CN104439237A - Preparation method for iron-carbon balls and preparation method for hollow carbon balls - Google Patents
Preparation method for iron-carbon balls and preparation method for hollow carbon balls Download PDFInfo
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- CN104439237A CN104439237A CN201410674307.XA CN201410674307A CN104439237A CN 104439237 A CN104439237 A CN 104439237A CN 201410674307 A CN201410674307 A CN 201410674307A CN 104439237 A CN104439237 A CN 104439237A
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Abstract
The invention provides a preparation method for iron-carbon balls and hollow carbon balls. The preparation method for the iron-carbon balls includes the following steps that one or two of plastic or recycled plastic and an iron-compound are fused and mixed to obtain a mixture; the mixture is heated, reacted and then cooled to obtain the iron-carbon balls. The preparation method for the hollow carbon balls includes the step that the iron-carbon balls and hydrochloric acid with the mass concentration of 5-15 wt% are mixed to obtain the hollow carbon balls. The iron-compound is adopted as a catalyst, the plastic or the recycled plastic is adopted as the carbon source material, and the iron-compound and the plastic or the recycled plastic are easy to obtain and low in cost. In the process of the preparing the hollow carbon balls from the iron-carbon balls, only the diluted hydrochloric acid is used instead of hydrofluoric acid, or concentrated nitric acid or other highly corrosive acid, and therefore operation is safe and easy.
Description
Technical field
The present invention relates to material with carbon element field, the particularly iron-preparation method of carbon ball and the preparation method of hollow carbon balls.
Background technology
Iron-carbon the ball of hollow carbon balls and nucleocapsid structure is the novel material with carbon element of a class.Hollow carbon balls density is low, electric conductivity and excellent heat conductivity, and specific area and pore volume greatly, are widely used in supported catalyst, adsorption fouling thing, prepare the industry such as ultracapacitor and lithium ion battery.Meanwhile, iron-carbon the ball of nucleocapsid structure also causes the attention of people gradually, this kind of material combines excellent properties and the advantage such as iron core catalytic activity and magnetic of hollow carbon balls, is with a wide range of applications at numerous areas such as magnetic absorption separation of heavy metal ions and organic pollution, photocatalysis to degrade organic matter, stored energy and biological monitorings.
Usually, hollow carbon balls material adopts arc discharge method, laser evaporization method, electrochemical vapor deposition and catalysis synthesis process to prepare.The normally organic hydrocarbon Small molecular of carbon source in these methods, such as methane and acetylene etc.Seldom have and adopt organic polymer to prepare the report of hollow carbon balls.Xuecheng Chen reports and utilizes cobalt acetate and organic modification montmonrillonite as combination catalyst, polypropylene is utilized to prepare hollow carbon balls (Xuecheng Chen as carbon source material, HangWang, Junhui He.Synthesis of carbon nanotubes and nanospheres withcontrolled morphology using different catalyst precursors.Nanotechnology 19 (2008) 325607).But the hollow carbon balls productive rate of preparation is lower, can not regulate and control size, needs to use hydrofluoric acid in a large number to remove remaining imvite simultaneously.JiangGong reports and utilizes polystyrene as carbon source material, cobaltosic oxide (or cobalt acetate or cobalt sesquioxide) and organic modification montmonrillonite is utilized to prepare the cobalt-carbon ball of nucleocapsid structure as combination catalyst, hollow carbon balls (Jiang Gong is obtained after purification, Jie Liu, XuechengChen, Xin Wen, Zhiwei Jiang, Ewa Mijowska, Yanhui Wang, Tao Tang.Synthesis, characterization and growth mechanism of mesoporous hollowcarbon nanospheres by catalytic carbonization of polystyrene.Microporous and Mesoporous Materials 176 (2013) 31 – 40).But cobaltosic oxide (or cobalt acetate or cobalt sesquioxide) is somewhat expensive, the toxicity of cobalt ions is comparatively large simultaneously, has potential threat to environment; In addition, purification cobalt-carbon ball is prepared in hollow carbon balls process to be needed to use hydrofluoric acid and red fuming nitric acid (RFNA) in a large number, and thus process is more loaded down with trivial details, more dangerous.
