CN101850960A - 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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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, being specifically related to a kind of is the method for feedstock production carbon micro-spheres with coal.
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 successfully synthesized.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 catalysis carbonization, 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 by graphite arc discharge and prepares carbon ball and catalytic pyrolysis organic hydrocarbon compound at high temperature, as 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, be not suitable for being extended to commercial scale production.Therefore, brought great limitation to its application.
Summary of the invention
For overcoming the deficiencies in the prior art, the invention provides a kind of is the method for feedstock production carbon micro-spheres with coal, this method with the product of the reaction of coal and sodium hydroxide or potassium hydroxide and methyl alcohol as carbon source, Trimethyllaurylammonium bromide or Tetradecyl Trimethyl Ammonium Bromide or cetyl trimethylammonium bromide are directed agents, with water and ethanol is solvent, prepares carbon micro-spheres in a large number.
Preparation method's concrete steps provided by the present invention are as follows:
(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 Tetradecyl Trimethyl Ammonium Bromide or cetyl trimethylammonium bromide, obtain mixture, described 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 reactor, seal tight reactor, be put in the process furnace, be heated to 300-700 ℃, it is reacted, stop heating behind the reaction 6-24h, reactor 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 described step (1) is bituminous coal, brown coal etc.The inventive method products obtained therefrom carbon micro-spheres purity height 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, production efficiency height.
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 the prior art, 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 tetrahydrofuran (THF) extractive reaction product.Then 1 gram tetrahydrofuran (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 dehydrated alcohol and distilled water then, vacuum-drying is 5 hours under 50 ℃ of temperature, becomes fine powder by mortar or ball milling at last, is the preparation carbon micro-spheres.Electron scanning micrograph as shown in drawings.
Embodiment 2: 1 gram Firing Shenhua Coal, 0.5 gram potassium hydroxide, 2 ml methanol are put in the autoclave pressure, are heated to 400 ℃, reacted 1 hour.After the still cooling, with tetrahydrofuran (THF) extractive reaction product.Then 1 gram tetrahydrofuran (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 dehydrated alcohol and distilled water then, vacuum-drying is 5 hours under 80 ℃ of temperature, becomes fine powder by 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 tetrahydrofuran (THF) extractive reaction product.Then 1 gram tetrahydrofuran (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 dehydrated alcohol and distilled water then, vacuum-drying is 5 hours under 60 ℃ of temperature, becomes fine powder by 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 tetrahydrofuran (THF) extractive reaction product.Then 1 gram tetrahydrofuran (THF) extraction product, 2 gram Tetradecyl Trimethyl Ammonium Bromide 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 dehydrated alcohol and distilled water then, vacuum-drying is 5 hours under 70 ℃ of temperature, becomes fine powder by 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 tetrahydrofuran (THF) extractive reaction product.Then 1 gram tetrahydrofuran (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 dehydrated alcohol and distilled water then, vacuum-drying is 5 hours under 60 ℃ of temperature, becomes fine powder by 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 tetrahydrofuran (THF) extractive reaction product.Then 1 gram tetrahydrofuran (THF) extraction product, 2 gram Tetradecyl Trimethyl Ammonium 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 400 ℃ of reactions 24 hours.After the still cooling, open still, pour out the black product, wash respectively with dehydrated alcohol and distilled water then, vacuum-drying is 5 hours under 80 ℃ of temperature, becomes fine powder by 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 preparation method's concrete steps are as follows:
(1) the reaction products therefrom is as carbon source down at 200-400 ℃ with coal and sodium hydroxide and methyl alcohol, and described 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 Tetradecyl Trimethyl Ammonium Bromide or cetyl trimethylammonium bromide, obtain mixture, the mass ratio of described 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 reactor, seal tight reactor, be put in the process furnace, be heated to 300-700 ℃, it is reacted, stop heating behind the reaction 6-24h, reactor 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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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103771403A (en) * | 2014-01-09 | 2014-05-07 | 新疆出入境检验检疫局 | Method of preparing multilayer graphene by using brown coal slags |
CN103818897A (en) * | 2014-01-09 | 2014-05-28 | 新疆出入境检验检疫局 | Method for preparing multilayer graphene by using semi coke |
Citations (3)
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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 |
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《Carbon》 19921231 Seong-Ho Yoon et al Preparation of carbonaceous spheres from suspensions of pitch materials 781-786 1 第30卷, 第5期 * |
《煤炭工程》 20091231 彭耀丽等 褐煤超临界醇解反应与产物组成分析 88-90 1 , 第2期 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103771403A (en) * | 2014-01-09 | 2014-05-07 | 新疆出入境检验检疫局 | Method of preparing multilayer graphene by using brown coal slags |
CN103818897A (en) * | 2014-01-09 | 2014-05-28 | 新疆出入境检验检疫局 | Method for preparing multilayer graphene by using semi coke |
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 |
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