CN101665250A - Polymerizing-pyrolytic method for preparing mesocarbon microbead in asphaltic base - Google Patents
Polymerizing-pyrolytic method for preparing mesocarbon microbead in asphaltic base Download PDFInfo
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- CN101665250A CN101665250A CN200910307781A CN200910307781A CN101665250A CN 101665250 A CN101665250 A CN 101665250A CN 200910307781 A CN200910307781 A CN 200910307781A CN 200910307781 A CN200910307781 A CN 200910307781A CN 101665250 A CN101665250 A CN 101665250A
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Abstract
The invention provides a polymerizing-pyrolytic method for preparing a mesocarbon microbead of asphaltic base, which solves the problems that in the prior art, the mesocarbon microbead has low yield,high cost, uneven shape and size and environmental pollution and the like. The polymerizing-pyrolytic method is used for preparing the mesocarbon microbead of asphaltic base, and the raw materials used for preparation comprise a basic material, a cross-linking agent and a catalyst, and the mesocarbon microbead of asphaltic base is prepared by processes of preparation of the raw materials, polymerization reaction, pyrolytic reaction, and separation and drying of pyrolysis products. The preparation method has high yield, controllable particle size, even size, good sphericity and low preparationcost.
Description
Technical field
The invention belongs to raw material of wood-charcoal material field, relate generally to a kind of heat of polymerization solution and prepare the asphaltic base MCMB.
Background technology
Since nineteen sixties Brooks and Taylor discovery MCMB, people form mechanism, structure, performance and application etc. to it and have carried out a large amount of research.MCMB has caused people's very big attention as the high-quality presoma of advanced raw material of wood-charcoal material.Characteristics such as MCMB has that narrow diameter distribution, density height, intensity are big, Heat stability is good, stable chemical performance, good conductivity, self sintering are good, carbon yield height are considered to prepare the high-quality presoma of high-performance carbon material.High-density high-strength charcoal material, active carbon with superhigh specific surface area, lithium ion battery electrode material, efficient liquid phase chromatographic stuffing, support of the catalyst etc. have been used to prepare at present.The method for preparing at present MCMB mainly contains thermal polycondensation process, emulsion process and suspension method.Thermal polycondensation process prepares MCMB mainly through two steps, and the one, generate mesophasespherule by thermal treatment condensed-nuclei aromatics compound with polymerization, the 2nd, utilize appropriate means that mesophasespherule is separated from mother liquor.Emulsion process prepare MCMB at first be by thermal treatment condensed-nuclei aromatics compound obtaining mesophase pitch, and then mesophase pitch is emulsified into mesophasespherule.Suspension method is that mesophase pitch is dissolved in the organic solvent, utilizes tensio-active agent and water or other solvent composition suspension, and powerful at a certain temperature stirring balling-up through filtering, obtains mesophasespherule then.After handling through oxidative stabilization, charing, the mesophasespherule that aforesaid method is obtained to obtain to have the MCMB of property.But there are problems such as yield is low, shape and size are inhomogeneous, environmental pollution in the above-mentioned method for preparing MCMB, makes that the preparation cost of MCMB is high, and this has limited MCMB further development and application greatly.
Summary of the invention
The purpose of this invention is to provide a kind of heat of polymerization solution and prepare the asphaltic base MCMB, solve low, the problems such as cost is high, shape and size are inhomogeneous, environmental pollution of MCMB yield in the prior art, method of the present invention prepares the yield height, particle diameter is controlled, size is even, good sphericity, preparation cost are low.
Heat of polymerization solution of the present invention prepares the asphaltic base MCMB: the raw material of described preparation usefulness comprises: basic raw material, linking agent and catalyzer, the separation and the drying process of the outfit of process raw material, polyreaction, pyrolytic reaction, pyrolysis product prepare the asphaltic base MCMB.
Compared with prior art, advantage that the present invention had and effect are:
(1) abundant raw material, wide material sources, cheap.
