CN101920956A - Method for highly-efficiently preparing asphalt-based mesocarbon microbeads - Google Patents
Method for highly-efficiently preparing asphalt-based mesocarbon microbeads Download PDFInfo
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- CN101920956A CN101920956A CN 201010282283 CN201010282283A CN101920956A CN 101920956 A CN101920956 A CN 101920956A CN 201010282283 CN201010282283 CN 201010282283 CN 201010282283 A CN201010282283 A CN 201010282283A CN 101920956 A CN101920956 A CN 101920956A
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Abstract
The invention provides a method for highly-efficiently preparing asphalt-based mesocarbon microbeads. The asphalt-based mesocarbon microbeads are prepared from raw materials comprising a basic raw material and an additive by the steps of the preparation of the raw materials, polymerization reaction, pyrolytic reaction, and the separation and drying of pyrolysis products, wherein the basic raw material comprises one or two of medium-temperature coal tar and high-temperature coal tar; and the additive comprises one or two of rosin and disproportionated rosin. The raw materials of the invention are abundant, environmentally-friendly and low in cost; and the prepared mesocarbon microbeads have the characteristics of high yield, uniform particle size distribution, particle size controllability, simple process and equipment, easy production, simple and convenient operation, no harmful gases produced in a preparation process, high performance and wide application.
Description
Technical field
The invention belongs to raw material of wood-charcoal material field, relate to a kind of method of highly-efficiently preparing asphalt-based MCMB.
Background technology
1973, the Honda of Japan and Yamada be with isolating mesophasespherule (MCMB) the pitch of solvent after thermal treatment, and utilize this microsphere to prepare non-bonding-agent high-density degree raw material of wood-charcoal material, after this started the upsurge of research intermediate phase in the world.The spherical laminate structure of MCMB is given the character of its numerous uniquenesses, as chemical stability, and thermostability, good conduction and thermal conductivity etc. are a kind of novel raw material of wood-charcoal material with very big potentiality to be exploited and application prospect.Can prepare binder free high-intensity high-density C/C matrix material from MCMB, high-performance liquid chromatography filler, active carbon with high specific surface area material, support of the catalyst, a series of high-performance carbon materials such as lithium ion battery negative material.Therefore, formation, structure, the performance of research MCMB have crucial meaning for the preparation and the application of raw material of wood-charcoal material, help expanding the research field of novel charcoal material.Main both at home and abroad at present employing emulsion process, suspension method and thermopolymerization legal system are equipped with MCMB.Yet these preparation methods have limitation in one aspect.The production process complexity that emulsion process prepares MCMB is loaded down with trivial details, the MCMB melting of preparing, must be before charing through melt processed not, and have difficulties in the preparation process, production cost is higher, therefore industrial prospect dimness is mainly used in some fields strict to the MCMB particle diameter, as the high-performance liquid chromatography filler.Suspension method is the same with emulsion process, and processing condition control difficulty is big, and MCMB needs through melt processed not.The legal processing requirement of hot polymerization does not have emulsion process and suspension method high like that, has that technology is simple, facility investment is few, preparation condition is easy to characteristics such as control, so preparation MCMB is still based on thermal polycondensation process.But the solvent-oil ratio of this method is big, low its production cost height that causes of the productive rate of MCMB.Therefore, exploring efficient, energy-conservation, easy, low-cost, free of contamination novel preparation method is MCMB Development of Preparation Technology trend.
Summary of the invention
The object of the present invention is to provide a kind of method of highly-efficiently preparing asphalt-based MCMB.Solved problems such as the MCMB yield is low in the prior art, cost is high, environmental pollution, MCMB productive rate height, the cost of method preparation of the present invention are low, pollution-free, can promote industrialization.
In order to realize above-mentioned purpose, the method of highly-efficiently preparing asphalt-based MCMB of the present invention, the raw material of described preparation usefulness comprises: basic raw material, additive, and the separation and the drying process of the outfit of process raw material, polyreaction, pyrolytic reaction, pyrolysis product prepare the asphaltic base carbon microspheres; Described basic raw material is a kind of of medium temperature coal pitch and high temperature coal-tar pitch or two kinds, and described additive is a kind of of rosin and nilox resin or two kinds.
