CN1100093C - Prepn. method of mesophase asphalt carbon microsphere - Google Patents
Prepn. method of mesophase asphalt carbon microsphere Download PDFInfo
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- CN1100093C CN1100093C CN99100008A CN99100008A CN1100093C CN 1100093 C CN1100093 C CN 1100093C CN 99100008 A CN99100008 A CN 99100008A CN 99100008 A CN99100008 A CN 99100008A CN 1100093 C CN1100093 C CN 1100093C
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- microballoon
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Abstract
The present invention relates to a preparation method of mesophase asphalt carbon miroshperes. Condensed aromatic raw materials and additives (accounting for 0.1 to 10 wt% of the aromatic raw materials) take part in thermal polycondensation reactions to generate mesophase asphalt containing the miroshperes. Then, the mesophase asphalt and industrial heavy oil whose boiling range is from 200 to 360 DEG C are mixed, thermally dissolved and filtered, the microspheres are separated from residue isotropic asphalt components by organic solvents, and the mesophase asphalt carbon mirospheres are obtained. The additives used by the method are graphitized carbon powder such as coke powder, graphite powder or mesophase mirospheres, etc., with the granularity of smaller than 100 mum, and the performance exertion of the easy graphitization of the carbon mirospheres is not influenced by the addition of the additives. The mesophase asphalt carbon mirospheres prepared by the method have the advantages of uniform granularity, high yield and high extraction efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of precursor-mesophase pitch carbon microspheres of raw material of wood-charcoal material, should
Method comprises with the condensed-nuclei aromatics to be middle asphalt carbon microballoon synthetic of raw material and to extract two processes.
Background technology
Mesophase pitch carbon microspheres (Mesocarbon Microbeads, MCMB) be a kind of novel high-performance charcoal material precursor, it also can be used as uses such as performance liquid chromatographic column filler, support of the catalyst, activated carbon with high specific surface area except can be used as high-density high-strength isotropic carbon material feedstock.What especially attract people's attention is that the electrode materials aspect that the mesophase pitch carbon microspheres is used for lithium-ion secondary cell demonstrates very excellent performance, causes worldwide research and development mutually unexpectedly.
The preparation method of mesophase pitch carbon microspheres mainly contains two kinds at present: emulsion process and polymerization.The build mesophase pitch is that raw material passes through high temperature dispersion medium emulsification balling-up to emulsion process to melt also, polymerization is handled by direct heat and is made at first polycondensation formation mesophase ball of condensed-nuclei aromatics raw material, adopts suitable means that bead is extracted from mother liquor pitch then.Polymerization is compared with emulsion process, has technology simple (not needing loaded down with trivial details not melting and the high temperature dispersing technology), the thermal response stage with regard to may command microballoon size and distribution and equipment characteristics such as less input, therefore, polymerization is present intermediate phase microballoon synthetic main method.As everyone knows, no matter coal-tar pitch or petroleum residual oil, the aromatic hydrocarbon molecule amount that all has broad distributes and certain content of heteroatoms, they can cause step-by-step polymerization because of molecular size and active difference carrying out thermal polycondensation when reaction, make the microsphere particle skewness, and be easy to generate between spheroid and melt and phenomenon, be difficult to obtain the uniform bead of a large amount of diameter Distribution.Therefore, select suitable aroamtic hydrocarbon raw material, additive and thermal polycondensation reaction conditions bigger to the generation and the form influence of microballoon.Have research to think, use additive, for example: the adding of materials such as a quinoline insolubles (comprise carbon black and other impurity, be called for short QI) or carbon black has the mesophase ball of promotion to generate, stop its grow up and melt and effect.(Carbon 35 (7) for Japanese Patent (JP07-126659) and document, 875 (1997)) introduced in coal tar and pitch or naphthalene catalysis synthetic asphalts and added carbon black, not only can improve the yield of intermediate phase microballoon, and the size of may command microballoon, make it more uniform distribution; Document (Journal of Materials Science29,4757 (1994)) report is controlled the generation of intermediate phase microballoon by a QI content in the control pitch and is grown up.In addition, (Carbon 32,1073 (1994) for document; Carbon 34,1473 (1996)) report adds organometallic compounds such as ferrocene, iron carbonyl and can effectively promote the even generation of intermediate phase microballoon and stop it to melt also in coal-tar pitch.Above-mentioned additive is that carbon black or a QI belong to difficult greying material, they mix in the middle of the microballoon that extracts, graphitization characteristic and other physicals (as conductivity) of intermediate phase microballoon have been reduced, increased foreign matter content, finally can influence MCMB performance performance (as when its during as the negative material of lithium-ion secondary cell, can reduce the reversible capacity and the cycle life of battery).At present, the method for extraction microballoon mainly contains two kinds from the mesophase pitch that contains microballoon: high temperature centrifugal separation (Extended Abstracts of 17
ThBiennial Conference on Carbon, p.409,1985; J.Electrochem.Soc.142,1041 (1995) and one step solvent extration (JP07-126659; USP 3956436).The cost of equipment height that the high temperature centrifugal separation needs, and melting and phenomenon of occurring between microballoon when being difficult to control centrifugal settling; One time solvent extration generally need be used intensive polar solvent, as using pyridine, quinoline etc., and the direct repeatedly extracting mesophase pitch of needs, this not only will consume a large amount of organic solvents, and because the solvent Gradient Effect, the pyridine equal solvent can produce serious etching to microballoon, makes the sphericity variation, thereby influences the quality of mesophase pitch microballoon.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method that can obtain the mesophase pitch carbon microspheres that quality is good, yield is high.This method is to adopt polymerization to add new additive in the condensed-nuclei aromatics raw material to make the mesophase pitch microballoon, extracts the mesophase pitch carbon microspheres through heavy oil thermosol and two steps of solvent extraction again.This method microspheres prepared epigranular, yield and extraction efficiency are all higher.