Summary of the invention
The technical problem that the present invention solves is to provide the iron-preparation method of carbon ball and the preparation method of hollow carbon balls, and simple and safe operation, cost is low.
The invention discloses the preparation method of a kind of iron-carbon ball, comprise the following steps:
(A) by one or both in plastics or recycled plastic and iron containing compounds melting mixing, mixture is obtained;
(B) heated by described mixture, after reaction, cooling, obtains iron-carbon ball.
The invention discloses a kind of preparation method of hollow carbon balls, comprise the following steps:
(A) by one or both in plastics or recycled plastic and iron containing compounds melting mixing, mixture is obtained;
(B) heated by described mixture, after reaction, cooling, obtains iron-carbon ball;
(C) be the mixed in hydrochloric acid of 5 ~ 15wt% by described iron-carbon ball and mass concentration, obtain hollow carbon balls.
Preferably, described iron containing compounds is one or more in the complex compound of the oxide of iron, the hydroxide of iron, molysite, ferrous salt, ferric complex and ferrous iron.
Preferably, described iron containing compounds is one or more in di-iron trioxide, ferrous oxide, tri-iron tetroxide, iron hydroxide, ferrous hydroxide, iron chloride, frerrous chloride, ferric bromide, ferrous bromide, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, iron sulfide, ferrous sulfide, ferric acetate, ferric oxalate, ferric carbonate, ferrocene and carbon back iron.
Preferably, one or more the addition in described plastics or recycled plastic is 30 ~ 97.5wt%, and the addition of described iron containing compounds is 2.5 ~ 70wt%.
The particle diameter of preferred described iron containing compounds is 5nm ~ 50 μm.
Preferably, in described step (A), the temperature of described melting mixing is 140 ~ 200 DEG C.
Preferably, described plastics are polypropylene, polyethylene, polystyrene, PETG, PLA, polycaprolactone or poly butylene succinate.
Preferably, the particle diameter of described iron-carbon ball is 5nm ~ 50 μm, and the carbon layers having thicknesses of described iron-carbon ball is 1 ~ 500nm, and the iron karyosome footpath of described iron-carbon ball is 5nm ~ 50 μm.
Preferably, the particle diameter of described hollow carbon balls is 5nm ~ 50 μm, and the carbon layers having thicknesses of described hollow carbon balls is 1 ~ 500nm.
Compared with prior art, the preparation method of iron of the present invention-carbon ball, comprises the following steps: by one or both in plastics or recycled plastic and iron containing compounds melting mixing, obtain mixture; Heated by described mixture, after reaction, cooling, obtains iron-carbon ball.The method that the present invention prepares hollow carbon balls is: be the mixed in hydrochloric acid of 5 ~ 15wt% by described iron-carbon ball and mass concentration, obtains hollow carbon balls.Have employed iron containing compounds in the present invention is catalyst, and plastics or recycled plastic are carbon source material, and both all easily obtain, and cost is low.Secondly, prepare in the process of hollow carbon balls by iron-carbon ball, use watery hydrochloric acid, do not need to use the acid of the severe corrosive such as hydrofluoric acid or red fuming nitric acid (RFNA), simple and safe operation.In addition, experimental result shows, the productive rate that the present invention prepares hollow carbon balls and iron-carbon ball is higher, is respectively more than 20% and more than 25%.
Accompanying drawing explanation
Fig. 1 is the high power transmission electron microscope photo of hollow carbon balls prepared by embodiment 2;
Fig. 2 is the low power transmission electron microscope photo of hollow carbon balls prepared by embodiment 2;
Fig. 3 is the high power transmission electron microscope photo of iron-carbon ball prepared by embodiment 4;
Fig. 4 is the low power transmission electron microscope photo of iron-carbon ball prepared by embodiment 4;
Fig. 5 is the high power transmission electron microscope photo of hollow carbon balls prepared by embodiment 5;
Fig. 6 is the low power transmission electron microscope photo of hollow carbon balls prepared by embodiment 5;
Fig. 7 is the high power transmission electron microscope photo of hollow carbon balls prepared by embodiment 7;
Fig. 8 is the low power transmission electron microscope photo of hollow carbon balls prepared by embodiment 7.
