CN101850960B - Method for preparing carbon micro-spheres by using coal as raw material - Google Patents
Method for preparing carbon micro-spheres by using coal as raw material Download PDFInfo
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- CN101850960B CN101850960B CN2010101920510A CN201010192051A CN101850960B CN 101850960 B CN101850960 B CN 101850960B CN 2010101920510 A CN2010101920510 A CN 2010101920510A CN 201010192051 A CN201010192051 A CN 201010192051A CN 101850960 B CN101850960 B CN 101850960B
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Abstract
The invention provides a method for preparing carbon micro-spheres by using coal as a raw material, and belongs to the technical field of coal made carbon materials with high additional values. The method comprises the following steps of: taking a product obtained through the reaction of the coal, sodium hydroxide and methanol as a carbon source, dissolving the reaction product carbon source into aqueous solution of ethanol, then adding a dodecyl trimethyl ammonium bromide or tetradecyl trimethyl ammonium bromide or hexadecyl trimethyl ammonium bromide directing agent into the solution to obtain a mixture, blending the mixture uniformly and filling the mixture into a reaction kettle, heating the mixture to between 300 and 700 DEG C in a heating furnace, stopping heating after the mixture is reacted for 6 to 24 hours, naturally cooling the reaction product to room temperature, washing the reaction product by using ethanol and then deionized water, and finally drying the reaction product to obtain black powdery carbon micro-spheres. The carbon micro-sphere product obtained by the method has high purity, the purity can reach 95 percent, and the average grain diameter of the product is 5 to 10 microns. The method has the characteristics of low-cost and easily obtained raw materials, easy operation, simple process, good reproducibility and suitability for scale production.
Description
Technical field
The coal system of the invention belongs to high added value carbon material technical field is specifically related to a kind of method of using coal as the feedstock production carbon micro-spheres.
Background technology
Since C60 and carbon nanotube discovery, worldwide just carried out comprehensive research to carbon materials.The different-shape carbon material has the potential using value in many aspects, and the carbon material that therefore has unique texture has caused people's extensive concern.Many different-shape carbon materials such as carbon green onion, Graphene, carbon pipe, carbon ball etc. are synthetic by successfully.In the carbon material of these different-shapes, the carbon ball is similar to soccerballene as a kind of type material owing to it or graphite properties comes into one's own.The performance of these similar quality and the many excellences of carbon ball; For example self sintering, unreactiveness, high-bulk-density, good electrical and thermal conductivity and oilness etc. make the carbon ball be widely used in the fields such as carrier of the preparation of diamond film, senior lubricant, special rubber accelerator, high-strength composite material, sorbent material, ion secondary battery cathode material lithium and catalyzer.
The method for preparing at present the carbon ball is a lot, comprises pyrolytic decomposition, arc discharge method, mixing oxycarbide catalyze, template and the solvent-thermal method etc. of chemical Vapor deposition process, carbon source and catalyzer.Wherein, solvent-thermal method is synthetic a kind of effective ways with special construction and performance compound and novel material.Yet, realize that the precondition of these application can be prepared carbon ball cheaply exactly on a large scale.Thereby the technology of preparing of carbon ball becomes the target of many scientist's scientific researches and engineering expert pursuit.In this respect, the direction of effort mainly concentrates on through graphite arc discharge and prepares carbon ball and catalytic pyrolysis organic hydrocarbon compound at high temperature, like methane etc.Yet all these technologies of preparing all face two difficult problems, the one, and raw materials cost or equipment cost are relatively more expensive; The 2nd, commercial scale prodn does not suit to be extended to.Therefore, brought great limitation to its application.
Summary of the invention
For overcoming the deficiency of prior art; The present invention provides a kind of method of using coal as the feedstock production carbon micro-spheres; This method with the product of the reaction of coal and sodium hydroxide or Pottasium Hydroxide and methyl alcohol as carbon source; Trimethyllaurylammonium bromide or TTAB or cetyl trimethylammonium bromide are directed agents, are solvent with water and ethanol, prepare carbon micro-spheres in a large number.
Preparing method's concrete steps provided by the present invention are following:
(1) the reaction products therefrom is as carbon source down at 200-400 ℃ with coal and sodium hydroxide and methyl alcohol, and wherein coal is 1 with the ratio of the quality of sodium hydroxide and methyl alcohol: 0.1-2: 0.1-15;
(2) after being dissolved in the reaction product of step (1) in the aqueous ethanolic solution; Add directed agents Trimethyllaurylammonium bromide or TTAB or cetyl trimethylammonium bromide; Obtain mixture, said carbon source is 1 with the ratio of the quality of directed agents: 0.2-2;
(3) pack into behind the mixture mixing with step (2) gained in the reaction kettle, seal tight reaction kettle, be put in the process furnace, be heated to 300-700 ℃, it is reacted, stop heating behind the reaction 6-24h, reaction kettle naturally cools to room temperature in process furnace;
(4) reaction product of step (3) is cleaned through ethanol earlier, use washed with de-ionized water again, obtain target product of the present invention: black powder shape carbon micro-spheres in oven dry under 60-80 ℃ after 3-8 hour at last.