What the preparation method of mesophase pitch carbon microspheres of the present invention was same as the prior art is; all be with aroamtic hydrocarbon raw material and additive uniform mixing; under protection of inert gas, in 350～500 ℃ of scopes, carry out the thermal polycondensation reaction; obtain containing the mesophase pitch of microballoon; with organic solvent microballoon and residual isotropic pitch are wherein carried out extracting and separating again, obtain the mesophase pitch carbon microspheres.Different is that the aroamtic hydrocarbon raw material that is adopted is: coal tar, coal-tar pitch, petroleum residual oil, petroleum pitch, polyvinyl chloride pitch or solvent refined coal.But additive adopts the greying carbon dust, and the consumption of additive is 0.1～10wt% of aroamtic hydrocarbon raw material, and additive particle size is less than 100 μ m.Before separating with organic solvent extraction, to filter with the enrichment microballoon with industrial heavy oil thermosol earlier, the boiling range of industrial heavy oil is in 200～360 ℃ of scopes.But the greying carbon dust that is adopted is: coke powder, Graphite Powder 99 or MCMB.The consumption of additive is 1～6wt% of aroamtic hydrocarbon raw material preferably.Additive particle size is preferably less than 30 μ m.
The synthesis condition of the mesophase pitch that mesophase pitch carbon microspheres preparation method of the present invention provides is the same with known technology; be with additive and aroamtic hydrocarbon raw material uniform mixing in proportion; under protection of inert gas, between 350～500 ℃, carry out the thermal polycondensation reaction; its residence time is no more than 20 hours, obtains containing the mesophase pitch of microballoon.Additive of the present invention is selected materials such as coke powder, Graphite Powder 99 or MCMB for use, but they are the greying material, and there is the performance performance that does not influence final MCMB in it.The granular size of additive has a significant impact the formation of intermediate phase microballoon, should select for use granularity less than 100 μ m.Particle is excessive, will weaken its generation that promotes bead and inhibition and melt effect also; Particle is too little, will increase the preparation cost of additive, preferably granularity＜30 μ m; The amount of additive should be 0.1～10wt% of aroamtic hydrocarbon raw material.Additive capacity is very few, will not have desired result, and the microballoon of generation melts also easily; During greater than 10wt%, system viscosity increases very fast, is difficult for forming the bigger intermediate phase spheroid of granularity, only may form the following small nucleus of 1 μ m, and too much additive to future MCMB use may produce detrimentally affect.Additive amount is preferably in 1～6wt% scope.
The separation of the intermediate phase microballoon that the preparation method of mesophase pitch carbon microspheres of the present invention provides is to adopt two step extraction process, the pitch and industrial heavy oil mixing thermosol that at first will contain the intermediate phase microballoon, through heat filtering enrichment intermediate phase microballoon, with organic solvent microballoon is separated with wherein residual isotropic pitch component then, obtain the mesophase pitch carbon microspheres.The industrial heavy oil that the first step was selected for use when microballoon extracted should have higher boiling range and lower viscosity, adopts the industrial heavy oil of boiling range in 200～360 ℃ of scopes for well, and its usage quantity is that 1～20 times of mesophase pitch weight is advisable.The heavy oil addition is very few, will make filtration difficulty and pitch meltage less; Addition is too much, and wastage of material has improved preparation cost.The second step solvent for use can be selected general solvent: benzene, toluene, tetrahydrofuran (THF), pyridine or quinoline etc. are colourless as the standard that pumps with the filtrate color.The mesophase pitch carbon microspheres of the present invention's preparation has all higher characteristics of epigranular, yield and extraction efficiency.
