CN114195127A - Preparation method of nano carbon material - Google Patents
Preparation method of nano carbon material Download PDFInfo
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- CN114195127A CN114195127A CN202110972953.4A CN202110972953A CN114195127A CN 114195127 A CN114195127 A CN 114195127A CN 202110972953 A CN202110972953 A CN 202110972953A CN 114195127 A CN114195127 A CN 114195127A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/30—Purity
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
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- Crystallography & Structural Chemistry (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention provides a preparation method of a nano carbon material, which comprises the following steps: mixing the raw materials with a first 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. The preparation method of the nano carbon material provided by the invention adopts multi-section microwave treatment with gradient power, adopts microwave treatment and flow with gradient power, and adjusts the component proportion of each section of microwave treatment according to requirements, and each section of microwave treatment can be well linked and matched, thereby obviously improving the yield, purity and quality of the carbon nano tube.
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 taking organic wastes including plastics, biomass and the like as raw materials.
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
In order to avoid the defects of the prior art, the invention designs the preparation method of the nano carbon material for improving the yield, purity and quality of the carbon nano tubes in the nano carbon material, so as to solve the problem of low production efficiency 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 nanocarbon material, comprising:
mixing the raw materials with a first 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 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.
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 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 ranges from 500W to 2000W, the microwave power of the second stage microwave treatment ranges from 800W to 3000W, and the microwave power of the third stage microwave treatment ranges from 1200W to 4500W.
As an example, in mixing the raw material with the first catalyst to form the material, the method further comprises:
the ratio of the mass ratio of the feedstock to the first catalyst ranges from 0.5:1 to 2: 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:
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.
as an embodiment, n is 3, and includes 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 1.5:1 to 4: 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.
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:
and adding a second catalyst in at least one microwave treatment from the second microwave treatment to the nth microwave treatment.
As an example, the second catalyst comprises an iron-nickel alloy or an iron-nickel compound.
As an example, the ratio of the mass ratio of iron to nickel in the second catalyst ranges from 4:1 to 100: 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 n-stage microwave treatment at least comprises a first stage microwave treatment and a second stage microwave treatment;
the second microwave treatment is repeated at least once.
As an example, the second stage microwave treatment comprises:
mixing the product obtained by the first stage of microwave treatment, iron-nickel alloy or iron-nickel compound with the mass being 0.05-0.2 time of that of the product obtained by the first stage of microwave treatment and raw materials with the mass being 1.5-5 times of that of the product obtained by the first stage of microwave treatment, and then carrying out microwave treatment;
mixing the product obtained in the step (1) with raw materials with the mass of 0.5-5 times that of the product obtained in the step (1), and then carrying out microwave treatment under the same conditions as the step (1);
repeating the step (2) at least once.
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:
n is 3, and 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 600W to 800W, and the duration is 10min to 20 min;
the microwave power of the second stage of microwave treatment is 900W to 1100W, and the duration is 10min to 25 min;
the microwave power of the third stage of microwave treatment is 1500W to 2000W, and the duration is 15min to 30 min.
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 first catalyst comprises a transition metal or a compound of a transition metal.
As an example, the first catalyst comprises iron or an iron compound or iron carbide.
As an example, the second catalyst comprises a transition metal or a compound of a transition metal; or, the first catalyst and the second catalyst both include a transition metal or a compound of a transition metal, and the composition of the first catalyst is different from that of the second catalyst.
As an example, the transition metal includes one or more of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, and tungsten.
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.
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.
The preparation method of the nano carbon material adopts multi-section type microwave treatment with gradient power and adopts microwave treatment and flow of the gradient power, and the component proportion of each section of microwave treatment is adjusted as required, each section of microwave treatment can be well linked and matched, the yield, the purity and the quality of the carbon nano tube are obviously improved, the average diameter of the prepared multi-walled carbon nano-tube is 5nm to 30nm, the purity can reach more than 90 percent, the yield of the multi-walled carbon nano-tube can reach more than 70 percent, the preparation method has no secondary pollution and meets the requirement of pollutant discharge, combustible gas rich in hydrogen, methane and other gases is generated in the preparation process, can be used for combustion power generation to generate heat or can be recycled and supplied to a 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
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 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 of multi-walled carbon nanotubes 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 of multi-walled carbon nanotubes 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 TEM image of a multi-walled carbon nanotube prepared from polypropylene as a raw material in example 2 of the present invention;
FIG. 10 is a thermogravimetric analysis 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 TEM image of a multi-walled carbon nanotube prepared from mixed PE and PP plastic as a raw material in example 3 of the present invention;
FIG. 13 is a thermogravimetric analysis chart of multi-walled carbon nanotubes prepared from straw (biomass) as a raw material in example 4 of the present invention;
FIG. 14 is a TEM image of a multi-walled carbon nanotube prepared from straw (biomass) as a raw material in example 4 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.
