CN113003557A - Carbon microsphere and preparation method thereof - Google Patents
Carbon microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a carbon microsphere and a preparation method thereof, belongs to the technical field of sustainable development and new materials, and solves the problem of low recycling rate of waste plastics in the prior art. The preparation material of the carbon microsphere comprises: waste plastic mixture, ferroferric oxide/carbon and Sn-SiO2‑Al2O3(ii) a The waste plastic mixture is at least one of polyvinyl chloride (PVC), Polyethylene (PE), polypropylene (PP), Polystyrene (PS) and polyethylene terephthalate (PET). A carbon microsphere and a preparation method thereof comprise the following steps: (1) uniformly mixing the waste plastics to obtain a waste plastic mixture; (2) waste plastic mixture, ferroferric oxide/carbon and Sn-SiO2‑Al2O3Mixing, carrying out primary heating pyrolysis reaction, and liquefying the product to obtain condensed cyclic tar; (3) the condensed cyclized tar is carbonized at high temperature to obtain the carbon microspheres. The invention realizes the recycling of waste plastics.
Description
Technical Field
The invention relates to the technical field of sustainable development and new materials, in particular to a carbon microsphere prepared from waste mixed plastics and a preparation method thereof.
Background
Plastics are widely used as new materials, and their use in agriculture, automobile industry, electronics, building materials, packaging materials and other fields is rapidly increasing due to their low cost, light weight, durability and easy processing and forming. The plastic product has stable chemical property and is not easy to degrade in natural environment, and if the plastic product can not be effectively applied naturally, a great deal of pollution can be caused. As a large amount of petroleum resources are consumed for producing the plastic monomer, the method has important significance from the perspective of resource recycling, and is one of important key technologies for sustainable development of human society and economy.
There are generally two ways to recycle waste plastics: material recovery and energy recovery. The material recovery includes direct physical recovery, but in reality, the recovered plastics cannot be used for high quality due to the complex composition of the waste plastics. Another material recovery is monomer recovery, which can be thermochemical to convert plastics into valuable monomers or fuel molecules. The energy recovery adopts the incineration mode to generate heat energy, and particularly, for some plastics containing chlorine, bromine or other heteroatoms, toxic substances are generated in the combustion process to cause serious secondary pollution. From the perspective of resource recycling, the waste plastics are very good carbon element raw materials, valuable chemicals, fuels and material precursors can be directionally obtained through a high-selectivity catalytic degradation process, carbon resources in the waste plastics are utilized most effectively, and great waste and secondary pollution are avoided.
Thermosetting polymers or thermosetting-like polymers are commonly used for preparing carbon material precursors, but for waste plastics, the waste plastics are usually a mixture of PVC/PE/PP/PS, have complex components and low melting points, generate low-boiling-point molecules in the carbonization process, and are not suitable for preparing high-performance carbon materials. But through the directional conversion process of the catalyst, the waste plastic mixture can be liquefied into a condensed tar substance, and some heteroatoms and additives are removed, and the condensed tar is an excellent precursor substance for preparing various high-performance carbon materials.
Disclosure of Invention
In view of the above analysis, the embodiment of the present invention aims to provide a method for preparing carbon microspheres from waste mixed plastics, so as to solve the problem of low high value-added recycling rate of the existing waste plastic resources.
The invention is realized by the following technical scheme:
a preparation material of carbon microspheres comprises: waste plastic mixture, ferroferric oxide/carbon and Sn-SiO2-Al2O3(ii) a The waste plastic mixture is polyvinyl chloride(PVC), Polyethylene (PE), polypropylene (PP), Polystyrene (PS), and polyethylene terephthalate (PET). The addition amount of the ferroferric oxide/carbon is 5-30% of the mass of the waste plastic mixture; Sn-SiO2-Al2O3The addition amount is 2-20% of the mass of the waste plastic mixture.
Further, the ferroferric oxide/carbon is particles formed by polymerizing ferroferric oxide powder and furfuryl alcohol, and the mass ratio range of the ferroferric oxide to the furfuryl alcohol is 70: 30-92: 8; the carbon content of the ferroferric oxide/carbon is 5-20%; the Sn-SiO2-Al2O3SiO 22With Al2O3The molar ratio range is 2: 1-10: 1, the loading capacity of tin is 1-10%.
