CN102585871B - Mesophase pitch and preparation method thereof - Google Patents
Mesophase pitch and preparation method thereof Download PDFInfo
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- CN102585871B CN102585871B CN201210004011.8A CN201210004011A CN102585871B CN 102585871 B CN102585871 B CN 102585871B CN 201210004011 A CN201210004011 A CN 201210004011A CN 102585871 B CN102585871 B CN 102585871B
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Abstract
The invention relates to mesophase pitch and a preparation method thereof. The mesophase pitch contains 5 to 13 mass percent of Al2O3, SiO2, B2O3, and ZrO2 impurities which have oxidation resistance. The preparation method comprises the following steps of: catalyzing polycyclic aromatic hydrocarbon by using a friedel-crafts alkylation catalyst to perform polycondensation on medium-temperature coal pitch or coal tar which is used as a raw material, wherein the friedel-crafts alkylation catalyst is any one or more of anhydrous AlCl3, ZrCl4, SiCl4, and BCl3; after polycondensation, adding water to perform hydrolysis; and performing pyrocondensation polymerization to covert pitch subjected to polycondensation into the mesophase pitch. The mesophase pitch contains antioxidants, and the prepared carbon material has excellent oxidation resistance.
Description
Technical field
The present invention relates to a kind of mesophase pitch and preparation method thereof.
Background technology
Carbon/graphite material has a series of good performances, as low density, high specific strength, high thermal stability, resistance to ablation, corrosion-resistant and stable friction factor etc., strength and stiffness when still keeping room temperature for 1650 ℃ particularly, 2000 ℃ still can keep excellent mechanical property, are desirable high-temperature structural materials.But carbon/graphite material is poor at aerobic environment lower surface antioxidant property, oxidation weight loss obviously declines the mechanical property of carbon/graphite material, thereby has limited the widespread use of carbon/graphite material in high-temperature oxygen atmosphere field.Solving carbon/graphite material oxidant protection under high temperature problem is the prerequisite that makes full use of carbon/graphite material.
In the evolution of Carbon Materials, Brooks and Taylor have found Carbonaceous mesophase, explained the process that isotropic pitch transforms to anisotropy charcoal, greatly promoted the development of carbon industry, for the novel charcoal materials such as preparation high-performance pitch-based carbon fiber are laid a good foundation.The appearance of Carbonaceous mesophase has made in the performance of asphalt base charcoal materials a new step, has successfully prepared the charcoal fiber of needle coke and ultra high modulus from centre phase.The excellent properties such as the high purity of mesophase pitch, carbon yield, low viscosity, height spinning property, have irreplaceable effect at high-performance carbon Material Field.When preparing Mesophase Pitch-based Carbon Fibers and other senior Carbon Materials, in the middle of require forming the material asphalt of phase there is heteroatoms and ash oontent is low, narrow molecular weight distribution, aromaticity are high, in structure containing features such as alkyl short chain groups.
Adopt mesophase pitch to prepare carbon/graphite material and there is unique advantage, but carbon/graphite material oxidation behavior is at high temperature more serious, need to carry out antioxidation treatment.Tradition anti-oxidation method has two kinds: ceramic particle matrix modification technology and coating technology.What when inter-modification is prepared anti-oxidant carbon/graphite material, introduce is ceramic particle, causes antioxidant composition skewness, and oxygen molecule can be diffused in matrix, causes carbon/graphite material generation oxidizing reaction.Adopt coating technology because the coefficient of expansion does not mate, need to introduce transition layer, cause coated material preparation cost higher.
Summary of the invention
The technical problem to be solved in the present invention is to improve the antioxidant property of carbon/graphite material and be used for preparing charcoal pottery compound material.But because the antioxidant property of existing matrix modification technology and coating technology acquisition is undesirable, therefore the present invention does not start with from the preparation method of carbon/graphite material, but from preparing the raw material of carbon/graphite material, by mesophase pitch preparation technology's improvement, improve the performance of mesophase pitch, and then prepare the carbon/graphite material with superior oxidation resistance energy.
The invention provides a kind of mesophase pitch, it is characterized in that: containing mass percent is the Al2O3 with antioxidant property or the SiO2 of 5-13%, B2O3, ZrO2 impurity.Above-mentioned impurity has typical anti-oxidant function in carbon/graphite material.
The invention provides the preparation method of this mesophase pitch: selecting medium temperature coal pitch or coal tar is raw material, Friedel-Crafts catalyst condensed-nuclei aromatics is coal-tar pitch polycondensation, Fu Ke alkane catalyzer be in anhydrous AlCl3, ZrCl4, SiCl4, BCl3 any one or more than one; After finishing, polycondensation adds water hydrolysis; Then carry out thermal polycondensation polycondensation asphalt is converted into mesophase pitch.