Through the research of the inventor, it is found that for carbon chain polymer substances such as plastics with complex structures, high-yield preparation of the nanocarbon material is difficult to realize by simple one-step microwave treatment, the microwave power has great influence on the yield, purity and quality of the nanocarbon material, the yield improvement of the nanocarbon material by adopting multi-step microwave treatment with equal power is very limited, and the purity or quality of the nanocarbon material is easily influenced by the multi-step microwave treatment with high power, so that the invention provides a preparation method of the nanocarbon material as shown in fig. 1 to 14, which comprises the following steps: mixing the raw materials with a first 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, the microwave treatment and the 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 average diameter of the multi-wall carbon nano tube prepared from the carbon nano tube 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%.
Wherein, when the raw material and the first 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 and decomposition on raw materials such as carbon chain polymers and the like, wherein in the first-stage microwave treatment, a first 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 first 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 produced by the second stage of microwave 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.
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 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.
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 substrate for growth of the nanocarbon material, a growth accumulation process of the nanocarbon material (the raw materials are subjected to a large amount of catalytic decomposition under the combined action of microwaves and a first catalyst, and continue to precipitate and grow on a carbon simple substance substrate formed by the first stage treatment and loading to generate the nanocarbon material) and a curing process of the carbon nanocarbon material (under the action of high-power microwaves and high temperature, the nanocarbon material generated by the second stage of microwave treatment is cured, and the amorphous carbon is converted into the nanocarbon material), and finally the required nanocarbon 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.
In one embodiment, the microwave power of the first stage microwave treatment ranges from 500W to 2000W, the microwave power of the second stage microwave treatment ranges from 800W to 3000W, and the microwave power of the third stage microwave treatment ranges from 1200W to 4500W.
As an example, in mixing the raw material with the first catalyst to form the material, the method further comprises: the ratio of the mass ratio of the feedstock to the first catalyst ranges from 0.5:1 to 2: 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 1.5:1 to 4: 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.
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 microwave treatment catalyst shows that the yield and the purity of the 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 nano carbon material is a multi-walled carbon nanotube, the iron-based and nickel catalyst is matched for use 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 nano carbon material, 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 n-stage microwave treatment at least comprises a first stage microwave treatment and a second stage microwave treatment; the second microwave treatment is repeated at least once.
Specifically, the second stage of microwave treatment comprises: mixing the product obtained by the first stage of microwave treatment, iron-nickel alloy or iron-nickel compound with the mass being 0.05-0.2 time of that of the product obtained by the first stage of microwave treatment and raw materials with the mass being 1.5-5 times of that of the product obtained by the first stage of microwave treatment, and then carrying out microwave treatment; mixing the product obtained in the step (1) with raw materials with the mass of 0.5-5 times that of the product obtained in the step (1), and then carrying out microwave treatment under the same conditions as the step (1); repeating the step (2) at least once.
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: n is 3, and 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 600W to 800W, and the duration is 10min to 20 min; the microwave power of the second stage of microwave treatment is 900W to 1100W, and the duration is 10min to 25 min; the microwave power of the third stage of microwave treatment is 1500W to 2000W, and the duration is 15min to 30 min.
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 first catalyst comprises a transition metal or a compound of a transition metal.
Specifically, the first catalyst comprises iron or an iron compound or iron carbide.
As an example, the second catalyst comprises a transition metal or a compound of a transition metal; or, the first catalyst and the second catalyst both include a transition metal or a compound of a transition metal, and the composition of the first catalyst is different from that 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 first catalyst and/or the second catalyst is less than 0.5 mm. The preferred catalyst particle size is 50nm to 500 μm.
As an example, the microwave power in each microwave treatment is 2.45GHz or 915 MHz.
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.
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 a comparison graph of the prepared multi-walled Carbon nanotubes and TPO of commercial multi-walled Carbon nanotubes (SigmaAldrich, 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 multi-walled carbon nano-tube by using polypropylene plastic as raw material
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 plastic particles are crushed and fully physically and mechanically mixed with 10g of ferroferric oxide powder; 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 a comparison graph of the prepared multi-walled Carbon nanotubes and TPO of commercial multi-walled Carbon nanotubes (SigmaAldrich, 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; then fully physically and mechanically mixing the powder with 10g of ferroferric oxide powder; 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; it was determined that the collected solid product had 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 (sigmaaaldrich, 698849Carbon nanotubes, multi-walled, > 98% Carbon basis, o.d.6-13nm) TPO was as shown in fig. 11, with the multi-walled Carbon nanotubes prepared having a diameter of about 8-25nm (fig. 12) and a multi-walled Carbon nanotube yield of 70.6%.