The preparation method of the carbon microsphere is characterized by comprising the following steps:
step 1: uniformly mixing more than two kinds of waste plastics to obtain a waste plastic mixture;
step 2: waste plastic mixture, ferroferric oxide/carbon and Sn-SiO2-Al2O3Mixing, carrying out primary heating pyrolysis reaction, and liquefying the product to obtain condensed cyclic tar;
and step 3: the condensed cyclized tar is carbonized at high temperature to obtain the carbon microspheres.
Further, in the step 1, polyvinyl chloride (PVC), Polyethylene (PE), polypropylene (PP), Polystyrene (PS) and Polyester (PET) are prepared according to the following raw materials in percentage by mass: 20-40%, PE: 20-25%, PP: 15-20%, PS: 20-25% and PET: 5 to 10 percent of waste plastic mixture is obtained by mechanical stirring and mixing at 30 r/min.
Further, in the step 2, the waste plastic mixture, ferroferric oxide/carbon and Sn-SiO2-Al2O3Mixing and adding the mixture into a tubular pyrolysis furnace to perform primary heating pyrolysis reaction to obtain a primary pyrolysis product; the temperature range of the primary heating pyrolysis is 350-550 ℃, the heating rate is 1-5 ℃/min, and the reaction time is 15-90 min.
Further, condensing the primary pyrolysis product, liquefying the primary pyrolysis product, collecting the liquefied primary pyrolysis product to obtain condensed cyclized tar, and absorbing tail gas generated by primary heating pyrolysis by using dilute alkali liquor.
Further, the condensed cyclized tar is gasified in a gasification region of a sectional type high-temperature tube furnace in the step 3, the gasification temperature range is 450-750 ℃, the gasified condensed cyclized tar gas is carried into a high-temperature pyrolysis region by carrier gas, and the carbon microspheres are prepared by direct high-temperature carbonization.
Further, the carrier gas is argon, and the flow rate of the argon gas is 60-300 ml/min.
Further, the temperature range of a high-temperature pyrolysis zone for preparing the carbon microspheres by high-temperature carbonization of the condensed cyclized tar is 800-1200 ℃.
Further, the mass concentration of the dilute alkali liquor is 5-10%.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
1. the invention provides a carbon microsphere and a preparation method thereof, wherein in the prior art, the pyrolysis technology of waste plastics is mainly used for preparing liquid hydrocarbon fuel of C7-C20, and ferroferric oxide/carbon catalyst and Sn-SiO are introduced while the waste plastics are pyrolyzed2-Al2O3A double-acid-site condensed-ring catalyst is prepared through liquefying waste plastic mixture to obtain condensed-ring tar substance, and preparing nano-class carbon microball material with particle size of 4.5-6.0 um and specific surface area of 1000m2/g-1200m2The yield of the carbon microspheres, namely the utilization rate of the waste plastics, reaches more than 40 percent.
2. In the prior art, the carbon microspheres are prepared by a gas-phase thermal cracking method, heavy tar such as deoiled asphalt and the like is used as a raw material, the thermal cracking temperature is over 1000 ℃, and the yield is 20-30%. The invention adopts waste plastic mixture, ferroferric oxide/carbon and Sn-SiO2-Al2O3Mixing, carrying out primary heating pyrolysis reaction, liquefying the product to obtain condensed cyclized tar, and carbonizing the condensed cyclized tar at high temperature to prepare the carbon microspheres with the yield of 40-50%.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a Scanning Electron Microscope (SEM) picture of carbon microspheres from example 1;
FIG. 2 shows the dechlorination process of PVC polymer chain.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
The invention provides a carbon microsphere, which is prepared from the following raw materials: waste plastic mixture, ferroferric oxide/carbon and Sn-SiO2-Al2O3(ii) a Wherein the waste plastic mixture is at least one of polyvinyl chloride (PVC), Polyethylene (PE), polypropylene (PP), Polystyrene (PS) and polyethylene terephthalate (PET).
The mixed waste plastic refers to urban plastic waste or recycled plastic mixture under actual conditions, and chlorine-containing plastic is widely applied to the fields of various packaging materials, clothes, cables, entertainment toy products, household daily necessities, automobile materials and the like, so that a certain amount of PVC is inevitably contained in the plastic waste under the actual conditions. Since the pyrolysis behaviour is different from that of other polyolefins and polyesters compared to PVC, special attention is required, the pyrolysis process of PVC is actually a dechlorination process, which makes the pyrolysis process of the whole mixed waste more complicated due to the presence of chlorine.