As preferably, the mass ratio of medium temperature coal pitch or coal tar and Friedel-Crafts catalyzer is 3.2-8:1.
As preferably, Friedel-Crafts catalyzer refers to nitrogen protection, mechanical stirring by coal-tar pitch polycondensation, pressure between 3-8MPa, reaction between 150-250 ℃, reaction 4-14 hour.
As preferably, after polycondensation finishes, add water hydrolysis specifically finger polycondensation finish after by pressure removal, cooling, add water, be heated to 250 ℃ of constant temperature and carry out mechanical stirring, react relief pressure after 0.5-1 hour, water is discharged.
As preferably, thermal polycondensation refers at vacuum tightness 100-300mmHg, and temperature 400-450 ℃ carries out thermal polycondensation in constant temperature time 5-18 hour, is also liquid phase charing.
The technology of the present invention effect is: process modification of the present invention is by selecting specific Friedel-Crafts catalyzer, be metal or nonmetallic muriate, in catalysis, after warm coal or coal tar polycondensation, this catalyzer can react with water, and the Al2O3 of generation, SiO2, B2O3 or ZrO2 bring into play antioxygenation in the carbon/graphite material of being prepared by mesophase pitch subsequently.The present invention does not carry out anti-oxidant doping treatment from the preparation method of carbon/graphite material, but from preparing the raw material of carbon/graphite material, by mesophase pitch preparation technology's improvement, improve the performance of mesophase pitch, and then prepare the carbon/graphite material with superior oxidation resistance energy.
Meanwhile, general while preparing Mesophase Pitch-based Carbon Fibers and other senior Carbon Materials, require in the middle of forming the material asphalt of phase to there is heteroatoms and ash oontent is low, narrow molecular weight distribution, aromaticity are high, in structure containing features such as alkyl short chain groups.The mesophase pitch with anti-oxidant function prepared by the present invention contains metal and nonmetallic impurity is higher, has broken through the limitation of original mesophase pitch specification of quality, has realized on the contrary the antioxidant property of Carbon Materials.
Embodiment
Below in conjunction with embodiment, further narration is provided by the present invention take coal-tar pitch or coal tar, alkylation catalyst and prepare the method for high impurity content mesophase pitch as raw material.
Embodiment 1:
Get medium temperature coal pitch 800g, AlCl3100g inserts in stainless steel autoclave, and temperature reaction under nitrogen protection and mechanical stirring, to 250 ℃, passes into nitrogen pressure and remains on 3MPa, stops and within 4 hours, obtains catalysis polycondensation asphalt.After by pressure removal, cooling, after add distilled water, be heated to 250 ℃ and carry out mechanical stirring, react 0.5 hour, rear relief pressure, discharges water.Then at vacuum tightness is 100-300mmHg, 430 ℃, stop thermal treatment in 8 hours and obtain 85% optically anisotropic mesophase pitch, softening temperature is 284 ℃.Ash oontent adopts GB/T2295-2008 method to measure, and ash impurities content is 5.02%.Ash content composition adopts XRD to analyze, and result is mainly Al2O3.
Embodiment 2:
Get medium temperature coal pitch 800g, ZrCl4100g, AlCl3100g inserts in stainless steel autoclave, and temperature reaction under nitrogen protection and mechanical stirring, to 200 ℃, passes into nitrogen pressure and remains on 3MPa, stops and within 6 hours, obtains catalysis polycondensation asphalt.After by pressure removal, cooling, after add distilled water, be heated to 250 ℃ and carry out mechanical stirring, react 1 hour, rear relief pressure, discharges water.Then at vacuum tightness is 100-300mmHg, 450 ℃, stop thermal treatment in 5 hours and obtain 80% optically anisotropic mesophase pitch, softening temperature is 284 ℃.Ash oontent adopts GB/T2295-2008 method to measure, and its ash oontent is 10.18%.Ash content composition adopts XRD to analyze, and result is mainly Al2O3 and ZrO2.