Detailed description of the invention
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses the preparation method of a kind of iron-carbon ball, comprise the following steps:
(A) by one or both in plastics or recycled plastic and iron containing compounds melting mixing, mixture is obtained;
(B) heated by described mixture, after reaction, cooling, obtains iron-carbon ball.
The present invention adopts plastics, recycled plastic or both mixtures to be carbon source material, under the catalytic action of iron containing compounds, by combustion reaction, has prepared iron-carbon ball.
In the present invention, one or both and iron containing compounds melting mixing first in plastics or recycled plastic, obtain mixture.Described plastics or recycled plastic are business-like product, low price.Described plastics are well known to those skilled in the art, are preferably one or more in polypropylene, polyethylene, polystyrene, PETG, PLA, polycaprolactone and poly butylene succinate.When adding different types of plastics or recycled plastic, the present invention is not particularly limited for the adding proportion of various plastics and recycled plastic.One or both addition in described plastics or recycled plastic is preferably 30 ~ 97.5wt%, is more preferably 50 ~ 85wt%.
Described iron containing compounds is catalyst, and toxicity is lower, low price, wide material sources.Described iron containing compounds be preferably in the complex compound of the oxide of iron, the hydroxide of iron, molysite, ferrous salt, ferric complex and ferrous iron one or more; Be more preferably in di-iron trioxide, ferrous oxide, tri-iron tetroxide, iron hydroxide, ferrous hydroxide, iron chloride, frerrous chloride, ferric bromide, ferrous bromide, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, iron sulfide, ferrous sulfide, ferric acetate, ferric oxalate, ferric carbonate, ferrocene and carbon back iron one or more; Most preferably be ferrocene.Using ferrocene as catalyst, itself contains carbon, and can be converted into carbon, catalytic efficiency is higher.The addition of described iron containing compounds is preferably 2.5 ~ 70wt%, is more preferably 15 ~ 50wt%.The particle diameter of described iron containing compounds is preferably 5nm ~ 50 μm, is more preferably 50 ~ 500nm.
Mixture prepared by one or both and iron containing compounds in plastics of the present invention or recycled plastic, can carry out in banbury, the temperature of described melting mixing is preferably 140 ~ 200 DEG C, is more preferably 180 ~ 190 DEG C.The time of described melting mixing is preferably 5 ~ 20 minutes, is more preferably 8 ~ 15 minutes.The rotating speed of described banbury is preferably 70 ~ 100 revs/min.
According to the present invention, by one or both in plastics or recycled plastic and iron containing compounds melting mixing, after obtaining mixture, heated by described mixture, after reaction, cooling, namely obtains iron-carbon ball.The temperature of described heating is preferably 500 ~ 1100 DEG C, is more preferably 700 ~ 900 DEG C.Described heating-up temperature is too high, and consume energy higher uneconomical, temperature is too low, then catalytic effect is poor.The described heat time is preferably plastics or recycled plastic and takes fire to without flame and produce.The iron obtained-carbon ball has nucleocapsid structure, take iron as core, has carbon shell in iron core outer wrap.The particle diameter of described iron-carbon ball and carbon layers having thicknesses adjustable extent are very wide, can be micron order or nanoscale, can prepare the iron-carbon ball of different size and different carbon layers having thicknesses as required.The particle diameter of described iron-carbon ball is preferably 5nm ~ 50 μm, and the carbon layers having thicknesses of described iron-carbon ball is preferably 1 ~ 500nm, and the iron karyosome footpath of described iron-carbon ball is preferably 5nm ~ 50 μm.In certain embodiments, be catalyst with di-iron trioxide, the iron obtained-carbon spherolite footpath is 150 ~ 200 nanometers, and carbon layers having thicknesses is 5 ~ 7 nanometers.In other embodiment, using tri-iron tetroxide as catalyst, the iron obtained-carbon spherolite footpath is 20 ~ 35 nanometers, and carbon layers having thicknesses is 1.5 ~ 2.5 nanometers.Carbon layers having thicknesses is less, and the relative molecular mass mark of iron core is higher, and during for capacitor or lithium battery, the performance of capacitor or lithium battery is better; Or during for adsorbing domain, magnetic is stronger, is more conducive to being separated.