Ferroferric oxide/carbon and Sn-SiO2-Al2O3Two catalysts in the preparation process of the carbon microsphere, and the main function of ferroferric oxide/carbon is to absorb HCl gas generated in the pyrolysis processAnd promote high-molecular pyrolysis reaction. In the reaction, ferroferric oxide adsorbs hydrogen chloride to form ferric chloride, the ferric chloride is a dechlorination catalyst, the dechlorination process of the PVC polymer chain is accelerated, meanwhile, the separated hydrogen chloride is gradually absorbed and converted into the ferric chloride to be solidified, and the dechlorination process is shown in figure 2.
The ferroferric oxide/carbon can be selected from commercial products, the product name is ferroferric oxide (99%), and the product model is CAS number 1317-61-9. The following preparation method can also be adopted: and (2) uniformly stirring and mixing 300-800 meshes of ferroferric oxide powder, furfuryl alcohol and a polymerization initiator, heating to 80 ℃ to initiate furfuryl alcohol polymerization until particles are solidified, heating to 450-650 ℃ to carbonize furfuryl alcohol polymer to obtain ferroferric oxide/carbon particles with the carbon content of 5-20%, wherein the average particle size of the ferroferric oxide/carbon particles is 0.5-1.5 mm. Wherein the mass ratio range of the ferroferric oxide to the furfuryl alcohol is 70: 30-92: 8, the polymerization initiator is p-toluenesulfonic acid, and the dosage of the p-toluenesulfonic acid is 0.05 times of the using mass of the furanmethanol. The particle size of 0.5-1.5 mm is favorable for direct liquefaction of primary pyrolysis products, airflow can smoothly pass through the solid layer in the liquefaction process, excessive pressure difference is avoided, particles are too small to easily cause blockage, and the contact time of reaction raw materials and catalyst particles with too large particles is short.
Specifically, the preparation method of the ferroferric oxide/carbon comprises the following steps: selecting 500-mesh ferroferric oxide powder, furfuryl alcohol and a polymerization initiator, stirring and mixing uniformly, heating to 80 ℃ to initiate furfuryl alcohol polymerization until particles are solidified, heating to 500 ℃ to initiate furfuryl alcohol polymer carbonization, and preparing ferroferric oxide/carbon with the average particle size of 1.0mm and the carbon content of 15%. Wherein, the polymerization initiator adopts p-benzene sulfonic acid, and the using amount of the p-benzene sulfonic acid is 0.05 times of the mass of the furan methanol. The organic carbon formed by carbonizing polyfuranyl alcohol has the following main functions: (1) the structure of the catalyst particles is adhesive, (2) the carbon structure can leave a large number of pores while keeping the effective adhesion of the particles, which is beneficial to the mass transfer and the heat transfer in the catalytic process, and (3) the carbon-containing structure is beneficial to increasing the adsorption capacity of the catalyst particles. Wherein the content of carbon is calculated by taking the mechanical strength and density of ferroferric oxide/carbon particles as the basis. The dosage of the ferroferric oxide/carbon is 5-30% of the feeding mass of the mixed waste plastic, and the ferroferric oxide/carbon is a dechlorination catalyst and a chlorine adsorbent in the heating pyrolysis reaction of the mixed waste plastic.
Sn-SiO2-Al2O3The supported catalyst is a Lewis solid acidifying agent and is prepared by coprecipitation of crystalline stannic chloride, tetraethyl silicate and aluminum isopropoxide, the main function of the supported catalyst is to promote the formation of an aromatic ring structure in the high-molecular pyrolysis process, and the catalytic synergistic process can further condense and cyclize a liquefied product to form tar similar to asphalt, so that the supported catalyst is favorable for serving as a precursor raw material for preparing various carbon materials. Sn-SiO2-Al2O3The use amount of the catalyst used as a catalyst for the thick cyclization is 2-20% of the mass of the waste mixed plastic, and the Sn-SiO2-Al2O3SiO 22With Al2O3The molar ratio is 2: 1-10: 1, wherein the loading amount of the tin is 1-10%. SiO 22With Al2O3The molar ratio is 2: 1-10: 1 making the catalyst SiO2-Al2O3The composite site has stronger acidity, which is beneficial to causing carbon-carbon double bond protonation in organic molecules and promoting the generation of benzene ring structures. The loading amount of tin is 1-10%, the tin catalytic sites have the function of catalyzing benzene ring molecules to generate fused ring polymerization to form aromatic ring compounds with large molecular weight, and the amount of tin in the catalyst determines the fused ring degree of the final liquefied product.
