CN103803530A - Preparation method of hollow carbon spheres and preparation method of cobalt-carbon spheres - Google Patents
Preparation method of hollow carbon spheres and preparation method of cobalt-carbon spheres Download PDFInfo
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Abstract
The invention provides a preparation method of hollow carbon spheres. The preparation method comprises the steps of a) fusing and mixing one or two of plastics and recycled plastics, modified montmorillonite and a cobalt compound to obtain a plastic mixture or a recycled plastic mixture, b) heating the plastic mixture or the recycled plastic mixture, reacting and cooling to obtain a compound, c) mixing the compound obtained in the step b) with hydrofluoric acid, reacting and centrifugally separating; mixing the separated solid material with an oxidizing acid, and reacting to obtain the hollow carbon spheres. The invention also provides a preparation method of cobalt-carbon spheres; the preparation process of the cobalt-carbon spheres is similar to the preparation process of the hollow carbon spheres, except that the step c) comprises mixing the compound with the aqueous solution of a strong base and reacting to obtain the cobalt-carbon spheres. The modified montmorillonite, the cobalt compound and the plastics are taken as the raw materials of reactions in the process of preparing the hollow carbon spheres or the cobalt-carbon spheres, and therefore, the yield of the prepared hollow carbon spheres or cobalt-carbon spheres is increased.
Description
Technical field
The present invention relates to material technology field, relate in particular to the preparation method of hollow carbon balls and the preparation method of cobalt-carbon ball.
Background technology
Cobalt-carbon ball of hollow carbon balls and nucleocapsid structure is a kind of novel carbon material.The feature of cobalt-carbon ball of hollow carbon balls and nucleocapsid structure is that it typically has a diameter from tens nanometers to hundreds of nanometer.
Nanometer, micron hollow carbon balls have good chemical stability, thermostability, electroconductibility, thermal conductivity, larger specific surface area and lower density, are a kind of carbon materials with wide application prospect.Due to the above-mentioned advantage of nanometer, micron hollow carbon balls, it is widely used in supported catalyst, absorb polluted matter, prepares the industry such as ultracapacitor and lithium ion battery, in order to meet the demand of nanometer, micron hollow carbon balls, need to there is the low and synthetic technology of nanometer that output is large, micron hollow carbon balls of preparation cost.Meanwhile, cobalt-carbon ball of nanometer, micron nucleocapsid structure also causes people's attention gradually, this class material combines the performance of nanometer, carbon micron-spheres excellence and the advantage of cobalt core catalytic activity and magnetic, has potential application prospect at aspects such as photocatalysis degradation organic contaminant, magnetic absorption separation of heavy metal ions and organic pollutant, energy storage and biological detection.
Conventionally, nanometer, micron hollow carbon balls adopt arc discharge method, laser evaporation method, electrochemical vapor deposition and catalysis synthesis process preparation.The normally organic hydrocarbon small molecules of carbon source in aforesaid method, as: methane, acetylene and ethene etc., seldom have and adopt the carbon source material of organic polymer as preparation nanometer, micron hollow carbon balls.Only Xuecheng Chen has reported using Cobaltous diacetate as catalyzer at present, and polypropylene is prepared the method for hollow carbon balls as carbon source; But hollow carbon balls productive rate prepared by the method very low (being less than 9%) and can not regulate and control the size of hollow carbon balls.The same method of cobalt-carbon ball that polymkeric substance prepares nanometer, micron nucleocapsid structure that adopts is also less.Bassem El Hamaoui has reported and has adopted the method for pyrolysis cobalt complex to prepare cobalt-carbon ball of nucleocapsid structure.This method preparation time is long, productive rate is lower, raw material is expensive, and the most important size of cobalt-carbon ball that makes is wayward.
Summary of the invention
The technical problem that the present invention solves is to provide hollow carbon balls that a kind of productive rate is higher and the preparation method of cobalt-carbon ball.
In view of this, the application provides a kind of preparation method of hollow carbon balls, comprises the following steps:
A) by plastics and recycled plastic one or both, modified montmorillonoid and cobalt compound melting mixing, obtain plastic hybrid or recycled plastic mixture;
B) by described plastic hybrid or the heating of recycled plastic mixture, cooling after reaction, obtain mixture;
C) mixture step b) being obtained mixes with hydrofluoric acid, and centrifugation after reaction mixes the solid material after separating with oxidizing acid, obtain hollow carbon balls after reaction.
Preferably, the content of one or both of described plastics and recycled plastic is 40wt%～95wt%, and the content of described modified montmorillonoid is 2.5wt%～20wt%, and the content of described cobalt compound is 2.5wt%～40wt%; The total amount of described modified montmorillonoid and described cobalt compound is not less than 5wt%.