Present invention also offers a kind of preparation method of hollow carbon balls, comprise the following steps:
(A) by one or both in plastics or recycled plastic and iron containing compounds melting mixing, mixture is obtained;
(B) heated by described mixture, after reaction, cooling, obtains iron-carbon ball;
(C) be the mixed in hydrochloric acid of 5 ~ 15wt% by described iron-carbon ball and mass concentration, obtain hollow carbon balls.
In the present invention, one or both and iron containing compounds melting mixing first in plastics or recycled plastic, obtain mixture.Described plastics or recycled plastic are business-like product, low price.Described plastics are well known to those skilled in the art, are preferably one or more in polypropylene, polyethylene, polystyrene, PETG, PLA, polycaprolactone and poly butylene succinate.When adding different types of plastics or recycled plastic, the present invention is not particularly limited for the adding proportion of various plastics and recycled plastic.One or both addition in described plastics or recycled plastic is preferably 30 ~ 97.5wt%, is more preferably 50 ~ 85wt%.
Described iron containing compounds is catalyst, and toxicity is lower, low price, wide material sources.Described iron containing compounds be preferably in the complex compound of the oxide of iron, the hydroxide of iron, molysite, ferrous salt, ferric complex and ferrous iron one or more; Be more preferably in di-iron trioxide, ferrous oxide, tri-iron tetroxide, iron hydroxide, ferrous hydroxide, iron chloride, frerrous chloride, ferric bromide, ferrous bromide, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, iron sulfide, ferrous sulfide, ferric acetate, ferric oxalate, ferric carbonate, ferrocene and carbon back iron one or more; Most preferably be ferrocene.Using ferrocene as catalyst, itself contains carbon, and can be converted into carbon, catalytic efficiency is higher.The addition of described iron containing compounds is preferably 2.5 ~ 70wt%, is more preferably 15 ~ 50wt%.The particle diameter of described iron containing compounds is preferably 5nm ~ 50 μm, is more preferably 50 ~ 500nm.
Mixture prepared by one or both and iron containing compounds in plastics of the present invention or recycled plastic, can carry out in banbury, the temperature of described melting mixing is preferably 140 ~ 200 DEG C, is more preferably 180 ~ 190 DEG C.The time of described melting mixing is preferably 5 ~ 20 minutes, is more preferably 8 ~ 15 minutes.The rotating speed of described banbury is preferably 70 ~ 100 revs/min.
According to the present invention, by one or both in plastics or recycled plastic and iron containing compounds melting mixing, after obtaining mixture, heated by described mixture, after reaction, cooling, namely obtains iron-carbon ball.The temperature of described heating is preferably 500 ~ 1100 DEG C, is more preferably 700 ~ 900 DEG C.Described heating-up temperature is too high, and consume energy higher uneconomical, temperature is too low, then catalytic effect is poor.The described heat time is preferably plastics or recycled plastic and takes fire to without flame and produce.The iron obtained-carbon ball has nucleocapsid structure, take iron as core, has carbon shell in iron core outer wrap.The particle diameter of described iron-carbon ball and carbon layers having thicknesses adjustable extent are very wide, can be micron order or nanoscale, can prepare the iron-carbon ball of different size and different carbon layers having thicknesses as required.The particle diameter of described iron-carbon ball is preferably 5nm ~ 50 μm, and the carbon layers having thicknesses of described iron-carbon ball is preferably 1 ~ 500nm, and the iron karyosome footpath of described iron-carbon ball is preferably 5nm ~ 50 μm.