Each component of described raw material is according to weight percent: basic raw material: 85-95%; Additive: 5-15%.
The concrete steps of described method are as follows:
(1) outfit of raw material:
According to described proportioning raw materials, basic raw material and additive are mixed.
(2) polymerization reaction parameter is:
Temperature: 120-200 ℃;
Time: 10-30 min;
Stirring velocity: 200-400 rpm;
Polyreaction protective atmosphere: N
2Perhaps Ar
2
(3) pyrolytic reaction: the good coal-tar pitch of step (2) polyreaction post-modification is encased in carries out pyrolytic reaction in the autoclave, the concrete parameter of pyrolytic reaction is as follows:
Temperature: 410-460 ℃
Time: 0.5-4 h
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.
Preferred concrete steps are as follows:
(1) outfit of raw material:
According to described proportioning raw materials, basic raw material and additive are mixed.
(2) polymerization reaction parameter is:
Temperature: 150-200 ℃;
Time: 10-30 min;
Stirring velocity: 200-400 rpm;
Polyreaction protective atmosphere: N
2Perhaps Ar
2
(3) pyrolytic reaction: the good coal-tar pitch of step (2) polyreaction post-modification is encased in carries out pyrolytic reaction in the autoclave, the concrete parameter of pyrolytic reaction is as follows:
Temperature: 430-460 ℃
Time: 1.5-4h
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.
The outfit of described raw material is that basic raw material and additive are mixed after 100 eye mesh screens sieve.
Described solvent separation adopts 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 is a pyridine, a kind of in quinoline or the tetrahydrofuran (THF); The weight ratio of solvent and pyrolysis product is 60:1, the solvent recuperation recycling.
The protective atmosphere flow of described step (2) and (3) is 50mL/min.
The present invention regulates productive rate, size, shape characteristic and the structure that MCMB is regulated MCMB by the ratio of controlled polymerization raw material and additive and temperature, the time of polymerization and pyrolytic reaction.
The present invention carries out modification with abundant, cheap, the green non-poisonous rosin of originating to coal-tar pitch, and the viscosity that not only can reduce mother liquor is beneficial to the separation of mesophase ball, and can control the speed of reaction of thermopolymerization, thereby its sphere diameter is more evenly distributed.In addition, rosiny adds a large amount of nucleus of formation, improves the yield of MCMB greatly.
Adopting the prepared MCMB particle diameter of production method of the present invention is 10-25 μ m, and productive rate is 50%-65%.
Compared with prior art, advantage that the present invention had and effect are:
(1) abundant raw material, environmental protection, cheap;
(2) MCMB 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 polarized light microscopy photo of the MCMB of example 1 preparation;
Fig. 2 is the SEM photo of the MCMB of example 1 preparation;
Fig. 3 is the polarized light microscopy photo of the MCMB of example 2 preparations;
Fig. 4 is the SEM photo of the MCMB of example 2 preparations;
Fig. 5 is the polarized light microscopy photo of the MCMB of example 3 preparations;
Fig. 6 is the SEM photo of the MCMB of example 3 preparations.
Embodiment
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 medium temperature coal pitch and rosin (85:15 according to a certain percentage, weight ratio) takes by weighing, pour the 100 eye mesh screens polymerization container of packing into after mixing that sieves together into, freely heated up before 100 ℃, speed with 5 ℃/min after 100 ℃ heats up, and begins to feed N from intensification
2, N
2Flow is 50mL/min.When temperature rises to 150 ℃, reaction 10min.With the polymeric modification pitch that obtains at N
2Protection is down in 450 ℃ and be incubated 2.5h, 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 13.3 μ m, and yield is 50.4%.Good sphericity, narrow diameter distribution.