Preferably, one or more in the oxide compound that described cobalt compound is cobalt, the oxyhydroxide of cobalt, the salt compounds of cobalt and the complex compound of cobalt.
Preferably, the oxide compound of described cobalt is one or more in cobaltous oxide, cobalt sesquioxide and tricobalt tetroxide; The oxyhydroxide of described cobalt is cobaltous hydroxide; The salt compounds of described cobalt is one or more in cobalt chloride, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate and cobaltous carbonate; The complex compound of described cobalt is one or both in dicyclopentadienylcobalt and carbon back cobalt.
Preferably, the particle diameter of described cobalt compound is 0.1～50 μ m; The particle diameter of described modified montmorillonoid is 0.5～50 μ m.
Preferably, described oxidizing acid is nitric acid, and the concentration of described nitric acid is 68.5wt%～98wt%.
Preferably, the particle diameter of described hollow carbon balls is 25nm～200nm, and the carbon-coating thickness of described hollow carbon balls is 4nm～20nm.
The application also provides a kind of preparation method of cobalt-carbon ball, comprises the following steps:
A) by plastics and recycled plastic one or both, modified montmorillonoid and cobalt compound melting mixing, obtain plastic hybrid or recycled plastic mixture;
B) by described plastic hybrid or the heating of recycled plastic mixture, cooling after reaction, obtain mixture;
C), by the aqueous solution of described mixture and highly basic, after reaction, obtain cobalt-carbon ball.
Preferably, described highly basic is sodium hydroxide, and the concentration of the aqueous solution of described sodium hydroxide is 20wt%～40wt%.
Preferably, the particle diameter of described cobalt-carbon ball is 25nm～200nm, and the carbon-coating thickness of described cobalt-carbon ball is 4nm～20nm, and cobalt core is 5nm～200nm.
The application provides the preparation method of a kind of hollow carbon balls and cobalt-carbon ball.In the process of preparation hollow carbon balls or cobalt-carbon ball, take cobalt compound as catalyzer, plastics or recycled plastic are that carbon source material has been prepared hollow carbon balls or cobalt-carbon ball; Modified montmorillonoid can impel the dispersion of cobalt compound, the good distribution of cobalt compound can effectively improve the productive rate of hollow carbon balls or cobalt-carbon ball, modified montmorillonoid can also impel plastics or recycled plastic degraded to generate small molecules hydrocarbon polymer and aromatics simultaneously, and small molecules hydrocarbon polymer and aromatics are the carbon sources of preparation hollow carbon balls or cobalt-carbon ball, therefore the application's preparation method can improve the productive rate of hollow carbon balls or cobalt-carbon ball.Secondly, cobalt compound has the effect of catalyzer, and in preparation process, the amount of cobalt compound can further be controlled productive rate and the size of hollow carbon balls and cobalt-carbon ball, and more cobalt compound can obtain productive rate higher and larger-size hollow carbon balls or cobalt-carbon ball.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the hollow carbon balls prepared of the present invention;
Fig. 2 is the transmission electron microscope photo of the hollow carbon balls prepared of the present invention;
Fig. 3 is the stereoscan photograph of cobalt-carbon ball of preparing of the present invention;
Fig. 4 is the transmission electron microscope photo of cobalt-carbon ball of preparing of the present invention.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The application is for the shortcoming that overcomes prior art hollow carbon balls and cobalt-carbon ball productive rate is lower, raw material is expensive, device complicated and the reaction times is grown, and a kind of business-like plastics take cheapness or recycled plastic are disclosed as raw material, under the effect of cobalt compound catalysis plastics or recycled plastic, the method for cobalt-carbon ball of the hollow carbon balls that synthetic yield is higher and nucleocapsid structure.
According to the present invention, first the embodiment of the present invention discloses a kind of preparation method of hollow carbon balls, comprises the following steps:
A) by plastics and recycled plastic one or both, modified montmorillonoid and cobalt compound melting mixing, obtain plastic hybrid or recycled plastic mixture;
B) by described plastic hybrid or the heating of recycled plastic mixture, cooling after reaction, obtain mixture;
C) mixture step b) being obtained mixes with hydrofluoric acid, and centrifugation after reaction mixes the solid material after separating with oxidizing acid, obtain hollow carbon balls after reaction.