According to the present invention, after obtaining iron-carbon ball, be the mixed in hydrochloric acid of 5 ~ 15wt% by described iron carbon ball and mass concentration, obtain hollow carbon balls.Described mass concentration is the hydrochloric acid of 5 ~ 15wt%, may be used for removing the iron core in iron-carbon ball, and relative to hydrofluoric acid and red fuming nitric acid (RFNA), safe and simple, more easily implement.Described incorporation time is preferably 24 ~ 48 hours.In order to ensure the purity of hollow carbon balls, preferably after iron-carbon ball mixes with watery hydrochloric acid, being separated, is then 7 by washed with de-ionized water to pH value.The particle diameter of the hollow carbon balls that the present invention obtains is preferably 5nm ~ 50 μm, and the carbon layers having thicknesses of described hollow carbon balls is preferably 1 ~ 500nm.The particle diameter of described hollow ball and carbon layers having thicknesses adjustable extent are very wide, can be micron order or nanoscale, can prepare the hollow carbon balls of different size and different carbon layers having thicknesses as required.
Have employed iron containing compounds in the present invention is catalyst, and plastics or recycled plastic are carbon source material, and both all easily obtain, and cost is low.Secondly, prepare in the process of hollow carbon balls by iron-carbon ball, use watery hydrochloric acid, do not need to use the acid of the severe corrosive such as hydrofluoric acid or red fuming nitric acid (RFNA), simple and safe operation.In addition, experimental result shows, the productive rate that the present invention prepares hollow carbon balls and iron-carbon ball is higher, is respectively more than 20% and more than 25%.
In order to understand the present invention further, be described in detail to the iron provided by the invention-preparation method of carbon ball and the preparation method of hollow carbon balls below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Add in banbury by weight the di-iron trioxide being 0.5 micron by 85% recovery polystyrene and 15% particle diameter simultaneously, under 180 DEG C and 80 revs/min, carry out melting mixing 10 minutes, be recycled polystyrene-di-iron trioxide mixture.
Get said mixture 10 grams to be put in 30 milliliters of crucibles, and add and be placed on crucible.Bottom gas burning lamp flame envelope heating crucible.After a few second, polymer takes fire.Now in crucible, temperature is 1000 DEG C.After polymer no longer burns, take off crucible, be put in shady and cool place and be cooled to room temperature.Now obtain iron-3.25 grams, the carbon ball of the nucleocapsid structure of black, yield is 32.5%.
Joining in above-mentioned black composite with the watery hydrochloric acid that mass concentration is 10%, place 24 hours, centrifugation, is 7 by washed with de-ionized water to pH.Now obtain the hollow carbon balls 2.21 grams that particle diameter is 150 ~ 200 nanometers, carbon layers having thicknesses is 5 ~ 7 nanometers, yield is 22.1%, and the efficiency of carbon con version reclaiming polystyrene is 27.6%.
Embodiment 2
Add in banbury by weight the di-iron trioxide being 0.5 micron by 55% recovery polypropylene and 45% particle diameter simultaneously, under 190 DEG C and 100 revs/min, carry out melting mixing 8 minutes, be recycled polypropylene-di-iron trioxide mixture.
Get said mixture 10 grams to be put in 30 milliliters of crucibles, and add and be placed on crucible.Bottom gas burning lamp flame envelope heating crucible.After a few second, polymer takes fire.Now in crucible, temperature is 900 DEG C.After polymer no longer burns, take off crucible, be put in shady and cool place and be cooled to room temperature.Now obtain iron-5.28 grams, the carbon ball of the nucleocapsid structure of black, yield is 52.8%.
Join in above-mentioned black composite with the watery hydrochloric acid that mass concentration is 15%, place 36 hours, centrifugation, by washed with de-ionized water to pH=7.Now obtain the hollow carbon balls 3.40 grams that particle diameter is 160 ~ 200 nanometers, carbon layers having thicknesses is 5 ~ 7 nanometers, yield is 34.0%, and reclaiming polyacrylic efficiency of carbon con version is 72.1%.
