CN1185491A - Process for preparing middle phase asphalt - Google Patents
Process for preparing middle phase asphalt Download PDFInfo
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- CN1185491A CN1185491A CN96122394A CN96122394A CN1185491A CN 1185491 A CN1185491 A CN 1185491A CN 96122394 A CN96122394 A CN 96122394A CN 96122394 A CN96122394 A CN 96122394A CN 1185491 A CN1185491 A CN 1185491A
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- crosslinking agent
- oligomer
- asphalt
- mesophase pitch
- heat treatment
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Abstract
A method for preparing intermediate asphalt includes mixing aromatic compound, crosslinking agent and catalyst in the ratio of 1mol : 0.2 -1.0 mol : 5 -20 wt% (total wt.of aromatic compound and crosslinking agent), making them conduct crosslinking reaction to produce aromic oligomer which is then passed through heat treatment for 10-25 hours at 340-380 degree C to obtain a high-quality asphalt. Said invention features in simple process, high yield of asphalt, low softening point (220-290 degree C), good rheidity and high H/C ratio, which is suitable to being as raw material for preparing high-property asphalt-base carbon fiber new materials etc..
Description
The invention belongs to the preparation method of mesophase pitch.
Mesophase pitch is the raw material of preparation high-performance pitch based carbon fiber, needle coke and other senior raw material of wood-charcoal material, itself also is a kind of raw material of wood-charcoal material of uniqueness.When producing the senior raw material of wood-charcoal material of high-performance pitch based carbon fiber and other, the material asphalt of phase has hetero atom and content of ashes is low, structure is formed homogeneous, aromaticity height, condensation degree are low, be rich in characteristics such as alkyl short chain and naphthene group in the structure in the middle of require forming, yet used feed coal tar asphalt and black petroleum products but can not satisfy above requirement fully usually, needs it is carried out preliminary treatment or/and the modification processing distributes to remove ash impurities and to adjust raw material mix and form.Japan Patent (NO.18421/83) has reported that the method that adopts hydrogenation means modulation mesophase pitch is a phase method in the middle of what is called is given.At first coal tar asphalt is mixed with hydrogen supply dissolvent and carry out hydrogenation treatment, then reach decompression distillation after filtration and isolate hydrogenation pitch, carry out then that heat treatment makes it be converted into mesophase pitch between high temperature, short time.Japan Patent NO.167788/81 has introduced the method for preparing mesophase pitch from petroleum catalytic cracking residual oil, at first with ash impurities and catalyst granules in the solvent extraction removal residual oil, and then, obtain mesophase pitch through heat treatment again through the suitable component of multiple-stage solvent processing acquisition as the mesophase pitch presoma.The method for preparing complex process, the preparation cost height, the performance increase rate of charcoal fiber is little, and therefore, adopting the pure aromatics compound to prepare the high-quality mesophase pitch by synthetic method has been basic tendency since the eighties.As Japan Patent (NO.83317/86,83318/86) a kind of AlCl that uses is proposed
3Make catalyst and set out by aromatic compounds such as naphthalenes that synthetic softening point is low, the technology of the spinnability mesophase pitch of good rheological property, but AlCl
3Use exist with reaction system and be difficult to separate and reclaim so that influence the shortcoming of final charcoal fibre property.Adopt HF/BF
3(Japan Patent 328193/92 etc.) make catalyst can partly solve use AlCl
3The problem that exists, and improved the reactivity of system, the pitch yield increases considerably, but because HF/BF
3Have strong corrosivity, thereby equipment and materials is had relatively high expectations, and have the problem of operation protection.It is aroamtic hydrocarbon raw material that United States Patent (USP) (USP 4670129) report adopts petroleum cuts C8-C10 alkylbenzene, prepares the method for low softening point mesophase pitch then through further heat treatment by the synthetic aromatic resins of formaldehyde/Bronsted acid catalytic crosslinking.This method is because employed raw material is an aromatic hydrocarbons mixture, and alkyl replaces the various and side chain uneven in length (containing methyl, ethyl, propyl group etc.) in position on the phenyl ring, therefore can influence the uniformity of carbonizing production, and the mesophase pitch yield of gained on the low side (＜10wt%).