Sn-SiO2-Al2O3Can be prepared by the following method: dissolving crystallized stannic chloride, tetraethyl silicate and aluminum isopropoxide in absolute ethyl alcohol, then adding ammonia water as a hydrolysis catalyst, standing for 1.5-3.0 h, filtering and drying the generated solid, and calcining for 0.5-2.0 h in air at the temperature of 650 ℃ to prepare Sn-SiO2-Al2O3A catalyst. Sn-SiO2-Al2O3The usage amount (mass) of each reactant in the preparation is as follows: 0.024-1.0% of crystallized stannic chloride, 2.0-4.0% of tetraethyl silicate, 0.4-4.0% of aluminum isopropoxide and the balance of absolute ethyl alcohol. Wherein the addition amount of ammonia water (mass concentration: 25%) is 15-30% of the total mass of tetraethyl silicate and aluminum isopropoxide.
Specifically, Sn-SiO2-Al2O3SiO 22With Al2O3The molar ratio is 6: 1, the preparation method comprises the following steps: dissolving crystalline stannic chloride, tetraethyl silicate and isopropyl aluminate in absolute ethyl alcohol, adding ammonia water as a hydrolysis catalyst, standing for 2.0h, filtering and drying the generated solid, and calcining at 550 ℃ for 1.0h to obtain Sn-SiO with the tin load of 6 percent2-Al2O3A catalyst. Wherein, Sn-SiO2-Al2O3The usage amount (mass) of each reactant in the preparation is as follows: 0.2 percent of crystallized stannic chloride, 3.0 percent of tetraethyl silicate, 1.0 percent of aluminum isopropoxide and the balance of absolute ethyl alcohol. The addition amount of the ammonia water is 25 percent of the total mass of the tetraethyl silicate and the isopropyl aluminate.
The invention provides a method for preparing carbon microspheres from waste mixed plastics, which comprises the following steps:
step 1: uniformly mixing the waste plastics;
waste polyvinyl chloride (PVC)/Polyethylene (PE)/polypropylene (PP)/Polystyrene (PS)/Polyester (PET) is prepared by the following raw materials in percentage by mass: 20-40%, PE: 20-25%, PP: 15-20%, PS: 20-25% and PET: 5-10 percent, and mechanically stirring and mixing at 30r/min to obtain a waste plastic mixture.
Step 2: waste plastic mixture, ferroferric oxide/carbon and Sn-SiO2-Al2O3Mixing, carrying out primary heating pyrolysis reaction, and liquefying the product to obtain condensed cyclic tar;
waste plastic mixture, ferroferric oxide/carbon and Sn-SiO2-Al2O3Mixing and adding the mixture into a tubular pyrolysis furnace to carry out primary heating pyrolysis reaction to obtain a primary pyrolysis product. Because the pyrolysis process has a large amount of volatile and high-temperature gas, the tubular pyrolysis furnace is favorable for the collection of pyrolysis products, and the tubular furnace can control the reaction temperature more accurately. The primary heating pyrolysis temperature range is 350-550 ℃, the temperature rise rate is 1-5 ℃/min, the reaction time is 15-90 min, and the pyrolysis process aims at carrying out homogenization treatment on the waste plastic mixture, removing heteroatoms and additives in the waste plastic, and simultaneously cracking high moleculesThe product is subjected to a cyclization treatment to form a cyclized dense tar that is susceptible to forming carbosphere. The primary pyrolysis product condenses, the condensation adopts the running water under the room temperature as cooling medium, the condenser is general snakelike condenser pipe, the organic polycyclic fused ring molecule of high boiling point that tubular pyrolysis furnace produced can be cooled off effectively to snakelike condenser pipe, collect after the liquefaction of primary pyrolysis product and obtain the thick cyclization tar, the noncondensable micromolecule gas that primary pyrolysis produced is got rid of with tail gas, tail gas utilizes the dilute alkali liquor of 5 ~ 10% to absorb the processing, the dilute alkali liquor of this concentration range is used for absorbing the acid gas molecule that the pyrolysis process produced has harm to the environment, such as hydrogen chloride, formic acid, acetic acid, acrylic acid, carbon dioxide.