Fig. 1 is the high power transmission electron microscope photo of hollow carbon balls prepared by embodiment 2;
Fig. 2 is the low power transmission electron microscope photo of hollow carbon balls prepared by embodiment 2.
Embodiment 3
By weight 80% polypropylene, polyethylene/polystyrene/(weight fraction is followed successively by 35% to PETG/polychloride vinyl, 40%, 18%, 4% and 3%) mixed plastic and 20% particle diameter are that the tri-iron tetroxide of 50 nanometers adds in banbury simultaneously, under 180 DEG C and 100 revs/min, carry out melting mixing 10 minutes, obtain polypropylene, polyethylene/polystyrene/PETG/polychloride vinyl mixed plastic-tri-iron tetroxide mixture.
Get said mixture 10 grams to be put in 30 milliliters of crucibles, and add and be placed on crucible.Bottom gas burning lamp flame envelope heating crucible.After a few second, polymer takes fire.Now in crucible, temperature is 800 DEG C.After polymer no longer burns, take off crucible, be put in shady and cool place and be cooled to room temperature.Now obtain iron-3.81 grams, the carbon ball of the nucleocapsid structure of black, yield is 38.1%.
Join in above-mentioned black composite with the watery hydrochloric acid that mass concentration is 15%, place 48 hours, centrifugation, by washed with de-ionized water to pH=7.Now obtain the hollow carbon balls 2.50 grams that particle diameter is 20 ~ 35 nanometers, carbon layers having thicknesses is 1.5 ~ 2.5 nanometers, yield is 25.0%, and the efficiency of carbon con version of polypropylene, polyethylene/polystyrene/PETG/polychloride vinyl mixed plastic is 37.0%.
Embodiment 4
By weight reclaiming 50%, polypropylene, polyethylene/polystyrene/(weight fraction is followed successively by 35% to PETG/polychloride vinyl, 40%, 18%, 4% and 3%) mixed plastic and 50% particle diameter are that the tri-iron tetroxide of 50 nanometers adds in banbury simultaneously, under 180 DEG C and 100 revs/min, carry out melting mixing 10 minutes, be recycled polypropylene, polyethylene/polystyrene/PETG/polychloride vinyl mixed plastic-tri-iron tetroxide mixture.
Get said mixture 10 grams to be put in 30 milliliters of crucibles, and add and be placed on crucible.Bottom gas burning lamp flame envelope heating crucible.After a few second, polymer takes fire.Now in crucible, temperature is 700 DEG C.After polymer no longer burns, take off crucible, be put in shady and cool place and be cooled to room temperature.Now obtain iron-5.51 grams, the carbon ball of the nucleocapsid structure of black, yield is 55.1%.
Fig. 3 is the high power transmission electron microscope photo of iron-carbon ball prepared by embodiment 4;
Fig. 4 is the low power transmission electron microscope photo of iron-carbon ball prepared by embodiment 4.
Embodiment 5
By weight reclaiming 50%, polypropylene, polyethylene/polystyrene/(weight fraction is followed successively by 35% to PETG/polychloride vinyl, 40%, 18%, 4% and 3%) mixed plastic and 50% particle diameter are that the tri-iron tetroxide of 50 nanometers adds in banbury simultaneously, under 180 DEG C and 100 revs/min, carry out melting mixing 10 minutes, be recycled polypropylene, polyethylene/polystyrene/PETG/polychloride vinyl mixed plastic-tri-iron tetroxide mixture.
Get said mixture 10 grams to be put in 30 milliliters of crucibles, and add and be placed on crucible.Bottom gas burning lamp flame envelope heating crucible.After a few second, polymer takes fire.Now in crucible, temperature is 700 DEG C.After polymer no longer burns, take off crucible, be put in shady and cool place and be cooled to room temperature.Now obtain iron-5.51 grams, the carbon ball of the nucleocapsid structure of black, yield is 55.1%.
