CN1124228C - Preparation method of mesophase carbon microsphere - Google Patents
Preparation method of mesophase carbon microsphere Download PDFInfo
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- CN1124228C CN1124228C CN00107908A CN00107908A CN1124228C CN 1124228 C CN1124228 C CN 1124228C CN 00107908 A CN00107908 A CN 00107908A CN 00107908 A CN00107908 A CN 00107908A CN 1124228 C CN1124228 C CN 1124228C
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- mcmb
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Abstract
The present invention belongs to the field of carbon materials, which mainly relates to the preparation of mesophase carbon microspheres. The process flow of the present invention comprises raw material preparation, polymerization reactions, separation and desiccation, and raw materials comprise 80 to 99.9 wt% of basic raw materials and 0.1 to 20 wt% of catalysts. The basic raw materials are one kind or the composition of two kinds of coal tar or coal pitch, and the catalysts are one kind or the composition of more than two kinds of halides of iron, cobalt and nickel or alkyl halide substitutes of the iron, the cobalt and the nickel. The parameters of the polymerization reactions comprise 350 to 500 DEG C of temperature, 1.0*10<3> to 1.0*10<7>Pa of pressure, 0.01 to 10h of time and inert gas protection.
Description
Technical field
The invention belongs to the carbon material field, relate generally to producing of MCMB.
Background technology
MCMB is one of novel carbon material of carbon material field focus development, and it is the key material that a series of cutting edge technologies of relevant departments make a breakthrough and develop.The MCMB powder can be used for various functional materialss, and its greying product is good lithium ion battery negative material.The extraordinary carbon product that with the MCMB is the raw material manufacturing has hyperfine structure and excellent isotropy, oxidation-resistance and ablation resistance, can be used as various structure component.
Producing of MCMB early mostly is to carry out under the state that does not use additive.Existing problems are that polymerization reaction time is long, polymeric reaction temperature is high, product yield is low.For overcoming these shortcomings, various additives had been developed in recent years.Adopt thermal treatment or hydrogen treatment to combine among the special public clear 62-25193 and make the pitch that does not contain free charcoal earlier, using aromatic solvent is solvable composition and insoluble composition with above-mentioned separated from bitumen, to mix after the insoluble composition change of the solvable composition of the solvent that the obtain ratio with solvent, heat-treat once more, realize that with this optical anisotropy microsphere is the high yield of MCMB.Among the Te Kaiping 7-26852, in coal tar or coal-tar pitch, add three rings or the aromatics more than three rings of 0.5-25% weight ratio, improve the yield of MCMB with this.Opening among the flat 7-126659 the spy, is the carbon black that adds the 0.5-10% weight ratio in coal tar or coal-tar pitch, has realized certain raising of MCMB productive rate.
Above-mentioned various deficiency of improving one's methods is, the process of perhaps producing is complicated, and perhaps added ingredients is difficult for obtaining, and perhaps the product recovery rate improves very not remarkable.
Summary of the invention
The object of the present invention is to provide a kind of raw material sources extensive, cost is low, and technology is simple, can obviously improve the preparation method of the MCMB of MCMB recovery rate.
At above-mentioned purpose, the technical process of MCMB preparation method of the present invention comprises raw material outfit, mixing, polyreaction, separation and drying.Now that each operation division is as follows:
(1) raw material is equipped with
When raw material was equipped with, raw material was formed and is comprised basic raw material and catalyzer, and the composition proportion (wt%) that its raw material is formed is:
Basic raw material 80-99.9%, catalyzer are 0.1-20%,
Basic raw material is any or both sums in coal tar or the coal-tar pitch;
Catalyzer is any or any two above sum in the halogenide of iron, cobalt, nickel;
Halogens be in fluorine, chlorine, bromine, the iodine any.
In addition, coal tar and coal-tar pitch can replace with petroleum industry heavy oil and petroleum pitch respectively, also can be replaced by the secondary heavy arene that above-mentioned raw materials processes.
Coal tar or coal-tar pitch or its surrogate can be liquid or solid-state, and catalyzer can directly use, and also can carry on other carrier and use.
(2) polyreaction:
The basic raw material that the composition proportion that will form according to raw material is equipped with is packed into and is carried out polyreaction in the polymerization reactor, and the parameter of polyreaction is as follows:
Pressure (Pa): 1.0 * 10
3-1.0 * 10
7Pa
Temperature (℃): 350-500
Time (h): 0.01-10
Atmosphere: the protective atmosphere that rare gas element or id reaction produce.
After the polyreaction, obtain the mixture of MCMB and matrix.
(4) separate
Adopt solvent separation, centrifugal separation or precipitation separation that MCMB is separated from the mixture of MCMB and matrix, obtain MCMB.
Solvent separation can adopt pyridine, quinoline equal solvent, also can adopt other aromatic hydrocarbons or alkane solvent, isolates MCMB with filter method from the mixed solution of gained.
Centrifugal separation is carried out on whizzer.
Precipitation separation is that liquid phase-solid-phase mixture that polymerization reactant and solvent form is carried out precipitate and separate in settling tank, and the gained solid formation is MCMB.
(5) drying
Through separating obtained MCMB after drying, promptly become MCMB of the present invention.Its drying temperature is 150-350 ℃, and vacuum tightness is 1.0 * 10
2-1.0 * 10
3Pa, volatile matter is controlled at 10-12%.
The present invention can pass through the parameter of kind, proportioning components and the polyreaction of adjustment raw material, granularity, size distribution and the condition of surface of control MCMB.