Embodiment 2
With high temperature coal-tar pitch and nilox resin (90:10 according to a certain percentage, weight ratio) takes by weighing, pour the 100 eye mesh screens polymerization container of packing into after mixing that sieves together into, freely heated up before 100 ℃, speed with 5 ℃/min after 100 ℃ heats up, and begins to feed N from intensification
2, N
2Flow is 50mL/min.When temperature rises to 200 ℃, reaction 20min., with the polymeric modification pitch that obtains at N
2Protection is down in 460 ℃ and be incubated 1.5h, 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 17.3 μ m, and yield is 55.1%.Good sphericity, narrow diameter distribution.
Embodiment 3
With medium temperature coal pitch and rosin (85:15 according to a certain percentage, weight ratio) takes by weighing, pour the 100 eye mesh screens polymerization container of packing into after mixing that sieves together into, freely heated up before 100 ℃, speed with 5 ℃/min after 100 ℃ heats up, and begins to feed N from intensification
2, N
2Flow is 50mL/min.When temperature rises to 200 ℃, reaction 30min.With the polymeric modification pitch that obtains at N
2Protection is down in 430 ℃ and be incubated 4h, 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 23.5 μ m, and yield is 63.5%.Sphericity is better, and size distribution is narrower.
Claims (7)
1. the method for a highly-efficiently preparing asphalt-based MCMB, it is characterized in that: the raw material of described preparation usefulness comprises: basic raw material, additive, and the separation and the drying process of the outfit of process raw material, polyreaction, pyrolytic reaction, pyrolysis product prepare the asphaltic base carbon microspheres; Described basic raw material is a kind of of medium temperature coal pitch and high temperature coal-tar pitch or two kinds, and described additive is a kind of of rosin and nilox resin or two kinds.
2. the method for highly-efficiently preparing asphalt-based MCMB according to claim 1 is characterized in that: each component of described raw material is according to weight percent: basic raw material: 85-95%; Additive: 5-15%.
3. the method for highly-efficiently preparing asphalt-based MCMB according to claim 2, it is characterized in that: the concrete steps of described method are as follows:
(1) outfit of raw material:
According to described proportioning raw materials, basic raw material and additive are mixed.
(2) polymerization reaction parameter is:
Temperature: 120-200 ℃;
Time: 10-30 min;
Stirring velocity: 200-400 rpm;
Polyreaction protective atmosphere: N
2Perhaps Ar
2
(3) pyrolytic reaction: the good coal-tar pitch of step (2) polyreaction post-modification is encased in carries out pyrolytic reaction in the autoclave, the concrete parameter of pyrolytic reaction is as follows:
Temperature: 410-460 ℃
Time: 0.5-4 h
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.
4. the method for highly-efficiently preparing asphalt-based MCMB according to claim 3 is characterized in that: the preferred concrete steps of institute are as follows:
(1) outfit of raw material:
According to described proportioning raw materials, basic raw material and additive are mixed.
(2) polymerization reaction parameter is:
Temperature: 150-200 ℃;
Time: 10-30 min;
Stirring velocity: 200-400 rpm;
Polyreaction protective atmosphere: N
2Perhaps Ar
2
(3) pyrolytic reaction: the good coal-tar pitch of step (2) polyreaction post-modification is encased in carries out pyrolytic reaction in the autoclave, the concrete parameter of pyrolytic reaction is as follows:
Temperature: 430-460 ℃
Time: 1.5-4h
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.
5. according to the method for claim 3 or 4 described highly-efficiently preparing asphalt-based MCMB, it is characterized in that: described solvent separation adopts 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 is a pyridine, a kind of in quinoline or the tetrahydrofuran (THF); The weight ratio of solvent and pyrolysis product is 60:1, the solvent recuperation recycling.
6. according to the method for claim 3 or 4 described highly-efficiently preparing asphalt-based MCMB, it is characterized in that: the protective atmosphere flow of described step (2) and (3) is 50mL/min.