In addition, said method forms the stage mutually and all adopts 〉=400 ℃ high-temperature heat treatment in the centre, not only waste energy, and be unfavorable for controlling the reaction uniformity and the extent of reaction, is easy to generate excessive polymerization.
The purpose of this invention is to provide and a kind ofly set out in the method for lower temperature synthesized high-performance mesophase pitch by pure aromatics, this method can improve the yield of mesophase pitch, and course of reaction is controlled easily.
The preparation method of mesophase pitch of the present invention, be with aromatic compound and crosslinking agent and catalyst mixed with 1mol: 0.2-1.0mol: 5-20wt% (aromatic hydrocarbons crosslinking agent gross weight), under 60-150 ℃, carry out the synthetic aromatic hydrocarbons oligomer that connects by methylene of cross-linking reaction, then with this aromatic hydrocarbons oligomer at 340-380 ℃ of following heat treatment 10-25 hour.
Being fit to aroamtic hydrocarbon raw material of the present invention is the alkylbenzene that is rich in methyl chains, can be durol, symmetrical trimethylbenzene.Be rich in the methyl chains aroamtic hydrocarbon raw material and can improve the reactivity of system and make in the methyl heat treatment afterwards and participate in demethylation and be dehydrogenated to ring, make the oligomer system be easy to be converted in the middle of the plane condensed-nuclei aromatics structure of phase, be beneficial to the MOLECULE DESIGN of carbonization reaction.
Described crosslinking agent is formaldehyde, metaformaldehyde, paraformaldehyde etc.
Described catalyst can be selected p-methyl benzenesulfonic acid, sulfuric acid, phosphoric acid, chloric acid etc. for use.
So the present invention selects the mol ratio 1 of durol and crosslinking agent: 0.2-1.0 is in order to control the composition structure of resulting polymers.If dosage of crosslinking agent excessive (＞1: 1), will produce highly cross-linked polymer, further be difficult for making low softening point during heat treatment, the mesophase pitch of high dissolubility, too low as if dosage of crosslinking agent, will reduce the yield of final mesophase pitch.
The temperature and the time of staying when the present invention wants controlling polymers synthetic.Reaction temperature is too high, will make the aggravation of side reaction and back reaction, generates some ether-oxygen bonds and alcoholic extract hydroxyl group key, introduces the generation that hetero atom is unfavorable for the high-quality mesophase pitch, though the prolongation of the time of staying can improve the yield of oligomer slightly, is unfavorable for energy-conservation.
The present invention its objective is to obtain a kind of aromatic hydrocarbons oligomer by methylene bridges that this oligomer preferably is made up of 2-7 raw material aromatic hydrocarbons unit by control crosslinking agent and catalyst amount and synthesis temperature and time.
Adopt Technology for Heating Processing under the lower temperature when the present invention modulates mesophase pitch, this not only can be avoided excessive dehydrogenation and polycondensation high temperature under, and the forerunner's configuration that is beneficial to the maintenance molecule obtains our needed high-performance mesophase pitch.It is best that heat treatment temperature adopts 350-370 ℃.
Compared with the prior art method of the present invention has the following advantages:
1. technology is simple, the product purity height, and the preliminary treatment that can save raw material removes a quinoline insolubles and adjusts a step of forming distribution, and directly reacts with pure aromatics, can keep the high-purity of product.
2. be easy to control the structure and the composition of product.Because the structure of molecule is fixed substantially in the synthetic oligomer process of the first step, limited reactions such as dehydrogenation demethylation only need take place and just can easily be converted into centre phase body on the spot in these molecules in the simple thermal treatment in second step.