The application in the process of preparation hollow carbon balls, first by plastics and recycled plastic one or both, modified montmorillonoid and cobalt compound melting mixing, obtain plastic hybrid or recycled plastic mixture.The present invention is using business-like plastics, recycled plastic or both mixtures as carbon source, described plastics, recycled plastic are well known to those skilled in the art, can be one or more in polypropylene, polyethylene, polystyrene, poly(lactic acid) and poly butylene succinate.Described cobalt compound is as catalyzer, is preferably one or more in oxyhydroxide, the salt compounds of cobalt and the complex compound of cobalt of oxide compound, cobalt of cobalt; The oxide compound of wherein said cobalt is preferably one or more in cobaltous oxide, cobalt sesquioxide and tricobalt tetroxide, the oxyhydroxide of described cobalt is preferably cobaltous hydroxide, the salt compounds of described cobalt is preferably one or more in cobalt chloride, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate and cobaltous carbonate, and the complex compound of described cobalt is preferably one or both in dicyclopentadienylcobalt and carbon back cobalt.More preferably cobalt sesquioxide, tricobalt tetroxide, Cobaltous diacetate, cobaltous hydroxide, rose vitriol, cobalt chloride or cobaltous carbonate of cobalt compound described in the application.Described in the application, modified montmorillonoid refers to the polynite of polynite through organic or inorganic modification.After modification, the original structure of polynite does not have substantial variation, just between montmorillonite layer, has inserted a small amount of organic molecule chain, such as hexadecylamine, or has inserted mineral ion, such as ammonium ion.
In the preparation process of described plastic hybrid or recycled plastic mixture, with the weight percent meter of described mixture, the content of described plastics, recycled plastic or both mixtures is preferably 40wt%～95wt%, the content of described cobalt compound is preferably 2.5wt%～40wt%, and the content of described modified montmorillonoid is preferably 2.5wt%～20wt%.In certain embodiments, the content of described plastics, recycled plastic or both mixtures is preferably 50wt%～90wt%, more preferably 60wt%～80wt%.In certain embodiments, the content of described modified montmorillonoid is preferably 5wt%～15wt%, more preferably 10wt%～13wt%.In certain embodiments, the content of described cobalt compound is preferably 10wt%～35wt%, more preferably 15wt%～30wt%.For the size that makes hollow carbon balls has better controllability, the particle diameter of described modified montmorillonoid is preferably 0.5 μ m～50 μ m, and more preferably 1 μ m～30 μ m, most preferably is 10 μ m～20 μ m; The particle diameter of described cobalt compound is preferably 0.1 μ m～50 μ m, and more preferably 1 μ m～35 μ m, most preferably is 5 μ m～30 μ m, most preferably is 10 μ m～20 μ m.
Modified montmorillonoid of the present invention can impel the dispersion of cobalt compound and plastic degradation to generate small molecules hydrocarbon polymer and aromatics, thereby improve the productive rate of hollow carbon balls, if therefore the content of described modified montmorillonoid is very few, the raising of the degree of scatter of cobalt compound is just not obvious, also not obvious thereby productive rate improves; If the too high levels of described modified montmorillonoid, economy is poor, and also can not improve a lot to the productive rate of hollow carbon balls.The content of described cobalt compound is more, and the productive rate of hollow carbon balls can be higher, and size is larger, and the content of cobalt compound is fewer, and the productive rate of hollow carbon balls also can be slightly low, and size is slightly little.Plastics described in the application or recycled plastic are less, and cobalt compound is more, and the hollow carbon balls productive rate of preparation could be higher, and size is larger; Described plastics or recycled plastic are more, and relatively less, the hollow carbon balls productive rate of preparation is just slightly low for cobalt compound, and size is less.
The preparation of plastic hybrid or recycled plastic mixture described in the application can be carried out in Banbury mixer, and the temperature of described melting mixing is preferably 140 ℃～200 ℃, more preferably 150 ℃～180 ℃; The time of described melting mixing is preferably 5～20min, more preferably 8min～15min; The rotating speed of described Banbury mixer is preferably 70～100 revs/min.
According to the present invention, after prepared by plastic hybrid or recycled plastic mixture, carry out the preparation of cobalt-carbon ball and montmorillonite composite.The process that the application prepares described mixture is specially:
Plastic hybrid or recycled plastic mixture are heated to 500～950 ℃, make plastic hybrid or recycled plastic mixture burns, it is rear cooling that described mixture stops burning, obtains mixture.
The application is in the process of preparing mixture, modified montmorillonoid impels plastic degradation to generate small molecules hydrocarbon polymer and aromatics, modified montmorillonoid is converted into polynite, meanwhile cobalt compound generation decomposition reaction, generate the oxygen compound of cobalt, these cobalt oxides are catalysis small molecules hydrocarbon polymer and aromatics degraded carbonization again, generates cobalt-carbon ball, has formed the mixture of cobalt-carbosphere and polynite with remaining polynite.