Coal in the said step (1) is bituminous coal, brown coal etc.The inventive method products obtained therefrom carbon micro-spheres purity is high, can reach 95%, product median size 5-10 μ m, and the size of carbon micro-spheres is more even.Carbon micro-spheres preparation method provided by the present invention has the following advantages:
1, cost is low: used raw material is the abundant coal of reserves, and is cheap and easy to get; And technological operation is simple.
2, temperature low (300-700 ℃), process stabilizing is easy to control.
3, can be used for the mass preparation carbon micro-spheres.
4, the processing of reactant is simple, process stabilizing, and production efficiency is high.
5, carbosphere provided by the invention, visual inspection are black and are with the glossy powder that flying-spot microscope is observed, and is that diameter is the ball-like structure of 5-10 micron.
6, carbon micro-spheres provided by the invention has extremely important using value for the delivery delivery means of constructing lithium cell of future generation, novel and efficient support of the catalyst, medicine, enzyme and proteinic protective and matrix material etc.
7, the present invention prepares carbon micro-spheres by coal, and compared with present technology, its maximum characteristics are exactly, and raw materials cost is cheap to be easy to get, processing ease, technology are simple, favorable reproducibility, suitability for scale production.
Description of drawings
Figure is the SEM figure of embodiment 1 products therefrom.
Embodiment
Embodiment 1: 1 gram triumph coal, 1 gram sodium hydroxide, 5 ml methanol are put in the autoclave pressure, are heated to 300 ℃, reacted 1 hour.After the still cooling, with THF extractive reaction product.Then 1 gram THF extraction product, 2 gram cetyl trimethylammonium bromides are dissolved in 10 milliliters of ethanol, add 20 ml waters again, above-mentioned solution is mixed.In the pressure valve of packing into then, in 600 ℃ of reactions 24 hours.After the still cooling, open still, pour out the black product, wash respectively with absolute ethyl alcohol and zero(ppm) water then, vacuum-drying is 5 hours under 50 ℃ of temperature, becomes fine powder through mortar or ball milling at last, is the preparation carbon micro-spheres.Electron scanning micrograph is shown in accompanying drawing.
Embodiment 2: 1 gram Firing Shenhua Coal, 0.5 gram Pottasium Hydroxide, 2 ml methanol are put in the autoclave pressure, are heated to 400 ℃, reacted 1 hour.After the still cooling, with THF extractive reaction product.Then 1 gram THF extraction product, 1 gram Trimethyllaurylammonium bromide are dissolved in 5 milliliters of ethanol, add 20 ml waters again, above-mentioned solution is mixed.In the pressure valve of packing into then, in 500 ℃ of reactions 24 hours.After the still cooling, open still, pour out the black product, wash respectively with absolute ethyl alcohol and zero(ppm) water then, vacuum-drying is 5 hours under 80 ℃ of temperature, becomes fine powder through mortar or ball milling at last, is the carbon micro-spheres of preparation.
Embodiment 3: 1 gram triumph coal, 0.1 gram sodium hydroxide, 15 ml methanol are put in the autoclave pressure, are heated to 400 ℃, reacted 1 hour.After the still cooling, with THF extractive reaction product.Then 1 gram THF extraction product, 0.5 gram cetyl trimethylammonium bromide are dissolved in 10 milliliters of ethanol, add 20 ml waters again, above-mentioned solution is mixed.In the pressure valve of packing into then, in 500 ℃ of reactions 24 hours.After the still cooling, open still, pour out the black product, wash respectively with absolute ethyl alcohol and zero(ppm) water then, vacuum-drying is 5 hours under 60 ℃ of temperature, becomes fine powder through mortar or ball milling at last, is the preparation carbon micro-spheres.
Embodiment 4: 1 gram shenfu coal, 2 gram sodium hydroxide, 10 ml methanol are put in the autoclave pressure, are heated to 300 ℃, reacted 1 hour.After the still cooling, with THF extractive reaction product.Then 1 gram THF extraction product, 2 gram TTABs are dissolved in 5 milliliters of ethanol, add 5 ml waters again, above-mentioned solution is mixed.In the pressure valve of packing into then, in 700 ℃ of reactions 24 hours.After the still cooling, open still, pour out the black product, wash respectively with absolute ethyl alcohol and zero(ppm) water then, vacuum-drying is 5 hours under 70 ℃ of temperature, becomes fine powder through mortar or ball milling at last, is the preparation carbon micro-spheres.
