous operation method for microwave pyrolysis of waste plastics |
| CN109759107B (en) * | 2019-03-22 | 2022-02-22 | 湘潭大学 | Composite catalyst and preparation method thereof |
| CN110562960B (en) * | 2019-09-05 | 2022-08-02 | 太原理工大学 | Preparation and purification method of coal-based carbon nano tube |
| CN112238122B (en) * | 2020-09-15 | 2023-06-23 | 介翔宇 | Treatment process for microwave catalytic decomposition of medical waste |
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| CN114195125A (en) * | 2020-10-26 | 2022-03-18 | 武汉新碳科技有限公司 | Preparation method of catalyst for preparing nano carbon material and catalyst |
| CN114195126A (en) * | 2020-10-26 | 2022-03-18 | 武汉新碳科技有限公司 | Preparation method of composite nano-carbon material and composite nano-material |
| WO2022089671A1 (en) * | 2020-10-26 | 2022-05-05 | 武汉新碳科技有限公司 | Preparation method for composite nano-carbon material and composite nanomaterial |
| WO2022089670A1 (en) * | 2020-10-26 | 2022-05-05 | 武汉新碳科技有限公司 | Method for preparing nano-carbon material |
| CN115432663A (en) * | 2021-06-04 | 2022-12-06 | 南京工程学院 | Method and device for preparing hydrogen and multi-walled carbon nanotubes by microwave pyrolysis of waste plastics |
| CN113620277A (en) * | 2021-06-10 | 2021-11-09 | 北京化工大学 | Method for preparing carbon nano tube and hydrogen by high-valued utilization of waste medical masks |
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