3. heat treatment temperature is low not only had been beneficial to energy-conservation but also had improved the yield of mesophase pitch, and had avoided the excessive pyrolysis of asphaltene molecule, was beneficial to the condensation degree of control product.
4. mesophase pitch performance height.This method can be made into that complete optical anisotropy, high dissolubility and meltbility, softening point are low, good spinnability, ashless, plane long-chain condensation molecule that molecular structure is complete vast position condensation configuration, and this mesophase pitch spinning and post processing at low temperatures prepares the high-performance pitch based carbon fiber.
It is following that the embodiment that provides will the present invention is described in detail.
Embodiment 1
With the 134g durol, temperature reaction under nitrogen protection and mechanical agitation in the three-neck flask of packing into after crosslinking agent metaformaldehyde 15g and catalyst p-methyl benzenesulfonic acid 7.5g mix stops to 105 ℃ and to obtain the solid shaped polymer in 6 hours.This polymer is pulverized behind porphyrize with hot ethanol flush away unreacted reactant, is neutrality with deionized water cyclic washing to upper water liquid then, remove dry behind the catalyst oligomer, its yield is 52wt%.EI-MS detects this oligomer of proof and mainly is made up of 2-5 durol monomer, between monomer by methylene bridges.Evening up polymers 20g puts into polycondensation vessel (3m1/3) under nitrogen bubble and heat-treats, temperature stopped 17 hours for 360 ℃, obtained the mesophase pitch that complete anisotropy presents big territory body microtextured, and softening point is 260 ℃, pyridine insoluble content 51.5wt%, H/C is than 0.86.To obtain maximum pulling strength after (260 ℃ of temperature stopped 180 minutes) and charing (1000 ℃ stop 15 minutes) are handled be 2500MPa in 328 ℃ of spinning with through not melting, the asphalt carbon fiber of modulus 168GPa.
Embodiment 2
The oligomer 20g that gets embodiment 1 obtains the mesophase pitch of 100% optical anisotropy content in 380 ℃ of heat treatments 6 hours, and this asphalt softening point is 290 ℃, can spinning between 340-360 ℃.
Embodiment 3
Get durol 134g; after mixing, metaformaldehyde 15g and p-methyl benzenesulfonic acid 7.5g pack in the three-neck flask; temperature reaction under nitrogen protection and mechanical agitation stops to 80 ℃ and to obtain solid polymer in 6 hours, calculates to such an extent that the oligomer yield is 32wt% after alcohol is washed and washed.360 ℃ stop the mesophase pitch that heat treatment in 17 hours obtains the big territory of 100% optical anisotropy body microtextured down, and softening point is 252 ℃.
Embodiment 4
Get durol 134g, in the three-neck flask of packing into after metaformaldehyde 30g and p-methyl benzenesulfonic acid 8.5g mix, temperature reaction under nitrogen protection and mechanical agitation was to 105 ℃ of stops 6 hours.Calculate to such an extent that the oligomer yield is 78wt% after the solid polymer alcohol that obtains is washed and washed.360 ℃ of following heat treatments obtained being the middle phase body of thin mosaic microscopic optical structure in 17 hours, 335 ℃ of softening points, and tool can not shine performance.
The optical anisotropy content data is estimated with the polarized light microscopy key among the above embodiment, and the softening point of pitch adopts conventional needling method to record.
Claims (6)
1. the preparation method of a mesophase pitch, it is characterized in that aromatic compound and crosslinking agent and catalyst mixed with 1mol: 0.2-1.0mol: 5-20wt% (aromatic hydrocarbons crosslinking agent gross weight), under 60-150 ℃, carry out the synthetic aromatic hydrocarbons oligomer that connects by methylene of cross-linking reaction, then with this aromatic hydrocarbons oligomer at 340-380 ℃ of following heat treatment 10-25 hour.
2. the method for claim 1 is characterized in that described aromatic compound is durol, multi-methyl benzene.