In ferroferric oxide/carbon and Sn-SiO2-Al2O3Under the catalytic action of the catalyst, the waste plastic mixture is liquefied into condensed cyclized tar after primary heating pyrolysis. The carrier gas in the liquefaction process is nitrogen, the usage amount of ferroferric oxide/carbon is 5-30% of the weight of the mixed waste plastic, and the Sn-SiO2-Al2O3The dosage of the condensed cyclization catalyst is 2-20% of the mixed waste plastic. The usage amount of the ferroferric oxide/carbon is calculated according to the content of chlorine in the waste plastic mixture, which is beneficial to removing impurity atoms and inhibiting the generation of chlorine-containing micromolecules. Sn-SiO2-Al2O3The amount of the compound (b) is measured based on the degree of condensation of the product, and the function of the compound (b) is to liquefy the product to form a condensed ring molecule suitable for preparing carbon microspheres.
And step 3: carbonizing the condensed cyclized tar at high temperature to prepare carbon microspheres;
the condensed cyclized tar is carbonized at high temperature in a sectional high-temperature tube furnace to obtain the carbon microspheres. The preparation process of the carbon microspheres adopts a sectional type high-temperature tube furnace, and the reaction of the high-temperature tube furnace is divided into three parts: a gasification section, a high-temperature carbonization section and a cooling collection section.
After the mixed waste plastic condensed cyclized tar is gasified in the gasification section, the gasified tar is carried into the high-temperature section by carrier gas argon to be directly carbonized at high temperature to prepare carbon microspheres, and the prepared carbon microspheres are collected in the cooling collection section.
Firstly, gasifying the condensed cyclized tar in a gasification area of a sectional type high-temperature tube furnace, wherein the gasification temperature range is 450-750 ℃, argon is used as a carrier gas, and the flow rate of the carrier gas is 60-300 ml/min. The temperature range is the boiling point range of fused ring aromatic hydrocarbon molecules, and the carbon microspheres with regular shapes and controllable sizes can be formed after gasification. If the liquid condensed cyclized tar is directly carbonized at high temperature, a coking process is caused, blocky porous coke is formed, and a carbon microsphere structure cannot be formed.
Secondly, the gasified condensed ring tar gas is carried into a high-temperature pyrolysis zone by carrier gas, and is directly carbonized at high temperature to prepare the carbon microspheres. The carrier gas is argon, the flow rate of the carrier gas is 60-300 ml/min, and the temperature of the high-temperature pyrolysis zone is 800-1200 ℃. The carrier gas can lead the gasified tar gas to be in a low-concentration dispersion state, which is beneficial to the generation of carbon microspheres under the high-temperature condition and prevents coking agglomeration. The temperature range of the high-temperature pyrolysis zone is the spheroidization temperature range of the graphite microcrystals, and is beneficial to forming the carbon microspheres.
And finally, the carbon microspheres are carried by carrier gas to enter a cooling and collecting section. The temperature range of the cooling collection section is 300-500 ℃, collection is carried out in the temperature range, the surface temperature of the generated carbon microspheres can not cause secondary aggregation of particles, and a product with good dispersibility can be obtained. The carbon microspheres are collected by the quartz cotton, and the quartz cotton is used as a collecting medium, so that the quartz cotton is high-temperature resistant and high in purity, and secondary pollution can not be brought to products.
Example 1
Table 1: composition of typical mixed waste plastics
Step 1: uniformly mixing the waste plastics;
waste polyvinyl chloride (PVC)/Polyethylene (PE)/polypropylene (PP)/Polystyrene (PS)/Polyester (PET) are mixed according to the proportion shown in the table 1 to obtain a waste plastic mixture.
Step 2: the waste plastic mixture is condensed and cyclized to obtain condensed and cyclized tar;
mixing 100g of waste plastic mixture with trioxaneIron/carbon and Sn-SiO2-Al2O3Mixing, ferroferric oxide/carbon and Sn-SiO2-Al2O3The amounts added are shown in Table 2. And carrying out primary heating pyrolysis on the mixture in a tubular pyrolysis furnace to obtain mixture gas, and carrying out liquefaction and cyclization reaction on the mixture gas to obtain the cyclized tar. The carrier gas is nitrogen, the temperature range of the primary heating pyrolysis reaction is 450 ℃, the heating rate in the pyrolysis process is 3 ℃/min, and the retention time at the set pyrolysis temperature is 30 min. And (4) condensing and collecting pyrolysis products, and absorbing tail gas by using 5% sodium hydroxide alkali liquor.