According to the present invention, finally prepared mixture is mixed with hydrofluoric acid, because the primary structure of polynite is silicon-dioxide and aluminium sesquioxide, silicon-dioxide can only be dissolved in hydrofluoric acid, reaction after described mixture mixes with hydrofluoric acid, dissolves the polynite in mixture, simultaneously the part cobalt in dissolved cobalt-carbon ball, then separate after centrifugal and obtain black solid material, above-mentioned black solid material is the mixture that has hollow carbon balls and part cobalt-carbon ball.The application mixes described black solid material subsequently with oxidizing acid, make oxidizing acid remove the cobalt in cobalt-carbon ball, thereby obtain pure hollow carbon balls.The particle diameter of the prepared hollow carbon balls of the present invention is 25nm～200nm, and carbon-coating thickness is 4nm～20nm.Described in the application, oxidizing acid can be nitric acid, can be also the mixture of nitric acid and sulfuric acid; The concentration of described nitric acid is preferably 68.5wt%～98wt%, and the concentration of described sulfuric acid is preferably greater than or equal to 70wt%; If described oxidizing acid is preferably the mixture of sulfuric acid and nitric acid, the volume ratio of described sulfuric acid and nitric acid is preferably 1:1.
The application also provides a kind of preparation method of cobalt-carbon ball, comprises the following steps:
A) by plastics and recycled plastic one or both, modified montmorillonoid and cobalt compound melting mixing, obtain plastic hybrid or recycled plastic mixture;
B) by described plastic hybrid or the heating of recycled plastic mixture, cooling after reaction, obtain mixture;
C), by the aqueous solution of described mixture and highly basic, after reaction, obtain cobalt-carbon ball.
The application is preparing in the process of cobalt-carbon ball, first by plastics and recycled plastic one or both, modified montmorillonoid and cobalt compound melting mixing, obtain plastic hybrid or recycled plastic mixture.The present invention is using business-like plastics, recycled plastic or both mixtures as carbon source, described plastics, recycled plastic are well known to those skilled in the art, can be one or more in polypropylene, polyethylene, polystyrene, poly(lactic acid) and poly butylene succinate.Described cobalt compound is as catalyzer, is preferably one or more in oxyhydroxide, the salt compounds of cobalt and the complex compound of cobalt of oxide compound, cobalt of cobalt; The oxide compound of wherein said cobalt is preferably one or more in cobaltous oxide, cobalt sesquioxide and tricobalt tetroxide, the oxyhydroxide of described cobalt is preferably cobaltous hydroxide, the salt compounds of described cobalt is preferably one or more in cobalt chloride, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate and cobaltous carbonate, and the complex compound of described cobalt is preferably one or both in dicyclopentadienylcobalt and carbon back cobalt.More preferably cobalt sesquioxide, tricobalt tetroxide, Cobaltous diacetate, cobaltous hydroxide, rose vitriol, cobalt chloride or cobaltous carbonate of cobalt compound described in the application.Described in the application, modified montmorillonoid refers to the polynite of polynite through organic or inorganic modification.
In the preparation process of described plastic hybrid or recycled plastic mixture, with the weight percent meter of described mixture, the content of described plastics, recycled plastic or both mixtures is preferably 40wt%～95wt%, the content of described cobalt compound is preferably 2.5wt%～40wt%, and the content of described modified montmorillonoid is preferably 2.5wt%～20wt%.In certain embodiments, the content of described plastics, recycled plastic or both mixtures is preferably 50wt%～90wt%, more preferably 60wt%～80wt%.In certain embodiments, the content of described modified montmorillonoid is preferably 5wt%～15wt%, more preferably 10wt%～13wt%.In certain embodiments, the content of described cobalt compound is preferably 10wt%～35wt%, more preferably 15wt%～30wt%.For the size that makes cobalt-carbon ball has better controllability, the particle diameter of described modified montmorillonoid is preferably 0.5 μ m～50 μ m, and more preferably 1 μ m～30 μ m, most preferably is 10 μ m～20 μ m; The particle diameter of described cobalt compound is preferably 0.1 μ m～50 μ m, and more preferably 1 μ m～35 μ m, most preferably is 5 μ m～30 μ m, most preferably is 10 μ m～20 μ m.
Modified montmorillonoid of the present invention can impel the dispersion of cobalt compound and plastic degradation to generate small molecules hydrocarbon polymer and aromatics, thereby improve the productive rate of cobalt-carbon ball, if therefore the content of described modified montmorillonoid is very few, the raising of the degree of scatter of cobalt compound is just not obvious, also not obvious thereby productive rate improves; If the too high levels of described modified montmorillonoid, economy is poor, and also can not improve a lot to the productive rate of cobalt-carbon ball.The content of described cobalt compound is more, and the productive rate of cobalt-carbon ball can be higher, and size is larger, and the content of cobalt compound is fewer, and the productive rate of cobalt-carbon ball also can be slightly low, and size is slightly little.Plastics described in the application or recycled plastic are less, and cobalt compound is more, and cobalt-carbon ball productive rate of preparation could be higher, and size is larger; Described plastics or recycled plastic are more, and relatively less, cobalt-carbon ball productive rate of preparation is just slightly low for cobalt compound, and size is less.