Embodiment
It is following that the embodiment that provides will the present invention is described in detail.
The preparation condition of intermediate phase microballoon provided by the present invention is listed in table 1.
Embodiment: will remove pyridine insoluble (being called for short PI) coal-tar middle oil or pitch (being the pyridine soluble composition), purify in the reactor of packing into after petroleum residual oil or pitch and the listed additive of table 1 mix by a certain percentage; after under nitrogen protection, carrying out the thermal polycondensation reaction; be cooled to room temperature rapidly, must contain the pitch of intermediate phase microballoon.This mesophase pitch is mixed by weight 1: 10 with a kind of catalytic cracking petroleum naphtha heavy component (280～360 ℃ of boiling ranges), below the heavy oil boiling point, stir thermosol, filtering enrichment intermediate phase microballoon with No. 5 acid funnels then, is that the extracting of solvent Soxhlet obtains MCMB with pyridine at last again.6 liang of required times of extraction in step of sequence number 1～sequence number all are no more than 6 hours in the table 1.
The yield of sequence number 1MCMB is 50% (based on material asphalt) in the table 1, and scanning electron microscope result shows, its epigranular, good sphericity.
The yield of sequence number 5MCMB is 24% (based on raw material residual oil) in the table 1, and scanning electron microscope result shows, its epigranular, good sphericity.
Comparative example 1 does not use additive, and the coal-tar middle oil pitch that directly will remove a PI is thermal polycondensation under the reaction conditions identical with table 1 sequence number 1, and the gained mesophase pitch is converted into 100% fully and melts and body texture, no mesophase ball existence.
Comparative example 2 is handled the mesophase pitch that contains microballoon in table 1 sequence number 1 without industrial heavy oil, directly with pyridine extracting in Soxhlet extractor, need the extracting of 18 hours ability clean, the scanning electron microscope result of the pyridine insoluble that obtains shows, non-spherical particle is more, and sphericity is relatively poor.Just but extracting is clean and the mesophase pitch of handling through heavy oil of identical weight only needs 3 hours.
The preparation condition of table 1 intermediate phase microballoon
| Sequence number | Aroamtic hydrocarbon raw material | Additive | The thermal polycondensation reaction conditions | ||
| Title | Consumption (wt%) * | Granularity (μ m) | Temperature-time | ||
| 1 | Coal-tar pitch | Graphite Powder 99 | 2 | ＜30 | 420℃-5min |
| 2 | Coal-tar pitch | Graphite Powder 99 | 2 | 90＜d＜100 | 420℃-5min |
| 3 | Coal-tar pitch | Coke powder | 10 | ＜30 | 420℃-5min |
| 4 | Coal-tar pitch | The intermediate phase microballoon | 6 | ＜13 | 410℃-30min |
| 5 | Petroleum residual oil | Graphite Powder 99 | 1 | ＜30 | 420℃-240min |
| 6 | Petroleum residual oil | Graphite Powder 99 | 0.1 | ＜30 | 420℃-300min |
*The aroamtic hydrocarbon raw material weight percent
Claims (4)
1, a kind of preparation method of mesophase pitch carbon microspheres; with aroamtic hydrocarbon raw material and additive uniform mixing; under protection of inert gas, in 350～500 ℃ of scopes, carry out the thermal polycondensation reaction; obtain containing the mesophase pitch of microballoon; with organic solvent microballoon and residual isotropic pitch are wherein carried out extracting and separating again; obtain the mesophase pitch carbon microspheres, it is characterized in that:
Aroamtic hydrocarbon raw material is: coal tar, coal-tar pitch, petroleum residual oil, petroleum pitch, polyvinyl chloride pitch or solvent refined coal;
But additive is the greying carbon dust, and the consumption of additive is 0.1～10wt% of aroamtic hydrocarbon raw material, additive particle size＜100 μ m;
Before separating with organic solvent extraction, to filter with the enrichment microballoon with industrial heavy oil thermosol earlier, the boiling range of industrial heavy oil is in 200～360 ℃ of scopes.
2, preparation method according to claim 1 is characterized in that: but the greying carbon dust is: coke powder, Graphite Powder 99 or MCMB.
3, preparation method according to claim 1 is characterized in that: the consumption of additive is 1～6wt% of aroamtic hydrocarbon raw material.