3. the method for claim 1 is characterized in that described crosslinking agent is formaldehyde, metaformaldehyde and paraformaldehyde.
4. the method for claim 1 is characterized in that described catalyst is p-methyl benzenesulfonic acid, phosphoric acid, chloric acid or sulfuric acid.
5. the method for claim 1 is characterized in that described aromatic hydrocarbons oligomer mainly is made of the 2-7 aggressiveness.
6. the method for claim 1 is characterized in that described heat treatment temperature is preferably 350-370 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96122394A CN1053001C (en) | 1996-12-20 | 1996-12-20 | Process for preparing middle phase asphalt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96122394A CN1053001C (en) | 1996-12-20 | 1996-12-20 | Process for preparing middle phase asphalt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1185491A true CN1185491A (en) | 1998-06-24 |
| CN1053001C CN1053001C (en) | 2000-05-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96122394A Expired - Fee Related CN1053001C (en) | 1996-12-20 | 1996-12-20 | Process for preparing middle phase asphalt |
Country Status (1)
| Country | Link |
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| CN (1) | CN1053001C (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315973C (en) * | 2003-12-11 | 2007-05-16 | 中国科学院山西煤炭化学研究所 | Highly heat-conductive charcoal/ charcoal composite material preparation method |
| CN101570904A (en) * | 2009-03-07 | 2009-11-04 | 垦利三合新材料科技有限责任公司 | Preparation method of asphalt carbon fiber |
| CN102504206A (en) * | 2011-10-26 | 2012-06-20 | 中国石油大学(华东) | Method for preparing high-viscosity heat-resistant resin with ethylene tar as raw material |
| CN103265966A (en) * | 2013-05-18 | 2013-08-28 | 中国石油大学(华东) | Preparation method of mesophase pitch with high mesophase content |
| CN103756707A (en) * | 2014-01-16 | 2014-04-30 | 神华集团有限责任公司 | Modified asphalt and preparation method thereof |
| CN103756708A (en) * | 2014-01-16 | 2014-04-30 | 神华集团有限责任公司 | Modified asphalt and preparation method thereof |
| CN104230620A (en) * | 2014-08-15 | 2014-12-24 | 中国科学院山西煤炭化学研究所 | Method for removing aluminum trichloride in aromatic oligomer |
| CN104790047A (en) * | 2015-04-24 | 2015-07-22 | 中国科学院山西煤炭化学研究所 | Preprocessing method for spinning mesophase pitch stock |
| CN104818041A (en) * | 2015-04-21 | 2015-08-05 | 广饶县康斯唯绅新材料有限公司 | Method of preparing meso-phase pitch by hydro-cracking tail oil |
| CN106867557A (en) * | 2017-03-09 | 2017-06-20 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of high softening point bitumen |
| CN107216903A (en) * | 2017-07-17 | 2017-09-29 | 青岛科技大学 | A kind of method that cross-linking modified sedimentation separation of FCC clarified oils prepares mesophase pitch |
| CN108264915A (en) * | 2018-03-21 | 2018-07-10 | 湖南大学 | A kind of preparation method for spinning mesophase pitch |
| CN113637147A (en) * | 2021-08-02 | 2021-11-12 | 武汉科技大学 | Preparation method of synthetic asphalt and product |
| CN114763480A (en) * | 2021-01-13 | 2022-07-19 | 中国石油化工股份有限公司 | Mesophase pitch and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0200965B1 (en) * | 1985-04-18 | 1991-02-06 | Mitsubishi Oil Company, Limited | Pitch for production of carbon fibers |
| JPH0627172B2 (en) * | 1985-10-02 | 1994-04-13 | 三菱石油株式会社 | Method for producing optically anisotropic pitch |