Embodiment 3:
Get medium temperature coal pitch 800g, SiCl4300g inserts in stainless steel autoclave, and temperature reaction under nitrogen protection and mechanical stirring, to 180 ℃, passes into nitrogen pressure and remains on 4MPa, stops and within 10 hours, obtains catalysis polycondensation asphalt.After by pressure removal, cooling, after add distilled water, be heated to 250 ℃ and carry out mechanical stirring, react 1 hour, rear relief pressure, discharges water.Then at vacuum tightness is 100-300mmHg, 420 ℃, stop thermal treatment in 10 hours and obtain 80% optically anisotropic mesophase pitch, softening temperature is 294 ℃.Ash oontent adopts GB/T2295-2008 method to measure, and its ash oontent is 12.59%.Ash content composition adopts XRD to analyze, and result is mainly SiO2
Embodiment 4:
Get medium temperature coal pitch 800g, BCl3120g, ZrCl4100g inserts in stainless steel autoclave, and temperature reaction under nitrogen protection and mechanical stirring, to 150 ℃, passes into nitrogen pressure and remains on 6MPa, stops and within 5 hours, obtains catalysis polycondensation asphalt.After by pressure removal, cooling, after add distilled water, be heated to 250 ℃ and carry out mechanical stirring, react 1 hour, rear relief pressure, discharges water.Then at vacuum tightness is 100-300mmHg, 430 ℃, stop thermal treatment in 10 hours and obtain 85% optically anisotropic mesophase pitch, softening temperature is 285 ℃.Ash oontent adopts GB/T2295-2008 method to measure, and its ash oontent is 10.57%.Ash content composition adopts XRD to analyze, and result is mainly B2O3, ZrO2.
Embodiment 5:
Get coal tar 800g, AlCl3200g inserts in stainless steel autoclave, and temperature reaction under nitrogen protection and mechanical stirring, to 200 ℃, passes into nitrogen pressure and remains on 3MPa, stops and within 8 hours, obtains catalysis polycondensation asphalt.After by pressure removal, cooling, after add distilled water, be heated to 250 ℃ and carry out mechanical stirring, react 1 hour, rear relief pressure, discharges water.Then at vacuum tightness is 100-300mmHg, 420 ℃, stop thermal treatment in 12 hours and obtain 80% optically anisotropic mesophase pitch, softening temperature is 278 ℃.Ash oontent adopts GB/T2295-2008 method to measure, and its ash oontent is 9.84%.Ash content composition adopts XRD to analyze, and result is mainly Al2O3.
Embodiment 6:
Get coal tar 800g, ZrCl4100g, AlCl3100g inserts in stainless steel autoclave, and temperature reaction under nitrogen protection and mechanical stirring, to 200 ℃, passes into nitrogen pressure and remains on 4MPa, stops and within 8 hours, obtains catalysis polycondensation asphalt.After by pressure removal, cooling, after add distilled water, be heated to 250 ℃ and carry out mechanical stirring, react 1 hour, rear relief pressure, discharges water.Then at vacuum tightness is 100-300mmHg, 430 ℃, stop thermal treatment in 12 hours and obtain 90% optically anisotropic mesophase pitch, softening temperature is 272 ℃.Ash oontent adopts GB/T2295-2008 method to measure, and its ash oontent is 8.04%.Ash content composition adopts XRD to analyze, and result is mainly Al2O3 and ZrO2.
Embodiment 7:
Get coal tar 800g, SiCl4250g inserts in stainless steel autoclave, and temperature reaction under nitrogen protection and mechanical stirring, to 200 ℃, passes into nitrogen pressure and remains on 7MPa, stops and within 14 hours, obtains catalysis polycondensation asphalt.After by pressure removal, cooling, after add distilled water, be heated to 250 ℃ and carry out mechanical stirring, react 1 hour, rear relief pressure, discharges water.Then at vacuum tightness is 100-300mmHg, 430 ℃, stop thermal treatment in 14 hours and obtain 85% optically anisotropic mesophase pitch, softening temperature is 287 ℃.Ash oontent adopts GB/T2295-2008 method to measure, and its ash oontent is 9.54%.Ash content composition adopts XRD to analyze, and result is mainly SiO2.
Embodiment 8:
Get coal tar 800g, BCl3120g, ZrCl4100g inserts in stainless steel autoclave, and temperature reaction under nitrogen protection and mechanical stirring, to 180 ℃, passes into nitrogen pressure and remains on 8MPa, stops and within 8 hours, obtains catalysis polycondensation asphalt.After by pressure removal, cooling, after add distilled water, be heated to 250 ℃ and carry out mechanical stirring, react 1 hour, rear relief pressure, discharges water.Then at vacuum tightness is 100-300mmHg, 400 ℃, stop thermal treatment in 18 hours and obtain 90% optically anisotropic mesophase pitch, softening temperature is 279 ℃.Ash oontent adopts GB/T2295-2008 method to measure, and its ash oontent is 10.84%.Ash content composition adopts XRD to analyze, and result is mainly B2O3, ZrO2.
In above embodiment, optical anisotropy content data is estimated with polarizing microscope, and the softening temperature of pitch adopts needling method to record.