4, preparation method according to claim 1 is characterized in that: additive particle size＜30 μ m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99100008A CN1100093C (en) | 1999-01-04 | 1999-01-04 | Prepn. method of mesophase asphalt carbon microsphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99100008A CN1100093C (en) | 1999-01-04 | 1999-01-04 | Prepn. method of mesophase asphalt carbon microsphere |
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| Publication Number | Publication Date |
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| CN1259546A CN1259546A (en) | 2000-07-12 |
| CN1100093C true CN1100093C (en) | 2003-01-29 |
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| CN99100008A Expired - Fee Related CN1100093C (en) | 1999-01-04 | 1999-01-04 | Prepn. method of mesophase asphalt carbon microsphere |
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Families Citing this family (16)
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|---|---|---|---|---|
| CN1124228C (en) * | 2000-05-26 | 2003-10-15 | 冶金工业部鞍山热能研究院 | Preparation method of mesophase carbon microsphere |
| CN101552333B (en) * | 2009-04-03 | 2011-01-05 | 湖州创亚动力电池材料有限公司 | Method of preparing carbon anode active material of lithium-ion battery |
| CN102653397A (en) * | 2011-03-01 | 2012-09-05 | 辽宁科技大学 | Preparation method of coal tar-based mesocarbon microbead |
| CN102225755B (en) * | 2011-05-26 | 2013-02-27 | 淄博矿业集团有限责任公司 | Preparation method of mesophase carbon microspheres from coal liquefaction residues |
| CN103011148A (en) * | 2012-12-19 | 2013-04-03 | 中国平煤神马集团开封炭素有限公司 | Method for preparing isotropical graphite |
| CN103420358B (en) * | 2013-08-02 | 2014-12-10 | 鲁南煤化工研究院 | Method for preparing mesocarbon microbeads |
| CN106115657B (en) * | 2016-06-12 | 2018-03-30 | 湖北鑫固久技术装备有限公司 | A kind of method of rotating vortex production carbon microspheres |
| CN106753495A (en) * | 2016-12-29 | 2017-05-31 | 中石化南京工程有限公司 | A kind of method of high temperature coal-tar/residual oil production carbosphere and dipping agent bitumen |
| CN107720721B (en) * | 2017-08-28 | 2019-11-01 | 煤炭科学技术研究院有限公司 | Mesocarbon microspheres and preparation method thereof |
| CN110499175A (en) * | 2019-09-04 | 2019-11-26 | 北京旭阳科技有限公司 | A method of super regular high-purity pitch coke is prepared by mid temperature pitch |
| CN111547715A (en) * | 2020-04-28 | 2020-08-18 | 鞍钢股份有限公司 | Method for improving yield of mesocarbon microbeads |
| CN112831334B (en) * | 2021-01-13 | 2022-07-29 | 中国石油大学(华东) | Preparation method of mesophase pitch and mesophase carbon microspheres |
| CN113247878B (en) * | 2021-06-30 | 2022-09-09 | 北京化工大学 | Preparation method and application of asphalt-based carbon microspheres |
| CN113353915B (en) * | 2021-07-19 | 2022-12-20 | 中国石油化工股份有限公司 | Mesocarbon microbeads, preparation method thereof, spherical porous activated carbon material and application thereof |
| CN113845114B (en) * | 2021-11-18 | 2023-06-20 | 湖南大学 | Preparation method of core-shell type mesophase carbon microsphere |
| CN115124852B (en) * | 2022-06-24 | 2023-12-15 | 武汉科技大学 | Impregnating asphalt for carbon-carbon composite material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0826659A (en) * | 1994-07-12 | 1996-01-30 | Hisaya Nakagawa | Hang-up device for concrete block for revetment |
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1999
- 1999-01-04 CN CN99100008A patent/CN1100093C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0826659A (en) * | 1994-07-12 | 1996-01-30 | Hisaya Nakagawa | Hang-up device for concrete block for revetment |
Non-Patent Citations (3)
| Title |
|---|
| CARMON NO.35 VOL.7 1997-01-01 EFFECTS OF CARBON BLACK ADDITION ON PREPARATION OF MESIO CARBON MICROBEADS YOZO KORAI * |
| CARMON NO.35 VOL.7 1997-01-01 EFFECTS OF CARBON BLACK ADDITION ON PREPARATION OF MESIO CARBON MICROBEADS YOZO KORAI;新型碳材料 VOL.13 NO.4 1998-01-01 热缩聚工艺条件对中间相微球形成的影响 宋怀河 * |
| 新型碳材料 VOL.13 NO.4 1998-01-01 热缩聚工艺条件对中间相微球形成的影响 宋怀河 * |
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