Join in the iron-carbon ball of above-mentioned nucleocapsid structure with the watery hydrochloric acid that mass concentration is 15%, place 24 hours, centrifugation, by washed with de-ionized water to pH=7.Now obtain the hollow carbon balls 3.55 grams that particle diameter is 25 ~ 40 nanometers, carbon layers having thicknesses is 1.5 ~ 2.5 nanometers, yield is 35.5%, and the efficiency of carbon con version reclaiming polypropylene, polyethylene/polystyrene/PETG/polychloride vinyl mixed plastic is 84.0%.
Fig. 5 is the high power transmission electron microscope photo of hollow carbon balls prepared by embodiment 5;
Fig. 6 is the low power transmission electron microscope photo of hollow carbon balls prepared by embodiment 5.
Embodiment 6
Add in banbury by weight the iron hydroxide being 0.75 micron by 70% polyethylene and 30% particle diameter simultaneously, under 160 DEG C and 80 revs/min, carry out melting mixing 10 minutes, obtain polyethylene-iron hydroxide mixture.
Get said mixture 10 grams to be put in 30 milliliters of crucibles, and add and be placed on crucible.Bottom gas burning lamp flame envelope heating crucible.After a few second, polymer takes fire.Now in crucible, temperature is 600 DEG C.After polymer no longer burns, take off crucible, be put in shady and cool place and be cooled to room temperature.Now obtain iron-3.80 grams, the carbon ball of the nucleocapsid structure of black, yield is 38.0%.
Join in the iron-carbon ball of the nucleocapsid structure of above-mentioned black with the watery hydrochloric acid that mass concentration is 10%, place 36 hours, centrifugation, by washed with de-ionized water to pH=7.Now obtain the hollow carbon balls 2.55 grams that particle diameter is 20 ~ 45 nanometers, carbon layers having thicknesses is 2 ~ 3 nanometers, yield is 25.5%, and poly efficiency of carbon con version is 42.5%.
Embodiment 7
Add in banbury by weight the iron hydroxide being 0.75 micron by 60% recovery PLA and 40% particle diameter simultaneously, under 190 DEG C and 80 revs/min, carry out melting mixing 8 minutes, be recycled PLA-iron hydroxide mixture.
Get said mixture 10 grams to be put in 30 milliliters of crucibles, and add and be placed on crucible.Bottom gas burning lamp flame envelope heating crucible.After a few second, polymer takes fire.Now in crucible, temperature is 500 DEG C.After polymer no longer burns, take off crucible, be put in shady and cool place and be cooled to room temperature.Now obtain iron-3.56 grams, the carbon ball of the nucleocapsid structure of black, yield is 35.6%.
Join in the iron-carbon ball of the nucleocapsid structure of above-mentioned black with the watery hydrochloric acid that mass concentration is 15%, place 36 hours, centrifugation, by washed with de-ionized water to pH=7.Now obtain the hollow carbon balls 2.15 grams that particle diameter is 25 ~ 35 nanometers, carbon layers having thicknesses is 2 ~ 3 nanometers, yield is 21.5%, and the efficiency of carbon con version reclaiming PLA is 73.1%.
Fig. 7 is the high power transmission electron microscope photo of hollow carbon balls prepared by embodiment 7;
Fig. 8 is the low power transmission electron microscope photo of hollow carbon balls prepared by embodiment 7.
Embodiment 8
Add in banbury by weight the ferrocene being 0.15 micron by 50% recycle polyethylene and 50% particle diameter simultaneously, under 160 DEG C and 100 revs/min, carry out melting mixing 8 minutes, be recycled polyethylene-ferrocene mixture.
Get said mixture 10 grams to be put in 30 milliliters of crucibles, and add and be placed on crucible.Bottom gas burning lamp flame envelope heating crucible.After a few second, polymer takes fire.Now in crucible, temperature is 800 DEG C.After polymer no longer burns, take off crucible, be put in shady and cool place and be cooled to room temperature.Now obtain iron-4.40 grams, the carbon ball of the nucleocapsid structure of black, yield is 44.0%.