(2) carbon microspheres yield height, size distribution is even, and size is controlled.
(3) technology and equipment are simple, are easy to produce, and is easy and simple to handle, and preparation process does not have obnoxious flavour to produce.
(4) excellent product performance, of many uses.
Description of drawings
Fig. 1 is the size distribution curve figure of the asphaltic base MCMB of embodiments of the invention 1 preparation.
Fig. 2 is the SEM photo of the asphaltic base MCMB of embodiments of the invention 1 preparation.
Fig. 3 is the size distribution curve figure of the asphaltic base MCMB of embodiments of the invention 2 preparations.
Fig. 4 is the SEM photo of the asphaltic base MCMB of embodiments of the invention 2 preparations.
Fig. 5 is the size distribution curve figure of the asphaltic base MCMB of embodiments of the invention 3 preparations.
Fig. 6 is the SEM photo of the asphaltic base MCMB of embodiments of the invention 3 preparations.
Embodiment
Each component of raw material is according to weight percent: basic raw material: 80-99.8%; Linking agent: 0.1-15%; Catalyzer: 0.1-5%.
Basic raw material is a kind of in low temperature coal-tar pitch or the medium temperature coal pitch or both; Linking agent is any or several in terephthalaldehyde, p-tolyl aldehyde, phenyl aldehyde or the formaldehyde; Catalyzer be in tosic acid or the oxalic acid one or both.
Preparation process is as follows:
(1) raw material is equipped with: according to described proportioning raw materials, linking agent and catalyzer are directly mixed with basic raw material; Raw material is equipped with or can carries on other carriers and uses, for example can further linking agent, catalyzer and basic raw material be dissolved in other solvents (as dehydrated alcohol, with the linking agent volume ratio is 1: 2) mix the lining, so that better reaction improves the polymerization degree.
By kind that changes linking agent and the yield that consumption is regulated MCMB.
(2) polyreaction: raw material packed into carry out polyreaction in the polymerization container, the parameter of polyreaction is as follows:
Temperature: 120-180 ℃
Polymerization reaction time: 0.5-8h
Polyreaction protective atmosphere: N2 or Ar2
Stirring velocity during polyreaction: 100-500rpm
By polyreaction, obtain the big modified coal pitch of molecular weight.
(3) pyrolytic reaction: the good coal-tar pitch of step (2) polyreaction post-modification is encased in carries out pyrolytic reaction in the autoclave, it is as follows that pyrolytic reaction is put into concrete parameter:
Temperature: 380-450 ℃
The pyrolytic reaction time: 0.5-8h
Pyrolytic reaction protective atmosphere: N
2Perhaps Ar
2
By pyrolytic reaction, obtain MCMB and substrate mixture.
(4) separation of pyrolysis product: pyrolysis product is joined in the solvent, and extracting is to colourless in apparatus,Soxhlet's; Insolubles after the extracting is the asphaltic base MCMB; Described solvent pyridine, a kind of in quinoline or the tetrahydrofuran (THF); The mass ratio of solvent and pyrolysis product is 60: 1, the solvent recuperation recycling.
(5) drying: the MCMB after step (4) separation through super-dry, is obtained described pitch intermediate phase based carbon microsphere, and drying parameter is: drying temperature: 80-180 ℃; Vacuum tightness: 1.0 * 10
2-1.0 * 10
3Pa.
The protective atmosphere flow of above step (2) and (3) is 50mL/min.
The present invention is by control kind, consumption and the polymerization of linking agent and the temperature of pyrolytic reaction, the size that the time is regulated MCMB, distributional pattern, configuration of surface and microlitic structure.
The yield that adopts the prepared MCMB of production method of the present invention is 25-45%, and size is 0.1-30 μ m.
Below be several specific embodiment of the present invention, further specify the present invention, but the present invention be not limited only to this.