Embodiment 5: 1 gram triumph coal, 1 gram sodium hydroxide, 10 ml methanol are put in the autoclave pressure, are heated to 350 ℃, reacted 2 hours.After the still cooling, with THF extractive reaction product.Then 1 gram THF extraction product, 0.5 gram cetyl trimethylammonium bromide are dissolved in 10 milliliters of ethanol, add 10 ml waters again, above-mentioned solution is mixed.In the pressure valve of packing into then, in 300 ℃ of reactions 24 hours.After the still cooling, open still, pour out the black product, wash respectively with absolute ethyl alcohol and zero(ppm) water then, vacuum-drying is 5 hours under 60 ℃ of temperature, becomes fine powder through mortar or ball milling at last, is the preparation carbon micro-spheres.
Embodiment 6: 1 gram triumph coal, 1 gram sodium hydroxide, 1 ml methanol are put in the autoclave pressure, are heated to 300 ℃, reacted 1 hour.After the still cooling, with THF extractive reaction product.Then 1 gram THF extraction product, 2 gram TTABs are dissolved in 10 milliliters of ethanol, add 20 ml waters again, above-mentioned solution is mixed.In the pressure valve of packing into then, in 400 ℃ of reactions 24 hours.After the still cooling, open still, pour out the black product, wash respectively with absolute ethyl alcohol and zero(ppm) water then, vacuum-drying is 5 hours under 80 ℃ of temperature, becomes fine powder through mortar or ball milling at last, is the preparation carbon micro-spheres.
Claims (1)
1. one kind is the method for feedstock production carbon micro-spheres with coal, it is characterized in that these preparing method's concrete steps are following:
(1) the reaction products therefrom is as carbon source down at 200-400 ℃ with coal and sodium hydroxide and methyl alcohol, and said coal is 1 with the ratio of the quality of sodium hydroxide and methyl alcohol: 0.1-2: 0.1-15;
(2) reaction product with step (1) extracts with THF; After being dissolved in extraction product in the aqueous ethanolic solution; Add directed agents Trimethyllaurylammonium bromide or TTAB or cetyl trimethylammonium bromide; Obtain mixture, the mass ratio of said step (1) products therefrom carbon source and directed agents is 1: 0.2-2;
(3) pack into behind the mixture mixing with step (2) gained in the reaction kettle, seal tight reaction kettle, be put in the process furnace, be heated to 300-700 ℃, it is reacted, stop heating behind the reaction 6-24h, reaction kettle naturally cools to room temperature in process furnace;
(4) reaction product of step (3) gained is cleaned through ethanol earlier, use washed with de-ionized water again, obtain target product of the present invention: black powder shape carbon micro-spheres in oven dry under 60-80 ℃ after 3-8 hour at last.
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| CN103771403B (en) * | 2014-01-09 | 2018-10-30 | 新疆出入境检验检疫局 | A method of preparing multi-layer graphene with lignite slag |
| CN103818897B (en) * | 2014-01-09 | 2019-01-29 | 新疆出入境检验检疫局 | A method of multi-layer graphene is prepared with semi-coke |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4259168A (en) * | 1978-12-14 | 1981-03-31 | Exxon Research And Engineering Co. | Treatment of coal to increase yields and improve physical characteristics of coal liquefaction distillates and bottoms |
| CN1644563A (en) * | 2005-01-06 | 2005-07-27 | 北京化工大学 | Preparation of polymer based carbon balls |
| CN1948148A (en) * | 2006-11-11 | 2007-04-18 | 大连理工大学 | Method of preparing ordered structure mesopore carbon using asphalt vinyl matter as raw material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4259168A (en) * | 1978-12-14 | 1981-03-31 | Exxon Research And Engineering Co. | Treatment of coal to increase yields and improve physical characteristics of coal liquefaction distillates and bottoms |
| CN1644563A (en) * | 2005-01-06 | 2005-07-27 | 北京化工大学 | Preparation of polymer based carbon balls |
| CN1948148A (en) * | 2006-11-11 | 2007-04-18 | 大连理工大学 | Method of preparing ordered structure mesopore carbon using asphalt vinyl matter as raw material |
Non-Patent Citations (2)
| Title |
|---|
| Seong-Ho Yoon et al.Preparation of carbonaceous spheres from suspensions of pitch materials.《Carbon》.1992,第30卷(第5期),781-786. * |
| 彭耀丽等.褐煤超临界醇解反应与产物组成分析.《煤炭工程》.2009,(第2期),88-90. * |
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