The above-mentioned foundation desirable embodiment of the present invention of take is enlightenment, and by above-mentioned description, relevant staff can, within not departing from the scope of this invention technological thought, carry out various change and modification completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to claim scope.__
Claims (6)
1. a mesophase pitch, is characterized in that: containing mass percent is the Al with antioxidant property of 5-13%
2o
3, SiO
2, B
2o
3or ZrO
2impurity; The preparation method of this mesophase pitch is: selecting medium temperature coal pitch or coal tar is raw material, and Friedel-Crafts catalyst condensed-nuclei aromatics is by coal-tar pitch polycondensation, and Friedel-Crafts catalyzer is anhydrous AlCl
3, ZrCl
4, SiCl
4, BCl
3in any one or more than one; After finishing, polycondensation adds water hydrolysis; Then carry out thermal polycondensation polycondensation asphalt is converted into mesophase pitch.
2. the preparation method of mesophase pitch described in claim 1, is characterized in that: selecting medium temperature coal pitch or coal tar is raw material, and Friedel-Crafts catalyst condensed-nuclei aromatics is by coal-tar pitch polycondensation, and Friedel-Crafts catalyzer is anhydrous AlCl
3, ZrCl
4, SiCl
4, BCl
3in any one or more than one; After finishing, polycondensation adds water hydrolysis; Then carry out thermal polycondensation polycondensation asphalt is converted into mesophase pitch.
3. the preparation method of mesophase pitch described in claim 2, is characterized by: the mass ratio of medium temperature coal pitch or coal tar and Friedel-Crafts catalyzer is 3.2-8:1.
4. the preparation method of mesophase pitch described in claim 2, is characterized by: Friedel-Crafts catalyzer refers to nitrogen protection, mechanical stirring by coal-tar pitch polycondensation, and pressure is between 3-8MPa, and reaction, between 150-250 ℃, is reacted 4-14 hour.
5. the preparation method of mesophase pitch described in claim 2, it is characterized by: after polycondensation finishes, add water hydrolysis specifically finger polycondensation finish after by pressure removal, cooling, add water, be heated to 250 ℃ and carry out mechanical stirring, react relief pressure after 1 hour, water is discharged.
6. the preparation method of mesophase pitch described in claim 2, is characterized by: thermal polycondensation refers at vacuum tightness 100-300mmHg, and temperature 400-450 ℃ carries out thermal polycondensation for constant temperature time 5-18 hour.
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| CN201210004011.8A CN102585871B (en) | 2012-01-09 | 2012-01-09 | Mesophase pitch and preparation method thereof |
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| CN102585871B true CN102585871B (en) | 2014-03-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899061B (en) * | 2012-11-02 | 2013-12-04 | 济宁碳素集团有限公司 | Method for preparing high-purity mesophase pitch and prepared high-purity mesophase pitch |
| CN103296255B (en) * | 2013-06-09 | 2016-05-11 | 东莞市卓高电子科技有限公司 | A kind of lithium ion battery negative material manufacturing process |
| CN104193037B (en) * | 2014-09-16 | 2016-01-27 | 王茜茜 | A kind of tar and waste water refining plant producing pitch |
| CN104193107B (en) * | 2014-09-16 | 2016-02-03 | 王茜茜 | A kind for the treatment of process of tar and waste water |
| CN104193106B (en) * | 2014-09-16 | 2016-02-03 | 王茜茜 | A kind of purifying method of tar and waste water |
| CN108611113B (en) * | 2018-04-24 | 2020-12-18 | 中国石油大学(华东) | Method for preparing mesophase pitch and carbon fiber by deep oxidation-catalytic polycondensation |
| CN108728147A (en) * | 2018-04-24 | 2018-11-02 | 中国石油大学(华东) | A kind of method that heavy oil fast pyrogenation pretreatment-catalyzed polycondensation prepares mesophase pitch and carbon fiber |
| CN110628449B (en) * | 2019-09-23 | 2022-05-06 | 安徽理工大学 | Method for preparing spinning-grade synthetic mesophase pitch |
| CN113149649A (en) * | 2021-03-29 | 2021-07-23 | 湖南长宇科技发展有限公司 | Mesophase-like asphalt and preparation method and application thereof |
| CN116675215B (en) * | 2023-06-21 | 2024-03-22 | 湖南大学 | Preparation method and application of soft carbon/hard carbon composite material |
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| US4457828A (en) * | 1982-03-30 | 1984-07-03 | Union Carbide Corporation | Mesophase pitch having ellipspidal molecules and method for making the pitch |
| CA1262007A (en) * | 1984-09-14 | 1989-09-26 | Ikuo Seo | Process for producing carbon fibers and the carbon fibers produced by the process |
| JPH068163B2 (en) * | 1989-02-02 | 1994-02-02 | 呉羽化学工業株式会社 | Method for manufacturing raw material pitch for carbon material |
| CN1800241A (en) * | 2005-11-30 | 2006-07-12 | 冷亮 | Preparation method of mesophase pitch carbon microspheres |
| CN102181299B (en) * | 2011-04-01 | 2013-04-24 | 常州黑玛新型碳材料工程技术研究中心有限公司 | Preparation method of intermediate-phase asphalt |
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