Embodiment 1
With the coal-tar pitch is raw material, and formaldehyde is linking agent, and oxalic acid is catalyzer, is that 100: 4: 2 ratios join in the there-necked flask in three's mass ratio, freely heats up before 100 ℃, and the speed with 5 ℃/min after 100 ℃ heats up, and begins to feed N from intensification
2, N
2Flow is 50mL/min, and at 130 ℃ of following reaction 2h, with the polymeric modification pitch that obtains at N
2Protection is down handled 2h in 420 ℃, and is extremely colourless through pyridine dissolving back (mass ratio of pyridine and pyrolysis product is 60: 1) extracting then, obtains particle diameter behind the vacuum drying and be the MCMB about 8 μ m, and yield is 30.74%.Good sphericity, narrow diameter distribution.
With the coal-tar pitch is raw material, and phenyl aldehyde is a linking agent, and tosic acid is a catalyzer, is that 100: 12: 2 ratios join in the there-necked flask in three's mass ratio, freely heats up before 100 ℃, and the speed with 5 ℃/min after 100 ℃ heats up, and begins to feed N from intensification
2, N
2Flow is 50mL/min, and at 130 ℃ of following reaction 3h, with the polymeric modification pitch that obtains at N
2Protection is down handled 2h down in 460 ℃, and is extremely colourless through pyridine (mass ratio of pyridine and pyrolysis product is 60: 1) extracting then, obtains particle diameter behind the vacuum drying and be the MCMB about 12 μ m, and yield is 40.62%.Good sphericity, rare melting also between the carbon microspheres.
Embodiment 3
With the coal-tar pitch is raw material, and p-tolyl aldehyde is a linking agent, and oxalic acid is catalyzer, is that 100: 8: 2 ratios join in the there-necked flask in three's mass ratio, freely heats up before 100 ℃, and the speed with 5 ℃/min after 100 ℃ heats up, and begins to feed N from intensification
2, N
2Flow is 50mL/min, and at 140 ℃ of following reaction 2h, with the polymeric modification pitch that obtains at N
2Protection is down handled 1h down in 450 ℃, and is extremely colourless through pyridine (mass ratio of pyridine and pyrolysis product is 60: 1) extracting then, obtains particle diameter behind the vacuum drying and be the MCMB about 10 μ m, and yield is 35.54%.Good sphericity, surface smoothness is good, rare melting also between the ball.
Claims (10)
1. a polymerization-pyrolysis method prepares the asphaltic base MCMB, it is characterized in that: the raw material of described preparation usefulness comprises: basic raw material, linking agent and catalyzer, the separation and the drying process of the outfit of process raw material, polyreaction, pyrolytic reaction, pyrolysis product prepare the asphaltic base carbon microspheres.
2. polymerization-pyrolysis method according to claim 1 prepares the asphaltic base MCMB, it is characterized in that: each component of described raw material is according to weight percent: basic raw material: 80-99.8%; Linking agent: 0.1-15%; Catalyzer: 0.1-5%.
3. heat of polymerization solution according to claim 2 prepares the asphaltic base MCMB, it is characterized in that: described basic raw material is a kind of in low temperature coal-tar pitch or the medium temperature coal pitch or both.
4. heat of polymerization solution according to claim 2 prepares the asphaltic base MCMB, it is characterized in that: described linking agent is any or several in terephthalaldehyde, p-tolyl aldehyde, phenyl aldehyde or the formaldehyde.
5. heat of polymerization solution according to claim 2 prepares the asphaltic base MCMB, it is characterized in that: described catalyzer be in tosic acid or the oxalic acid one or both.