The preparation of plastic hybrid or recycled plastic mixture described in the application can be carried out in Banbury mixer, and the temperature of described melting mixing is preferably 140 ℃～200 ℃, more preferably 150 ℃～180 ℃; The time of described melting mixing is preferably 5～20min, more preferably 8min～15min; The rotating speed of described Banbury mixer is preferably 70～100 revs/min.
According to the present invention, after prepared by plastic hybrid or recycled plastic mixture, the cobalt-carbon ball carrying out and the preparation of montmorillonite composite.The process that the application prepares described mixture is specially:
Plastic hybrid or recycled plastic mixture are heated to 500～950 ℃, make plastic hybrid or recycled plastic mixture burns, it is rear cooling that described mixture stops burning, obtains mixture.
The application is in the process of preparing mixture, modified montmorillonoid impels plastic degradation to generate small molecules hydrocarbon polymer and aromatics, modified montmorillonoid is converted into polynite, meanwhile cobalt compound generation decomposition reaction, generate the oxygen compound of cobalt, these cobalt oxides are catalysis small molecules hydrocarbon polymer and aromatics degraded carbonization again, generates cobalt-carbon ball, has formed the mixture of cobalt-carbosphere and polynite with remaining polynite.
According to the present invention, finally by the aqueous solution of described mixture and highly basic, after reaction, obtain cobalt-carbon ball of nucleocapsid structure.Aluminium sesquioxide in polynite in described mixture can only react with highly basic, and in preparation process, can not cause the minimizing of cobalt, thereby has obtained cobalt-carbon ball.Described highly basic is preferably sodium hydroxide, and the concentration of described sodium hydroxide is preferably 20wt%～40wt%.The time of described reaction is preferably 12～24h.For the purity the application who guarantees cobalt-carbon ball preferably the product deionized water obtaining after reaction is cleaned to pH be 7, obtain pure cobalt-carbon ball.
The application provides the preparation method of a kind of hollow carbon balls and cobalt-carbon ball.In the process of preparation hollow carbon balls or cobalt-carbon ball, take cobalt compound as catalyzer, plastics or recycled plastic are that carbon source material has been prepared hollow carbon balls or cobalt-carbon ball; Modified montmorillonoid can impel the dispersion of cobalt compound, the good distribution of cobalt compound can effectively improve the productive rate of hollow carbon balls or cobalt-carbon ball, modified montmorillonoid can also impel plastics or recycled plastic degraded to generate small molecules hydrocarbon polymer and aromatics simultaneously, and small molecules hydrocarbon polymer and aromatics are the carbon sources of preparation hollow carbon balls or cobalt-carbon ball, therefore the application's preparation method can improve the productive rate of hollow carbon balls or cobalt-carbon ball.Secondly, cobalt compound has the effect of catalyzer, and in preparation process, the amount of cobalt compound can further be controlled productive rate and the size of hollow carbon balls and cobalt-carbon ball, and more cobalt compound can obtain higher yields and larger-size hollow carbon balls or cobalt-carbon ball.On the other hand, the carbon source material adopting in the present invention is business-like plastics or recycled plastic, cheap, and source is abundant; The cobalt compound adopting is easy to get, and the mixing equipment using is the common equipment of materials processing, synthesizes the equipment simple general-purpose of cobalt-carbon ball of the controlled nanometer of size, micron hollow carbon balls and nucleocapsid structure, easy to implement.Comprehensive above-mentioned advantage, adopts the cost of cobalt-carbon ball of the controlled nanometer of method preparation size of the present invention, micron hollow carbon balls and nucleocapsid structure to have advantage than other method.Experimental result shows, the productive rate of hollow carbon balls prepared by the present invention reaches as high as 45%, and the productive rate of cobalt-carbon ball reaches as high as 75%.
In order further to understand the present invention, below in conjunction with embodiment, the preparation method of hollow carbon balls provided by the invention and cobalt-carbon ball is elaborated, protection scope of the present invention is not limited by the following examples.
The raw material adopting in following examples is commercially available prod.
By weight be that the modified montmorillonoid of 0.5 micron 5%, the cobalt sesquioxide that particle diameter is 0.5 micron 10% add in Banbury mixer by 85%% polystyrene and particle diameter simultaneously, under 190 ℃ and 70 revs/min, carry out melting mixing 5 minutes, obtain polystyrene blends.
