CN1108986C - Preparation of interphase carbon microball - Google Patents
Preparation of interphase carbon microball Download PDFInfo
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- CN1108986C CN1108986C CN00120796A CN00120796A CN1108986C CN 1108986 C CN1108986 C CN 1108986C CN 00120796 A CN00120796 A CN 00120796A CN 00120796 A CN00120796 A CN 00120796A CN 1108986 C CN1108986 C CN 1108986C
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- raw material
- mcmb
- preparation
- pitch
- catalyzer
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Abstract
The present invention belongs to the field of carbon materials, and raw materials of the carbon materials are prepared from asphalt and heavy oil. A preparation method of a mesophase carbon microsphere of the present invention comprises raw material preparation, polymerization reactions and the separation and the desiccation of polymerisate, and the 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 the asphalt or the aromatic heavy oil, and the catalysts are one kind or the composition of more than two kinds of nitrates of iron, nickel and cobalt. The present invention has the characteristics of high yield of products, controllable particle size, uniform particle size distribution, etc.
Description
Technical field
The invention belongs to the carbon material field, relate generally to the method for producing MCMB by pitch, aromatic series mink cell focus.
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, the product recovery rate 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 recovery rate 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 recovery rate 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.
In JPO4-161183, be raw material with the naphthalene, with HF-BF
3Being catalyzer, though this kind Catalytic processes can improve the MCMB recovery rate, is raw material with pure naphthalene, has limited the selection of raw material, and has improved production cost.
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, the composition of raw material comprised basic raw material and catalytic materials, and the proportioning (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 any two above sum in pitch or the aromatic series mink cell focus.
Catalyzer is any or any two above sum in the nitrate of iron, cobalt, nickel.
The aromatic series mink cell focus can be in coal tar, petroleum industry heavy oil, carbolineum or the naphthalene polycyclic aromatic hydrocarbons any; Pitch can be coal-tar pitch or petroleum pitch.
Described aromatic raw material does not have softening temperature, free charcoal or the restriction of Q1 content.Can be the monomer of above-mentioned basic raw material, also can be their proportioning thing or mixture, goes back the secondary heavy arene that is processed to form by above-mentioned raw materials, as by-product tar or the by-product pitch that produces when producing MCMB.
Above-mentioned catalyzer can directly mix with basic raw material, also can carry on other carrier and use, for example make pelleted catalyst with definite shape, like this catalyzer with can use repeatedly after MCMB is separated, and can improve the purity of MCMB.
(2) polyreaction:
To form basic raw material that proportioning is equipped with and catalyzer according to raw material and pack into and carry out polyreaction in the polymerization reactor, the parameter of polyreaction is as follows:
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.
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 recovery rate 25-70% of MCMB.
Adopt method of the present invention, do not carrying out under the isolating situation of MCMB, can directly produce the high pitch of spherical intermediate phase 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 recovery rate height has been broken through and it is generally acknowledged that the MCMB recovery rate is no more than 20% routine.In the prior art, as the particle diameter≤10 μ m of MCMB, its recovery rate usually＜10%.
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.Separate subsequent drying after the polyreaction.Polyreaction, separate mode and drying parameter are as shown in table 2.After drying, promptly obtain MCMB of the present invention.The granularity and the recovery rate thereof of gained MCMB are as shown in table 3.
In order to contrast, there is related parameter also to add in the corresponding table three comparative examples of the MCMB of other method preparation of available technology adopting.
The raw material of table 1 embodiment and comparative example is formed proportioning (Wt%)
Table 2 embodiment polyreaction, separation and drying parameter
The particle diameter and the recovery rate of table 3 embodiment and comparative example gained intermediate phase centre microballoon
Claims (3)
1, a kind of preparation method of MCMB comprises raw material outfit, polyreaction, separation and drying, it is characterized in that:
When raw material was equipped with, the composition of raw material comprised basic raw material and catalyzer, and the proportioning (Wt%) that 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 pitch or the aromatic series mink cell focus;
Catalyzer is any or any two above sum in the nitrate of iron, cobalt, nickel;
The parameter of polyreaction is as follows:
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, preparation method according to claim 1, it is characterized in that the aromatic series mink cell focus can be in coal tar, petroleum industry heavy oil, mattress oil or the naphthalene polycyclic aromatic hydrocarbons any.
3, preparation method according to claim 1 is characterized in that pitch can be coal-tar pitch or petroleum pitch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00120796A CN1108986C (en) | 2000-07-14 | 2000-07-14 | Preparation of interphase carbon microball |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00120796A CN1108986C (en) | 2000-07-14 | 2000-07-14 | Preparation of interphase carbon microball |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1278513A CN1278513A (en) | 2001-01-03 |
| CN1108986C true CN1108986C (en) | 2003-05-21 |
Family
ID=4588409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00120796A Expired - Lifetime CN1108986C (en) | 2000-07-14 | 2000-07-14 | Preparation of interphase carbon microball |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1108986C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341777C (en) * | 2006-04-11 | 2007-10-10 | 太原理工大学 | Method of preparing carbon pellets by using heavy oil residue as raw material |
| CN102633245A (en) * | 2011-05-27 | 2012-08-15 | 天津市贝特瑞新能源材料有限责任公司 | Control method of intermediate phase carbon microball D50 and device for producing intermediate phase carbon microball |
| CN106082168B (en) * | 2016-06-06 | 2018-02-09 | 安徽科达洁能新材料有限公司 | A kind of method that carbonaceous mesophase spherules are efficiently prepared using medium temperature coal pitch |
| 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 |
| CN109179371A (en) * | 2018-10-24 | 2019-01-11 | 武汉科技大学 | A kind of mesocarbon microspheres and the method using pitch hot tearing oil preparation mesocarbon microspheres |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4600496A (en) * | 1983-05-26 | 1986-07-15 | Phillips Petroleum Company | Pitch conversion |
| JPH01299890A (en) * | 1988-05-27 | 1989-12-04 | Nippon Steel Corp | Pitch reforming method |
| JPH10255770A (en) * | 1997-03-14 | 1998-09-25 | Adokemuko Kk | Manufacture of graphite material for battery and battery |
-
2000
- 2000-07-14 CN CN00120796A patent/CN1108986C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4600496A (en) * | 1983-05-26 | 1986-07-15 | Phillips Petroleum Company | Pitch conversion |
| JPH01299890A (en) * | 1988-05-27 | 1989-12-04 | Nippon Steel Corp | Pitch reforming method |
| JPH10255770A (en) * | 1997-03-14 | 1998-09-25 | Adokemuko Kk | Manufacture of graphite material for battery and battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1278513A (en) | 2001-01-03 |
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