Example 4:
preparation of multi-walled 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 ferroferric oxide (Fe)3O4) Fully mixing the powder physically and mechanically; will be mixed withPutting the combined sample into a first-stage microwave reactor, and purging under the argon condition (100ml/min) for 10 minutes; setting the microwave power at 800W and the frequency at 2.45GHz, and reacting for 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 particles are crushed and fully physically and mechanically mixed with 10g of ferroferric oxide powder; 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 particles are crushed and fully physically and mechanically mixed with 10g of ferroferric oxide 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 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%.
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 (28)
1. A method for preparing a nano carbon material is characterized by comprising the following steps: the method comprises the following steps:
mixing the raw materials with a first 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.
2. 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:
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.
3. 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 microwave power of the microwave treatment is greater than or equal to 200W.
4. The production method according to claim 3, characterized in that:
n is 3, and comprises 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.
5. The method of claim 4, wherein: the microwave power range of the first stage of microwave treatment is 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.
6. The method of claim 4, 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 800W to 3000W, and the microwave power range of the third stage microwave treatment is 1200W to 4500W.
7. The method of claim 1, wherein: in the mixing configuration of raw materials and first catalyst forms the material, still include:
the ratio of the mass ratio of the feedstock to the first catalyst ranges from 0.5:1 to 2: 1.
8. 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:
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.
9. the method of claim 8, wherein:
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 1.5:1 to 4: 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.
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:
the duration of each microwave treatment is in the range of 5min to 30 min.
11. 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:
and adding a second catalyst in at least one microwave treatment from the second microwave treatment to the nth microwave treatment.
12. The method of claim 11, wherein: the second catalyst comprises an iron-nickel alloy or an iron-nickel compound.
13. The method of manufacturing according to claim 12, wherein: the ratio of the mass ratio of iron to nickel in the second catalyst ranges from 4:1 to 100: 1.
14. 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 n-stage microwave treatment at least comprises a first stage microwave treatment and a second stage microwave treatment;
the second microwave treatment is repeated at least once.
15. The method of claim 14, wherein: the second stage of microwave treatment comprises:
(1) mixing the product obtained by the first stage of microwave treatment, iron-nickel alloy or iron-nickel compound with the mass being 0.05-0.2 time of that of the product obtained by the first stage of microwave treatment and raw materials with the mass being 1.5-5 times of that of the product obtained by the first stage of microwave treatment, and then carrying out microwave treatment;
(2) mixing the product obtained in the step (1) with raw materials with the mass of 0.5-5 times that of the product obtained in the step (1), and then carrying out microwave treatment under the same conditions as the step (1);
repeating the step (2) at least once.
16. 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:
n is 3, and 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 600W to 800W, and the duration is 10min to 20 min;
the microwave power of the second stage of microwave treatment is 900W to 1100W, and the duration is 10min to 25 min;
the microwave power of the third stage of microwave treatment is 1500W to 2000W, and the duration is 15min to 30 min.
17. The method of claim 1, wherein: the starting material comprises a carbon chain polymer.
18. The method of claim 1, wherein: the raw materials comprise one or more of plastics, chemical fibers, tires, medical wastes, biomass and household garbage.
19. The method of claim 1, wherein: the first catalyst comprises a transition metal or a compound of a transition metal.
20. The production method according to claim 1 or 19, characterized in that: the first catalyst comprises iron or an iron compound or iron carbide.
21. The method of claim 11, wherein: the second catalyst comprises a transition metal or a compound of a transition metal; or, the first catalyst and the second catalyst both include a transition metal or a compound of a transition metal, and the composition of the first catalyst is different from that of the second catalyst.
22. The production method according to claim 19 or 21, characterized in that: the transition metal comprises one or more of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum and tungsten.
23. The method of claim 1, wherein: the microwave power in each microwave treatment is 2.45GHz or 915 MHz.
24. 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.
25. The method of claim 24, wherein: in the purification of the product of the last microwave treatment, the method further comprises the following steps:
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.
26. The method of claim 25, 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:
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.
27. The method of claim 25, wherein: the product obtained after the drying and washing further comprises:
drying the washed product in microwave for a preset period of time.
28. The method of claim 24, wherein: in the purification of the product of the last microwave treatment, the method further comprises the following steps:
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.
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| US9487708B2 (en) * | 2011-01-19 | 2016-11-08 | Pyrowave Inc. | Catalyst for distributed batch microwave pyrolysis, system and process thereof |
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