Get 10 grams of said mixtures and be put in 30 milliliters of crucibles, and add and be placed on crucible.With gas burning lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.Now in crucible, temperature is 500 ℃.Polymkeric substance takes off crucible after no longer burning, and is put in shady and cool place and is cooled to room temperature.2.5 grams of cobalt-carbon ball/montmorillonite composites that now obtain nucleocapsid structure, yield is 25%.
Join in above-mentioned black composite with the hydrofluoric acid that mass concentration is 10%, place 24 hours.After centrifugation, obtain black carbon powder.Then adding volume ratio is the vitriol oil of 1:1 and the mixture of concentrated nitric acid, reflux after 2 hours, taking-up carries out centrifugation, by washed with de-ionized water to pH=7, the particle diameter that obtains purifying is that 25 nanometer～40 nanometers, carbon-coating thickness are 1.5 grams of the hollow carbon balls of 4 nanometer～8 nanometers, yield is 15%.
Embodiment 2
By weight be that the modified montmorillonoid of 40 micron 5%, the tricobalt tetroxide that particle diameter is 2 micron 15% add in Banbury mixer by 80% recovery polystyrene and particle diameter simultaneously, under 180 ℃ and 100 revs/min, carry out melting mixing 10 minutes, obtain polystyrene blends.
Get 10 grams of said mixtures and be put in 50 milliliters of crucibles, and add and be placed on crucible.With gas burning lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.Now in crucible, temperature is 600 ℃.Polymkeric substance takes off crucible after no longer burning, and is put in shady and cool place and is cooled to room temperature.3.8 grams of cobalt-carbon ball/montmorillonite composites that now obtain nucleocapsid structure, yield is 38%.
Join in above-mentioned black composite with the hydrofluoric acid that mass concentration is 20%, place 36 hours.After centrifugation, obtain black carbon powder.Then adding volume ratio is the vitriol oil of 1:1 and the mixture of concentrated nitric acid, reflux after 4 hours, taking-up carries out centrifugation, by washed with de-ionized water to pH=7, the particle diameter that obtains purifying is that 40 nanometer～60 nanometers, carbon-coating thickness are 2.5 grams of the hollow carbon balls of 5 nanometer～10 nanometers, yield is 25%.
Embodiment 3
By weight being that the modified montmorillonoid of 10 micron 10%, the Cobaltous diacetate that particle diameter is 5 micron 30% add in Banbury mixer by 50% polystyrene and 10% polypropylene and particle diameter simultaneously, under 190 ℃ and 70 revs/min, carry out melting mixing 15 minutes, obtain polystyrene/polypropylene miser.
Get 10 grams of said mixtures and be put in 30 milliliters of crucibles, and add and be placed on crucible.With gas burning lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.Now in crucible, temperature is 700 ℃.Polymkeric substance takes off crucible after no longer burning, and is put in shady and cool place and is cooled to room temperature.5.6 grams of cobalt-carbon ball/montmorillonite composites that now obtain nucleocapsid structure, yield is 56%.
Join in above-mentioned black composite with the hydrofluoric acid that mass concentration is 30%, place 48 hours.After centrifugation, obtain black carbon powder.Then adding volume ratio is the vitriol oil of 1:1 and the mixture of concentrated nitric acid, reflux after 2 hours, taking-up carries out centrifugation, by washed with de-ionized water to pH=7, the particle diameter that obtains purifying is that 70 nanometer～90 nanometers, carbon-coating thickness are 3.5 grams of the hollow carbon balls of 10 nanometer～20 nanometers, yield is 35%.
Embodiment 4
Be that the modified montmorillonoid of 1 micron, the cobaltous hydroxide that 40% particle diameter is 10 microns add in Banbury mixer simultaneously by 15% polystyrene, 15% polypropylene and 20% polyethylene and 10% particle diameter by weight, under 190 ℃ and 100 revs/min, carry out melting mixing 20 minutes, obtain polystyrene/polypropylene, polyethylene mixture.
Get 10 grams of said mixtures and be put in 50 milliliters of crucibles, and add and be placed on crucible.With gas burning lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.Now in crucible, temperature is 700 ℃.Polymkeric substance takes off crucible after no longer burning, and is put in shady and cool place and is cooled to room temperature.6.8 grams of cobalt-carbon ball/montmorillonite composites that now obtain nucleocapsid structure, yield is 68%.
Join in above-mentioned black composite with the hydrofluoric acid that mass concentration is 20%, place 24 hours.After centrifugation, obtain black carbon powder.Then adding volume ratio is the vitriol oil of 1:1 and the mixture of concentrated nitric acid, reflux after 4 hours, taking-up carries out centrifugation, by washed with de-ionized water to pH=7, the particle diameter that obtains purifying is that 90 nanometer～120 nanometers, carbon-coating thickness are 4.5 grams of the hollow carbon balls of 10 nanometer～20 nanometers, yield is 45%.