6. prepare the asphaltic base MCMB according to claim 1,2,3,4 or 5 described polymerization-pyrolysis methods, it is characterized in that: preparation process is as follows:
(1) raw material is equipped with: according to described proportioning raw materials, linking agent and catalyzer are directly mixed with basic raw material;
(2) polyreaction: raw material packed into carry out polyreaction in the polymerization container, the parameter of polyreaction is as follows:
Temperature: 120-180 ℃
Polymerization reaction time: 0.5-8h
Polyreaction protective atmosphere: N
2Perhaps Ar
2
Stirring velocity during polyreaction: 100-500rpm;
(3) pyrolytic reaction: the good coal-tar pitch of step (2) polyreaction post-modification is encased in carries out pyrolytic reaction in the autoclave, it is as follows that pyrolytic reaction is put into concrete parameter:
Temperature: 380-450 ℃
The pyrolytic reaction time: 0.5-8h
Pyrolytic reaction protective atmosphere: N
2Perhaps Ar
2
(4) separation of pyrolysis product: adopt solvent separation that the asphaltic base MCMB is separated from pyrolysis product;
(5) drying: the MCMB after step (4) separation through super-dry, is obtained described pitch intermediate phase based carbon microsphere, and drying parameter is: drying temperature: 80-180 ℃; Vacuum tightness: 1.0 * 10
2-1.0 * 10
3Pa.
7. polymerization-pyrolysis method according to claim 6 prepares the asphaltic base MCMB, it is characterized in that: the raw material of described step (1) is equipped with and mixes with linking agent, catalyzer and in basic raw material is dissolved in other solvents, and described other solvents and linking agent volume ratio are 1: 2.
8. heat of polymerization solution according to claim 7 prepares the asphaltic base MCMB, it is characterized in that: described other solvents are dehydrated alcohol.
9. polymerization-pyrolysis method according to claim 6 prepares the asphaltic base MCMB, it is characterized in that: the solvent separation of described step (4) joins pyrolysis product in the solvent for adopting, and extracting is to colourless in apparatus,Soxhlet's; Insolubles after the extracting is the asphaltic base MCMB; Described solvent pyridine, a kind of in quinoline or the tetrahydrofuran (THF); The mass ratio of solvent and pyrolysis product is 60: 1, the solvent recuperation recycling.
10. polymerization-pyrolysis method according to claim 6 prepares the asphaltic base MCMB, it is characterized in that: the protective atmosphere flow of described step (2) and (3) is 50mL/min.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920956A (en) * | 2010-09-15 | 2010-12-22 | 福州大学 | Method for highly-efficiently preparing asphalt-based mesocarbon microbeads |
| CN102381701A (en) * | 2011-08-01 | 2012-03-21 | 福州大学 | Method for numerously preparing asphalt-based graphene material with low cost |
| CN102479943A (en) * | 2010-11-30 | 2012-05-30 | 上海杉杉科技有限公司 | Hard carbon cathode material, preparation method and use thereof |
| CN102815689A (en) * | 2012-08-22 | 2012-12-12 | 华北电力大学 | Preparation method of carbon micron ball material with even particle size |
| CN105238429A (en) * | 2015-10-19 | 2016-01-13 | 太原理工大学 | Method for preparing low-toxicity modified coal pitch for road building |
| CN105923620A (en) * | 2016-04-25 | 2016-09-07 | 辽宁科技大学 | Preparation method for isotropic mesocarbon microbeads |
| CN107601450A (en) * | 2017-09-01 | 2018-01-19 | 赛鼎工程有限公司 | A kind of production technology of coal tar pitch MCMB |
| CN107673322A (en) * | 2017-11-02 | 2018-02-09 | 太原理工大学 | A kind of NEW TYPE OF COMPOSITE raw material of wood-charcoal preparation method for material of high conductivity low thermal coefficient of expansion |