And step 3: preparing carbon microspheres from the condensed cyclized tar;
the preparation process of the carbon microspheres adopts a sectional type high-temperature tube furnace, 20g of liquefied tar is placed in a quartz boat in a gasification area, and the adopted temperature range is 550 ℃; argon is used as carrier gas in the process, and the flow rate range of the gas is 100 ml/min. The temperature range adopted by high-temperature carbonization is 950 ℃, and quartz wool is adopted to collect the carbon microspheres in a cooling area at 400 ℃.
Table 2: waste mixed plastic, ferroferric oxide/carbon and Sn-SiO2-Al2O3Composition of
Example 2
Step 1: uniformly mixing the waste plastics;
waste polyvinyl chloride (PVC)/Polyethylene (PE)/polypropylene (PP)/Polystyrene (PS)/Polyester (PET) are mixed according to the table 1 to obtain a waste plastic mixture.
Step 2: the waste plastic mixture is condensed and cyclized to obtain condensed and cyclized tar;
mixing waste plastic 100g with ferroferric oxide/carbon 20g and Sn-SiO2-Al2O312 g. Liquefaction and cyclization were carried out in a tubular pyrolysis furnace, the conversion was carried out in a nitrogen atmosphere, and the liquefaction conditions are shown in table 3. And condensing and collecting pyrolysis products. The tail gas is absorbed by 10% sodium hydroxide lye.
And step 3: preparing carbon microspheres from the condensed cyclized tar;
20g of the condensed cyclized tar was placed in a quartz boat in a gasification zone of a sectional high-temperature tube furnace at 550 ℃ with argon as a carrier gas and a gas flow rate of 100 ml/min. After gasifying the condensed cyclized tar in the gasification section, carrying the gasified condensed cyclized tar into the high-temperature section by using carrier gas argon to directly carbonize at high temperature to prepare carbon microspheres, wherein the temperature range adopted by the high-temperature carbonization is 950 ℃, and quartz wool is adopted to collect the carbon microspheres in the cooling zone at 400 ℃.
Table 3: primary heating pyrolysis reaction condition
Example 3
Step 1: uniformly mixing the waste plastics;
waste polyvinyl chloride (PVC)/Polyethylene (PE)/polypropylene (PP)/Polystyrene (PS)/Polyester (PET) are mixed according to the table 1 to obtain a waste plastic mixture.
Step 2: the waste plastic mixture is condensed and cyclized to obtain condensed and cyclized tar;
mixing 100g of waste plastic with 20g of ferroferric oxide/carbon and Sn-SiO2-Al2O312g were mixed to obtain a blend. And carrying out primary heating pyrolysis on the mixture in a tubular pyrolysis furnace to obtain mixture gas, and carrying out liquefaction and cyclization reaction on the mixture gas to obtain the cyclized tar. The carrier gas is nitrogen, the temperature range of the primary heating pyrolysis reaction is 450 ℃, the heating rate in the pyrolysis process is 3 ℃/min, and the retention time at the set pyrolysis temperature is 30 min. And (4) condensing and collecting pyrolysis products, and absorbing tail gas by using 10% sodium hydroxide alkali liquor.
And step 3: preparing carbon microspheres from the condensed cyclized tar;
20g of the fused cyclized tar was placed in a quartz boat in the gasification zone of a sectional high-temperature tube furnace, and the high-temperature gas phase carbonization conditions were carried out using the data shown in Table 4. After the condensed cyclized tar is gasified in the gasification section, the gasified condensed cyclized tar is carried into the high-temperature section by carrier gas argon and is directly carbonized at high temperature to prepare the carbon microspheres. The carbon microspheres are collected by quartz wool in a cooling zone at 400 ℃.
Table 4: high temperature carbonization reaction conditions
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A carbon microsphere, wherein the carbon microsphere is prepared from the following materials: waste plastic mixture, ferroferric oxide/carbon and Sn-SiO2-Al2O3(ii) a The waste plastic mixture is at least one of polyvinyl chloride (PVC), Polyethylene (PE), polypropylene (PP), Polystyrene (PS) and polyethylene terephthalate (PET);
the addition amount of the ferroferric oxide/carbon is 5-30% of the mass of the waste plastic mixture; Sn-SiO2-Al2O3The addition amount is 2-20% of the mass of the waste plastic mixture.