Join in the iron-carbon ball of the nucleocapsid structure of above-mentioned black with the watery hydrochloric acid that mass concentration is 20%, place 48 hours, centrifugation, by washed with de-ionized water to pH=7.Now obtain the hollow carbon balls 3.51 grams that particle diameter is 20 ~ 45 nanometers, carbon layers having thicknesses is 2 ~ 5 nanometers, yield is 35.1%, and the efficiency of carbon con version of recycle polyethylene is 81.9%.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.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 improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments 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 iron-carbon ball, comprises the following steps:
(A) by one or both in plastics or recycled plastic and iron containing compounds melting mixing, mixture is obtained;
(B) heated by described mixture, after reaction, cooling, obtains iron-carbon ball.
2. a preparation method for hollow carbon balls, comprises the following steps:
(A) by one or both in plastics or recycled plastic and iron containing compounds melting mixing, mixture is obtained;
(B) heated by described mixture, after reaction, cooling, obtains iron-carbon ball;
(C) be the mixed in hydrochloric acid of 5 ~ 15wt% by described iron-carbon ball and mass concentration, obtain hollow carbon balls.
3. the preparation method according to claim 1 or 2 any one, is characterized in that, described iron containing compounds is one or more in the complex compound of the oxide of iron, the hydroxide of iron, molysite, ferrous salt, ferric complex and ferrous iron.
4. preparation method according to claim 3, it is characterized in that, described iron containing compounds is one or more in di-iron trioxide, ferrous oxide, tri-iron tetroxide, iron hydroxide, ferrous hydroxide, iron chloride, frerrous chloride, ferric bromide, ferrous bromide, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, iron sulfide, ferrous sulfide, ferric acetate, ferric oxalate, ferric carbonate, ferrocene and carbon back iron.
5. preparation method according to claim 4, is characterized in that, one or more the addition in described plastics or recycled plastic is 30 ~ 97.5wt%, and the addition of described iron containing compounds is 2.5 ~ 70wt%.
6. the preparation method according to claim 1 or 2 any one, is characterized in that, the particle diameter of described iron containing compounds is 5nm ~ 50 μm.
7. the preparation method according to claim 1 or 2 any one, is characterized in that, in described step (A), the temperature of described melting mixing is 140 ~ 200 DEG C.
8. the preparation method according to claim 1 or 2 any one, is characterized in that, described plastics are polypropylene, polyethylene, polystyrene, PETG, PLA, polycaprolactone or poly butylene succinate.
9. preparation method according to claim 1, is characterized in that, the particle diameter of described iron-carbon ball is 5nm ~ 50 μm, and the carbon layers having thicknesses of described iron-carbon ball is 1 ~ 500nm, and the iron karyosome footpath of described iron-carbon ball is 5nm ~ 50 μm.
10. preparation method according to claim 2, is characterized in that, the particle diameter of described hollow carbon balls is 5nm ~ 50 μm, and the carbon layers having thicknesses of described hollow carbon balls is 1 ~ 500nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084341A (en) * | 2015-08-07 | 2015-11-25 | 同济大学 | Method for preparing hollow carbon nanospheres through non-template method and application of hollow carbon nanospheres |
| US10138129B2 (en) | 2016-05-24 | 2018-11-27 | Ford Global Technologies, Llc | Carbon spheres and methods of making the same |
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| CN105084341A (en) * | 2015-08-07 | 2015-11-25 | 同济大学 | Method for preparing hollow carbon nanospheres through non-template method and application of hollow carbon nanospheres |
| CN105084341B (en) * | 2015-08-07 | 2017-03-08 | 同济大学 | Non-template method prepares the application of the method for hollow Nano carbon ball and hollow Nano carbon ball |
| US10138129B2 (en) | 2016-05-24 | 2018-11-27 | Ford Global Technologies, Llc | Carbon spheres and methods of making the same |
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