| CN109065884A (en) * | 2018-08-17 | 2018-12-21 | 东莞市凯金新能源科技股份有限公司 | The preparation method and material of acid wash purification resistance material artificial graphite pore-creating negative electrode material |
| CN112645303A (en) * | 2021-01-13 | 2021-04-13 | 中国石油大学(华东) | High-performance mesocarbon microbeads and preparation method thereof |
| CN112645304A (en) * | 2021-01-13 | 2021-04-13 | 中国石油大学(华东) | Method for preparing high-performance mesocarbon microbeads from heavy oil |
| CN113174274A (en) * | 2021-04-21 | 2021-07-27 | 上海应用技术大学 | Method for preparing modified mesophase pitch by utilizing coal liquefaction residues |
| CN115340083A (en) * | 2022-08-18 | 2022-11-15 | 郑州中科新兴产业技术研究院 | Small-particle-size asphalt-based carbon microsphere and preparation method thereof |
| CN115340381A (en) * | 2022-09-22 | 2022-11-15 | 东莞市鸿亿导热材料有限公司 | Graphite heat dissipation material and preparation method thereof |
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2009
- 2009-09-25 CN CN200910307781A patent/CN101665250A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920956A (en) * | 2010-09-15 | 2010-12-22 | 福州大学 | Method for highly-efficiently preparing asphalt-based mesocarbon microbeads |
| CN102479943A (en) * | 2010-11-30 | 2012-05-30 | 上海杉杉科技有限公司 | Hard carbon cathode material, preparation method and use thereof |
| CN102381701A (en) * | 2011-08-01 | 2012-03-21 | 福州大学 | Method for numerously preparing asphalt-based graphene material with low cost |
| CN102815689A (en) * | 2012-08-22 | 2012-12-12 | 华北电力大学 | Preparation method of carbon micron ball material with even particle size |
| CN105238429A (en) * | 2015-10-19 | 2016-01-13 | 太原理工大学 | Method for preparing low-toxicity modified coal pitch for road building |
| CN105238429B (en) * | 2015-10-19 | 2017-10-24 | 太原理工大学 | A kind of preparation method built the road with low toxicity modified coal pitch |
| CN105923620A (en) * | 2016-04-25 | 2016-09-07 | 辽宁科技大学 | Preparation method for isotropic mesocarbon microbeads |
| CN105923620B (en) * | 2016-04-25 | 2017-12-12 | 辽宁科技大学 | A kind of preparation method of isotropism MCMB |
| CN107601450A (en) * | 2017-09-01 | 2018-01-19 | 赛鼎工程有限公司 | A kind of production technology of coal tar pitch MCMB |
| CN107601450B (en) * | 2017-09-01 | 2020-06-12 | 赛鼎工程有限公司 | Production process of coal tar pitch mesocarbon microbeads |
| CN107673322A (en) * | 2017-11-02 | 2018-02-09 | 太原理工大学 | A kind of NEW TYPE OF COMPOSITE raw material of wood-charcoal preparation method for material of high conductivity low thermal coefficient of expansion |
| CN109065884A (en) * | 2018-08-17 | 2018-12-21 | 东莞市凯金新能源科技股份有限公司 | The preparation method and material of acid wash purification resistance material artificial graphite pore-creating negative electrode material |
| CN112645303A (en) * | 2021-01-13 | 2021-04-13 | 中国石油大学(华东) | High-performance mesocarbon microbeads and preparation method thereof |
| CN112645304A (en) * | 2021-01-13 | 2021-04-13 | 中国石油大学(华东) | Method for preparing high-performance mesocarbon microbeads from heavy oil |
| CN113174274A (en) * | 2021-04-21 | 2021-07-27 | 上海应用技术大学 | Method for preparing modified mesophase pitch by utilizing coal liquefaction residues |
| CN115340083A (en) * | 2022-08-18 | 2022-11-15 | 郑州中科新兴产业技术研究院 | Small-particle-size asphalt-based carbon microsphere and preparation method thereof |
| CN115340083B (en) * | 2022-08-18 | 2024-03-15 | 郑州中科新兴产业技术研究院 | Small-particle-size asphalt-based carbon microsphere and preparation method thereof |
| CN115340381A (en) * | 2022-09-22 | 2022-11-15 | 东莞市鸿亿导热材料有限公司 | Graphite heat dissipation material and preparation method thereof |
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Application publication date: 20100310 |