7. according to the method for claim 3 or 4 described highly-efficiently preparing asphalt-based MCMB, it is characterized in that: the outfit of described raw material is that basic raw material and additive are mixed after 100 eye mesh screens sieve.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942172A (en) * | 2012-11-22 | 2013-02-27 | 长沙理工大学 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
| CN105905883A (en) * | 2016-04-15 | 2016-08-31 | 神华集团有限责任公司 | Mesocarbon microbead and preparation method thereof |
| CN107021471A (en) * | 2017-05-31 | 2017-08-08 | 中国科学院山西煤炭化学研究所 | A kind of method that medium temperature coal pitch prepares MCMB |
| CN107537561A (en) * | 2017-08-23 | 2018-01-05 | 周逸 | Catalytic cracking or the preparation for the catalyst containing C H bond structure polymer of degrading |
| 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 |
| CN107934934A (en) * | 2018-01-11 | 2018-04-20 | 中国科学院过程工程研究所 | A kind of method for efficiently preparing asphalt base mesocarbon microspheres |
| CN108455558A (en) * | 2018-03-27 | 2018-08-28 | 中国科学院过程工程研究所 | A kind of preparation method of novel mesocarbon microspheres |
| 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 |
| CN112831335A (en) * | 2021-01-13 | 2021-05-25 | 中国石油大学(华东) | Method for preparing mesophase pitch and mesophase carbon microspheres from heavy oil |
| CN112877087A (en) * | 2021-01-13 | 2021-06-01 | 中国石油大学(华东) | Preparation process of spinnable mesophase pitch and pitch-based carbon fiber |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665250A (en) * | 2009-09-25 | 2010-03-10 | 福州大学 | Polymerizing-pyrolytic method for preparing mesocarbon microbead in asphaltic base |
-
2010
- 2010-09-15 CN CN 201010282283 patent/CN101920956A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665250A (en) * | 2009-09-25 | 2010-03-10 | 福州大学 | Polymerizing-pyrolytic method for preparing mesocarbon microbead in asphaltic base |
Non-Patent Citations (2)
| Title |
|---|
| 《Journal of Analytical and Applied Pyrolysis》 20090314 Qilang Lin et al Effect of rosin to coal-tar pitch on carbonization behavior and optical texture of resultant semi-cokes 第8-13页 1-7 第86卷, 第1期 2 * |
| 《煤炭转化》 20091031 柯余良等 新型中间相炭微球的制备及表征 第89-91页 1-7 第32卷, 第4期 2 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942172B (en) * | 2012-11-22 | 2014-08-20 | 长沙理工大学 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
| CN102942172A (en) * | 2012-11-22 | 2013-02-27 | 长沙理工大学 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
| CN105905883A (en) * | 2016-04-15 | 2016-08-31 | 神华集团有限责任公司 | Mesocarbon microbead and preparation method thereof |
| CN107021471A (en) * | 2017-05-31 | 2017-08-08 | 中国科学院山西煤炭化学研究所 | A kind of method that medium temperature coal pitch prepares MCMB |
| CN107537561A (en) * | 2017-08-23 | 2018-01-05 | 周逸 | Catalytic cracking or the preparation for the catalyst containing C H bond structure polymer of degrading |
| CN107601450B (en) * | 2017-09-01 | 2020-06-12 | 赛鼎工程有限公司 | Production process of coal tar pitch 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 |
| CN107934934A (en) * | 2018-01-11 | 2018-04-20 | 中国科学院过程工程研究所 | A kind of method for efficiently preparing asphalt base mesocarbon microspheres |
| CN108455558A (en) * | 2018-03-27 | 2018-08-28 | 中国科学院过程工程研究所 | A kind of preparation method of novel mesocarbon microspheres |
| CN108455558B (en) * | 2018-03-27 | 2021-05-14 | 中国科学院过程工程研究所 | Preparation method of novel mesocarbon microbeads |
| 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 |
| CN112831335A (en) * | 2021-01-13 | 2021-05-25 | 中国石油大学(华东) | Method for preparing mesophase pitch and mesophase carbon microspheres from heavy oil |
| CN112877087A (en) * | 2021-01-13 | 2021-06-01 | 中国石油大学(华东) | Preparation process of spinnable mesophase pitch and pitch-based carbon fiber |
| CN112877087B (en) * | 2021-01-13 | 2022-07-29 | 中国石油大学(华东) | Preparation process of spinnable mesophase pitch and pitch-based carbon fiber |
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Application publication date: 20101222 |