CN102399563A - Method for preparing general type coal series asphalt with spinnability by solvent extraction and oxidative thermopolymerization - Google Patents
Method for preparing general type coal series asphalt with spinnability by solvent extraction and oxidative thermopolymerization Download PDFInfo
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- CN102399563A CN102399563A CN2010102776659A CN201010277665A CN102399563A CN 102399563 A CN102399563 A CN 102399563A CN 2010102776659 A CN2010102776659 A CN 2010102776659A CN 201010277665 A CN201010277665 A CN 201010277665A CN 102399563 A CN102399563 A CN 102399563A
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Abstract
The invention discloses a method for preparing general type coal series asphalt with spinnability by solvent extraction and oxidative thermopolymerization. The method comprises the following steps: tasking coal tar soft asphalt as a raw material, extracting and separating by using a mixed solvent of aliphatic hydrocarbon and aromatic hydrocarbon; taking the obtained refined asphalt as a raw material, carrying out oxidative thermopolymerization in a stainless steel reaction vessel, performing flash evaporation after finishing the oxidative thermopolymerization to obtain the general type coal series asphalt with spinnability. According to the invention, a solvent extraction method is used for removing a first quinoline insoluble substance of the asphalt, a process of oxidative thermopolymerization and flash evaporation is used to obtain the product, so that the disadvantages of wide molecular weight distribution of asphalt during the heat treatment process and high secondary quinoline insoluble substance content can be overcome. The general type coal series asphalt with spinnability has optical isotropy under the spinning temperature, has the characteristics of narrow molecular weight distribution, high softening point, good spinnability and high product yield, and is suitable for preparing general carbon fiber.
Description
Technical field
The present invention relates to the coal tar soft asphalt is the universal spinning property bituminous of feedstock production method.Particularly a kind of SX, heat of oxidation polymerization prepare universal coal measures spinning property bituminous method
Background technology
Thomel is a kind of new carbon of rising the sixties in 20th century, and it has high temperature resistant, corrosion-resistant, advantages such as thermal expansivity is little, dimensional stability good, high specific strength and high ratio modulus, is a kind of ideal functional materials and structured material.Originally as aerospace industry and military aircraft materials demand is grown up.Nowadays be widely used in fields such as commerce, civil aviation, style, industry and communications and transportation, had broad application prospects.The widespread use of high-performance carbon fibre matrix material has further promoted the thomel industrial expansion.Thomel can be divided into polyacrylonitrile base, asphaltic base, Zantrel base three major types by raw material sources.Asphalt base carbon fiber can be divided into petroleum pitch-based carbon fiber and coal-tar pitch base carbon fibre again.Asphalt base carbon fiber is wide, cheap with its raw material sources, the high current research hot of research and development that becomes of carbonization yield.Mechanical property according to thomel can be divided into common carbon fiber and high-performance carbon fibre.Common carbon fiber tensile strength is that 600～1400Mpa, Young's modulus are 30～100Gpa, mainly as thermoinsulating material, antistatic material and strongthener etc.High-performance carbon fibre tensile strength is 2000～3500Mpa, and Young's modulus is 100～400Gpa, is mainly used in aerospace material, sports equipment etc.Common carbon fiber uses isotropic pitch to form as the raw material spinning.Isotropic pitch needs higher softening temperature, contains the higher coking value of lower quinoline insolubles and under spinning temperature, has optical isotropy.
Consult pertinent literature, Chinese patent open (bulletin) number CN101624529A has reported a kind of " producing and manufacturing technique of spinnable coal tar ", and this method is to be raw material with the coal dust, obtains spinning property pitch through extracting, high-temperature and high-pressure hydrogenation, flash distillation.This method technology more complicated, condition is harsh, and productive rate is low; Open (bulletin) number CN86103441A of Chinese patent; Reported a kind of " preparation method of coal-tar pitch carbon fiber material "; This method is through with adding the post-heat-treated of coal tar heavy cut in the coal-tar pitch; Obtain spinning property pitch through filtration, flash distillation, the spun asphaltene molecule amount distribution of acquisition is wide, softening temperature is low, spinning property is poor.
Summary of the invention
The purpose of this invention is to provide a kind of SX, heat of oxidation polymerization prepares universal coal measures spinning property bituminous method.
SX provided by the invention, heat of oxidation polymerization prepare universal coal measures spinning property pitch method and comprise the following steps:
A. be raw material with the coal tar soft asphalt, carry out extracting and separating with the mixed solvent of aliphatic hydrocarbon and aromatic hydrocarbon.