| JPS62270685A (en) * | 1986-05-19 | 1987-11-25 | Maruzen Petrochem Co Ltd | Production of mesophase pitch |
| JPS63315614A (en) * | 1987-06-19 | 1988-12-23 | Mitsubishi Oil Co Ltd | Production of highly electrically conductive graphite fiber |
| US5259947A (en) * | 1990-12-21 | 1993-11-09 | Conoco Inc. | Solvated mesophase pitches |
| US5198101A (en) * | 1991-12-13 | 1993-03-30 | Conoco Inc. | Process for the production of mesophase pitch |
-
1996
- 1996-12-20 CN CN96122394A patent/CN1053001C/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315973C (en) * | 2003-12-11 | 2007-05-16 | 中国科学院山西煤炭化学研究所 | Highly heat-conductive charcoal/ charcoal composite material preparation method |
| CN101570904A (en) * | 2009-03-07 | 2009-11-04 | 垦利三合新材料科技有限责任公司 | Preparation method of asphalt carbon fiber |
| CN102504206A (en) * | 2011-10-26 | 2012-06-20 | 中国石油大学(华东) | Method for preparing high-viscosity heat-resistant resin with ethylene tar as raw material |
| CN103265966A (en) * | 2013-05-18 | 2013-08-28 | 中国石油大学(华东) | Preparation method of mesophase pitch with high mesophase content |
| CN103265966B (en) * | 2013-05-18 | 2014-10-22 | 中国石油大学(华东) | Preparation method of mesophase pitch with high mesophase content |
| CN103756707A (en) * | 2014-01-16 | 2014-04-30 | 神华集团有限责任公司 | Modified asphalt and preparation method thereof |
| CN103756708A (en) * | 2014-01-16 | 2014-04-30 | 神华集团有限责任公司 | Modified asphalt and preparation method thereof |
| CN103756707B (en) * | 2014-01-16 | 2015-06-03 | 神华集团有限责任公司 | Modified asphalt and preparation method thereof |
| CN103756708B (en) * | 2014-01-16 | 2015-07-15 | 神华集团有限责任公司 | Modified asphalt and preparation method thereof |
| CN104230620B (en) * | 2014-08-15 | 2016-04-20 | 中国科学院山西煤炭化学研究所 | A kind of method of aluminum chloride in Arene removal oligopolymer |
| CN104230620A (en) * | 2014-08-15 | 2014-12-24 | 中国科学院山西煤炭化学研究所 | Method for removing aluminum trichloride in aromatic oligomer |
| CN104818041A (en) * | 2015-04-21 | 2015-08-05 | 广饶县康斯唯绅新材料有限公司 | Method of preparing meso-phase pitch by hydro-cracking tail oil |
| CN104790047A (en) * | 2015-04-24 | 2015-07-22 | 中国科学院山西煤炭化学研究所 | Preprocessing method for spinning mesophase pitch stock |
| CN106867557A (en) * | 2017-03-09 | 2017-06-20 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of high softening point bitumen |
| CN107216903A (en) * | 2017-07-17 | 2017-09-29 | 青岛科技大学 | A kind of method that cross-linking modified sedimentation separation of FCC clarified oils prepares mesophase pitch |
| CN108264915A (en) * | 2018-03-21 | 2018-07-10 | 湖南大学 | A kind of preparation method for spinning mesophase pitch |
| CN114763480A (en) * | 2021-01-13 | 2022-07-19 | 中国石油化工股份有限公司 | Mesophase pitch and preparation method and application thereof |
| CN114763480B (en) * | 2021-01-13 | 2024-03-12 | 中国石油化工股份有限公司 | Mesophase pitch and preparation method and application thereof |
| CN113637147A (en) * | 2021-08-02 | 2021-11-12 | 武汉科技大学 | Preparation method of synthetic asphalt and product |
| CN113637147B (en) * | 2021-08-02 | 2023-09-22 | 武汉科技大学 | Preparation method of synthetic asphalt and product |
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| Publication number | Publication date |
|---|---|
| CN1053001C (en) | 2000-05-31 |
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