2. The carbon microsphere according to claim 1, wherein the ferroferric oxide/carbon is a particle formed by polymerizing ferroferric oxide powder and furfuryl alcohol, and the mass ratio range of the ferroferric oxide powder to the furfuryl alcohol is 70: 30-92: 8; the carbon content of the ferroferric oxide/carbon is 5-20%; the Sn-SiO2-Al2O3SiO 22With Al2O3The molar ratio range is 2: 1-10: 1, the loading capacity of tin is 1-10%.
3. A preparation method of carbon microspheres, which is used for preparing the carbon microspheres of claims 1-2, and is characterized by comprising the following steps:
step 1: uniformly mixing more than two kinds of waste plastics to obtain a waste plastic mixture;
step 2: waste plastic mixture, ferroferric oxide/carbon and Sn-SiO2-Al2O3Mixing, carrying out primary heating pyrolysis reaction, and liquefying the product to obtain condensed cyclic tar;
and step 3: the condensed cyclized tar is carbonized at high temperature to obtain the carbon microspheres.
4. The preparation method of carbon microspheres according to claim 3, wherein in the step 1, polyvinyl chloride (PVC), Polyethylene (PE), polypropylene (PP), Polystyrene (PS) and Polyester (PET) are prepared according to the following raw materials in percentage by mass: 20-40%, PE: 20-25%, PP: 15-20%, PS: 20-25% and PET: 5 to 10 percent of waste plastic mixture is obtained by mechanical stirring and mixing at the stirring speed of 30 r/min.
5. The preparation method of carbon microspheres according to claim 3, wherein the waste plastic mixture, ferroferric oxide/carbon and Sn-SiO in the step 22-Al2O3Mixing and adding the mixture into a tubular pyrolysis furnace to perform primary heating pyrolysis reaction to obtain a primary pyrolysis product; the temperature range of the primary heating pyrolysis reaction is 350-550 ℃, the heating rate is 1-5 ℃/min, and the reaction time is 15-90 min.
6. The method for preparing carbon microspheres according to claim 5, wherein the primary pyrolysis product is condensed, condensed tar is collected after liquefaction of the primary pyrolysis product, and tail gas generated by primary heating pyrolysis is absorbed by dilute alkali solution.
7. The method as claimed in claim 3, wherein the condensed cyclized tar obtained in step 3 is gasified in a gasification region of a sectional type high temperature tube furnace, the gasification temperature is 450-750 ℃, the gasified condensed cyclized tar gas is carried into the high temperature pyrolysis region by a carrier gas, and the carbon microspheres are directly prepared by high temperature carbonization.
8. The method of claim 7, wherein the carrier gas is argon, and the flow rate of the argon gas is in the range of 60 to 300 ml/min.
9. The method for preparing carbon microspheres according to claim 7, wherein the temperature of the pyrolysis zone for preparing the carbon microspheres by high-temperature carbonization of the condensed cyclic tar is 800-1200 ℃.
10. The method for preparing carbon microspheres according to claim 6, wherein the mass concentration of the dilute alkali solution is 5-10%.
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| US20060062714A1 (en) * | 2004-06-15 | 2006-03-23 | Changchun Institute Of Applied Chemistry Chinese Academy Of Science | Method of preparation for carbon nanotube material |
| JP2007302520A (en) * | 2006-05-12 | 2007-11-22 | Tokai Carbon Co Ltd | Carbon microsphere and its manufacturing method |
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| US20060062714A1 (en) * | 2004-06-15 | 2006-03-23 | Changchun Institute Of Applied Chemistry Chinese Academy Of Science | Method of preparation for carbon nanotube material |
| JP2007302520A (en) * | 2006-05-12 | 2007-11-22 | Tokai Carbon Co Ltd | Carbon microsphere and its manufacturing method |
| CN101817520A (en) * | 2010-04-27 | 2010-09-01 | 中国科学技术大学 | Method for manufacturing carbon microspheres by using waste macromolecules |
| CN106554789A (en) * | 2016-11-22 | 2017-04-05 | 新奥生态环境治理有限公司 | A kind of method for comprehensively treating rubbish |
| CN107934938A (en) * | 2017-12-06 | 2018-04-20 | 武汉光谷环保科技股份有限公司 | The method that two-phase method catalytic pyrolysis waste plastic prepares carbon nanotubes |
| CN110182784A (en) * | 2019-06-25 | 2019-08-30 | 陕西科技大学 | A kind of adjustable iron-containing N doping Lauxite base carbon material in aperture and preparation method thereof |
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