Embodiment 5
By weight be that the modified montmorillonoid of 5 microns, the rose vitriol that 40% particle diameter is 20 microns add in Banbury mixer by 50% poly(lactic acid) and 10% particle diameter simultaneously, under 180 ℃ and 70 revs/min, carry out melting mixing 10 minutes, obtain poly-lactic acid mixture.
Get 10 grams of said mixtures and be put in 30 milliliters of crucibles, and add and be placed on crucible.With gas burning lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.Now in crucible, temperature is 800 ℃.Polymkeric substance takes off crucible after no longer burning, and is put in shady and cool place and is cooled to room temperature.5.0 grams of cobalt-carbon ball/montmorillonite composites that now obtain nucleocapsid structure, yield is 50%.
Join in above-mentioned black composite with the hydrofluoric acid that mass concentration is 10%, place 36 hours.After centrifugation, obtain black carbon powder.Then adding volume ratio is the vitriol oil of 1:1 and the mixture of concentrated nitric acid, reflux after 3 hours, take out carry out centrifugation, by washed with de-ionized water to pH=7.The particle diameter that now obtains purifying is that 70 nanometer～100 nanometers, carbon-coating thickness are 3.0 grams of the hollow carbon balls of 10 nanometer～20 nanometers, and yield is 30%.
Embodiment 6
By weight being that the modified montmorillonoid of 10 microns, the cobalt chloride that 30% particle diameter is 1 micron add in Banbury mixer by 40% polystyrene and 20% polypropylene and 10% particle diameter simultaneously, under 190 ℃ and 70 revs/min, carry out melting mixing 20 minutes, obtain polystyrene/polypropylene miser.
Get 10 grams of said mixtures and be put in 50 milliliters of crucibles, and add and be placed on crucible.With gas burning lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.Now in crucible, temperature is 800 ℃.Polymkeric substance takes off crucible after no longer burning, and is put in shady and cool place and is cooled to room temperature.5.9 grams of cobalt-carbon ball/montmorillonite composites that now obtain nucleocapsid structure, yield is 59%.
Join in above-mentioned black composite with the sodium hydroxide that mass concentration is 40%, reflux 48 hours, after separation, to pH=7, obtain cobalt-carbon ball of purifying by washed with de-ionized water.The particle diameter that now obtains purifying is that 70 nanometer～95 nanometers, carbon-coating thickness are that 10 nanometer～20 nanometers, cobalt core are 5 grams, cobalt-carbon ball of 50 nanometer～85 nanometers, and yield is 50%.
Embodiment 7
Be that the modified montmorillonoid of 20 microns, the cobaltous carbonate that 40% particle diameter is 10 microns add in Banbury mixer simultaneously by 20% recovery polystyrene, 15% polypropylene and 15% polyethylene and 10% particle diameter by weight, under 180 ℃ and 100 revs/min, carry out melting mixing 5 minutes, obtain polystyrene/polypropylene, polyethylene mixture.
Get 10 grams of said mixtures and be put in 30 milliliters of crucibles, and add and be placed on crucible.With gas burning lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.Now in crucible, temperature is 900 ℃.Polymkeric substance takes off crucible after no longer burning, and is put in shady and cool place and is cooled to room temperature.7.0 grams of cobalt-carbon ball/montmorillonite composites that now obtain nucleocapsid structure, yield is 70%.
Join in above-mentioned black composite with the sodium hydroxide that mass concentration is 30%, reflux 36 hours, after separation, to pH=7, obtain cobalt-carbon ball of purifying by washed with de-ionized water.The particle diameter that now obtains purifying is that 100 nanometer～130 nanometers, carbon-coating thickness are that 15 nanometer～25 nanometers, cobalt core are 6.3 grams, cobalt-carbon ball of 75 nanometer～115 nanometers, and yield is 63%.
Embodiment 8
By weight be that the modified montmorillonoid of 10 microns, the tricobalt tetroxide that 40% particle diameter is 4 microns add in Banbury mixer by 55% polystyrene and 5% particle diameter simultaneously, under 180 ℃ and 100 revs/min, carry out melting mixing 5 minutes, obtain polystyrene blends.
Get 10 grams of said mixtures and be put in 30 milliliters of crucibles, and add and be placed on crucible.With gas burning lamp flame envelope heating crucible bottom.After several seconds, polymkeric substance takes fire.Now in crucible, temperature is 850 ℃.Polymkeric substance takes off crucible after no longer burning, and is put in shady and cool place and is cooled to room temperature.8.15 grams of cobalt-carbon ball/montmorillonite composites that now obtain nucleocapsid structure, yield is 81.5%.