The granularity that adopts method of the present invention to produce MCMB is 0.1-100 μ m, the yield 25-70% of MCMB.
Adopt method of the present invention, can produce the high pitch of MCMB content.
Compared with prior art, the present invention has following advantage:
1, raw material sources are wide, and are cheap, and cost is low.
2, production technique is simple, is easy to combine with existing production technique, is convenient to industrialization.
3, product yield height has been broken through and it is generally acknowledged that the MCMB yield is no more than 20% routine;
4, product cut size, form, controllable microstructure;
5, the product produced of this method has extensive use.
Embodiment
Adopt method of the present invention,, prepared many batches of MCMB according to its technical process.Wherein the raw material moiety proportioning of six batches of tests is as shown in table 1.The raw material polymerization reactor of packing into after mixing carries out polyreaction, and its reaction parameter is as shown in table 2.Separate after the polyreaction, subsequent drying, separate mode and drying parameter are as shown in table 3.After drying, promptly obtain MCMB of the present invention.The granularity and the recovery rate thereof of gained MCMB are as shown in table 4.
In order to contrast, in prior art, three comparative examples that adopt other method to prepare MCMB have related parameter also to add in the corresponding table.
The moiety proportioning (wt%) of table 1 embodiment raw material
Table 2 embodiment polymerization reaction parameter
Table 3 embodiment polymeric reaction product separate mode and drying parameter
The particle diameter and the recovery rate of table 4 embodiment MCMB
Claims (2)
1, a kind of preparation method of MCMB, its technical process comprises raw material outfit, polyreaction, separation, drying, it is characterized in that:
When (1) raw material was equipped with, raw material was formed and is comprised basic raw material and catalyzer, and the composition proportion (wt%) that its raw material is formed is:
Basic raw material 80-99.9%, catalyzer are 0.1-20%,
Basic raw material is any or both sums in coal tar or the coal-tar pitch;
Catalyzer is the above sum of halogenide any or any two of iron, cobalt, nickel;
Halogens be in fluorine, chlorine, bromine, the iodine any;
(2) parameter of polyreaction is:
Pressure (Pa): 1.0 * 10
3-1.0 * 10
7
Temperature (℃): 350-500
Time (h): 0.01-10
Atmosphere: the protective atmosphere that rare gas element or id reaction produce.
2, method according to claim 1 is characterized in that coal tar or coal-tar pitch can replace with petroleum industry heavy oil or petroleum pitch respectively, also can be replaced by the secondary heavy arene that above-mentioned raw materials processes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00107908A CN1124228C (en) | 2000-05-26 | 2000-05-26 | Preparation method of mesophase carbon microsphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00107908A CN1124228C (en) | 2000-05-26 | 2000-05-26 | Preparation method of mesophase carbon microsphere |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1272453A CN1272453A (en) | 2000-11-08 |
| CN1124228C true CN1124228C (en) | 2003-10-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00107908A Expired - Fee Related CN1124228C (en) | 2000-05-26 | 2000-05-26 | Preparation method of mesophase carbon microsphere |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387695C (en) * | 2005-11-19 | 2008-05-14 | 燕山大学 | Mesophase carbon alloy lubricating additive and its preparing method |
| CN101811694A (en) * | 2010-05-27 | 2010-08-25 | 王磊 | Method for preparing artificial graphite mesocarbon microbeads |
| 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 |
| CN104293366A (en) * | 2014-10-21 | 2015-01-21 | 华侨大学 | Method for preparing isotropic coke through catalytic carbonization |
| CN105238428A (en) * | 2015-10-10 | 2016-01-13 | 湖南大学 | Medium temperature coal pitch modification method and product |
| CN105858640B (en) * | 2016-06-27 | 2017-10-17 | 太原理工大学 | A kind of carbosphere preparation method of size tunable |
| CN109319758B (en) * | 2018-10-10 | 2020-09-22 | 中钢集团鞍山热能研究院有限公司 | Co-production process method of mesocarbon microbeads and negative electrode material coke |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03239796A (en) * | 1990-02-17 | 1991-10-25 | Toho Gas Co Ltd | Preparation of meso-phase carbon-microbeads |
| EP0585193A1 (en) * | 1992-07-10 | 1994-03-02 | Repsol Petroleo S.A. | Method for the industrial manufacture of carbon-containing mesophase microspheres and derived carbon objects |
| CN1259546A (en) * | 1999-01-04 | 2000-07-12 | 北京化工大学 | Prepn. method of mesophase asphalt carbon microsphere |
| JP3239796B2 (en) * | 1997-04-28 | 2001-12-17 | 松下電器産業株式会社 | Charger |
-
2000
- 2000-05-26 CN CN00107908A patent/CN1124228C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03239796A (en) * | 1990-02-17 | 1991-10-25 | Toho Gas Co Ltd | Preparation of meso-phase carbon-microbeads |
| EP0585193A1 (en) * | 1992-07-10 | 1994-03-02 | Repsol Petroleo S.A. | Method for the industrial manufacture of carbon-containing mesophase microspheres and derived carbon objects |
| JP3239796B2 (en) * | 1997-04-28 | 2001-12-17 | 松下電器産業株式会社 | Charger |
| CN1259546A (en) * | 1999-01-04 | 2000-07-12 | 北京化工大学 | Prepn. method of mesophase asphalt carbon microsphere |
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| CN1272453A (en) | 2000-11-08 |
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