Join in above-mentioned black composite with the sodium hydroxide that mass concentration is 30%, reflux 24 hours, after separation, to pH=7, obtain cobalt-carbon ball of purifying by washed with de-ionized water.The particle diameter that now obtains purifying is that 100 nanometer～130 nanometers, carbon-coating thickness are that 15 nanometer～25 nanometers, cobalt core are 7.50 grams, cobalt-carbon ball of 75 nanometer～115 nanometers, and yield is 75.0%.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.To be apparent for those skilled in the art to the multiple modification of these embodiment, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a preparation method for hollow carbon balls, comprises the following steps:
A) by plastics and recycled plastic one or both, modified montmorillonoid and cobalt compound melting mixing, obtain plastic hybrid or recycled plastic mixture;
B) by described plastic hybrid or the heating of recycled plastic mixture, cooling after reaction, obtain mixture;
C) mixture step b) being obtained mixes with hydrofluoric acid, and centrifugation after reaction mixes the solid material after separating with oxidizing acid, obtain hollow carbon balls after reaction.
2. preparation method according to claim 1, it is characterized in that, the content of one or both of described plastics and recycled plastic is 40wt%～95wt%, and the content of described modified montmorillonoid is 2.5wt%～20wt%, and the content of described cobalt compound is 2.5wt%～40wt%; The total amount of described modified montmorillonoid and described cobalt compound is not less than 5wt%.
3. preparation method according to claim 1, is characterized in that, one or more in the oxide compound that described cobalt compound is cobalt, the oxyhydroxide of cobalt, the salt compounds of cobalt and the complex compound of cobalt.
4. preparation method according to claim 3, is characterized in that, the oxide compound of described cobalt is one or more in cobaltous oxide, cobalt sesquioxide and tricobalt tetroxide; The oxyhydroxide of described cobalt is cobaltous hydroxide; The salt compounds of described cobalt is one or more in cobalt chloride, rose vitriol, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate and cobaltous carbonate; The complex compound of described cobalt is one or both in dicyclopentadienylcobalt and carbon back cobalt.
5. preparation method according to claim 1, is characterized in that, the particle diameter of described cobalt compound is 0.1～50 μ m; The particle diameter of described modified montmorillonoid is 0.5～50 μ m.
6. preparation method according to claim 1, is characterized in that, described oxidizing acid is nitric acid, and the concentration of described nitric acid is 68.5wt%～98wt%.
7. according to the preparation method described in claim 1～5 any one, it is characterized in that, the particle diameter of described hollow carbon balls is 25nm～200nm, and the carbon-coating thickness of described hollow carbon balls is 4nm～20nm.
8. a preparation method for cobalt-carbon ball, comprises the following steps:
A) by plastics and recycled plastic one or both, modified montmorillonoid and cobalt compound melting mixing, obtain plastic hybrid or recycled plastic mixture;
B) by described plastic hybrid or the heating of recycled plastic mixture, cooling after reaction, obtain mixture;
C), by the aqueous solution of described mixture and highly basic, after reaction, obtain cobalt-carbon ball.
9. preparation method according to claim 8, is characterized in that, described highly basic is sodium hydroxide, and the concentration of the aqueous solution of described sodium hydroxide is 20wt%～40wt%.
10. the preparation method described according to Claim 8～9 any one, is characterized in that, the particle diameter of described cobalt-carbon ball is 25nm～200nm, and the carbon-coating thickness of described cobalt-carbon ball is 4nm～20nm, and the particle diameter of cobalt core is 5nm～200nm.
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| CN104445148A (en) * | 2014-11-19 | 2015-03-25 | 中国科学院长春应用化学研究所 | Preparation method of monodispersed hollow carbon spheres |
| CN104439237A (en) * | 2014-11-20 | 2015-03-25 | 中国科学院长春应用化学研究所 | Preparation method for iron-carbon balls and preparation method for hollow carbon balls |
| CN116239102A (en) * | 2023-02-08 | 2023-06-09 | 广东碳语新材料有限公司 | Method for preparing polyhedral carbon-shell material by using waste plastics |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104445148A (en) * | 2014-11-19 | 2015-03-25 | 中国科学院长春应用化学研究所 | Preparation method of monodispersed hollow carbon spheres |
| CN104439237A (en) * | 2014-11-20 | 2015-03-25 | 中国科学院长春应用化学研究所 | Preparation method for iron-carbon balls and preparation method for hollow carbon balls |
| CN116239102A (en) * | 2023-02-08 | 2023-06-09 | 广东碳语新材料有限公司 | Method for preparing polyhedral carbon-shell material by using waste plastics |
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