Aliphatic solvents comprises: sherwood oil, kerosene, diesel oil, Yellow Protopet 2A, the wherein a kind of or arbitrary proportion arbitrary combination with them.Aromatic hydrocarbon solvent comprises: benzene,toluene,xylene, heavy aromatics, lightweight washing oil, heavy wash oil, methylnaphthalene, a carbolineum, their wherein a kind of or arbitrary proportion arbitrary combination.The quality of mixed solvent is 1.2～0.5 times of coal tar soft asphalt quality, in the mixed solvent quality of aliphatic solvents and aromatic hydrocarbon solvent than ratio control in 1: 1.5～0.4 scope.The extracting and separating temperature is controlled at 80 ℃～150 ℃, and the extracting and separating time was controlled at 0.5～5 hour.The extraction phase distillation that obtains is removed solvent, obtain the refined asphaltic bitumen of quinoline insolubles quality percentage content＜0.1%.
B. be raw material with the refined asphaltic bitumen that obtains, in stainless steel cauldron, carry out heat of oxidation polymerization, 200～450 ℃ of treatment temps, 2～10 hours treatment times, air flow quantity 0.08～0.20m
3/ h.
C. after the heat of oxidation finishing polymerization, under 200～350 ℃ of temperature, carry out flash distillation, flash distillation vacuum tightness is 0.02～0.08Mpa, and the treatment time is 0.1～1 hour, obtains universal coal measures spinning property pitch.
The present invention compared with prior art, its significant beneficial effect is embodied in:
Adopt solvent extraction method to remove quinoline insolubles of bituminous, adopt atmospheric oxidation thermopolymerization flash distillation to obtain product; Overcome pitch MWD broad in heat treatment process; The shortcoming that secondary quinoline insolubles content is higher; And in treating processes, do not add catalyzer, and avoided the difficulty of catalyst separating, do not need the complex solvent separation process.The universal coal measures spinning property pitch of this method preparation has optical isotropy under spinning temperature, MWD is narrower, softening temperature is high, good spinnability, product yield are high, is fit to the preparation common carbon fiber.
Embodiment
With the universal coal measures spinning property of prepared in laboratory bituminous embodiment, the present invention is further explained below, but therefore do not limit the present invention.Used raw material is a coal tar soft asphalt among the embodiment.
Embodiment 1
The first step: the coal tar soft asphalt of the 600g that in the there-necked flask of 1L, packs into, 22 ℃ of coal tar soft asphalt softening temperatures; Coking value quality percentage 32.2%; Quinoline insolubles quality percentage 2.95%; Toluene insolubles quality percentage 11.51%; The kerosene and the heavy wash oil mixed solvent that add 0.8: 1 ratio of mass ratio are total to 480g, at 130 ℃ of following heated and stirred 30min, and static then 75min; Tell extraction phase; Steam solvent and obtain refined asphaltic bitumen, its yield quality percentage is 50%, and each item index is as shown in table 1.
Second step: the refined asphaltic bitumen that the first step is made carries out heat of oxidation polymerization, 260 ℃ of temperature of reaction, reaction times 5h, air flow quantity 0.16m
3/ h obtains oxidized bitumen, and the quality percentage yield is 92%.
The 3rd step: second step was made oxidized bitumen carry out underpressure distillation, control vacuum tightness is 0.06MPa, distillation time 10 minutes.
The 4th step: with the oxidized bitumen cool to room temperature after the underpressure distillation, obtain universal spinning property carbobitumen, each item physical index is as shown in table 1.
The universal spinning property carbobitumen that obtains is carried out the spinning evaluation, and spinning property is fine.Process thomel through overstabilization and charing processing, each item index is as shown in table 2.
Embodiment 2
The first step: identical with the first step among the embodiment 1, the Yellow Protopet 2A and the lightweight washing oil mixed solvent that just add 0.75: 1 ratio of mass ratio are total to 540g.
Second step: the refined asphaltic bitumen that the first step is made carries out heat of oxidation polymerization, 260 ℃ of temperature of reaction, reaction times 6h, air flow quantity 0.16m
3/ h obtains oxidized bitumen.
The 3rd step: identical with the step of the 3rd among the embodiment 1.
The 4th step; Identical with the step of the 4th in the case study on implementation 1.
The spinning property pitch of gained carries out the spinning evaluation with spinning equipment, has good spinning property.Process thomel through overstabilization and charing processing, each item index is shown in table 1 and table 2.
Embodiment 3
The first step: identical with the first step in the case study on implementation 1, the diesel oil and the heavy wash oil mixed solvent that just add 0.85: 1 ratio of mass ratio are total to 450g.
Second step: with the polymerization of the refined asphaltic bitumen heat of oxidation, 260 ℃ of temperature of reaction, reaction times 7h, air flow quantity 0.16m
3/ h gets oxidized bitumen.
The 3rd step: identical with the step of the 3rd in the case study on implementation 1.
The 4th step: identical with the step of the 4th in the case study on implementation 1.
The spinning property pitch that obtains is carried out the spinning evaluation, and spinning property is better.Process thomel through overstabilization and charing processing, each item index is shown in table 1 and table 2.
Embodiment 4
The first step: identical with the first step in the case study on implementation 1, the sherwood oil and the heavy aromatics mixed solvent that just add 0.95: 1 ratio of mass ratio are total to 580g.
Second step: refined asphaltic bitumen is carried out heat of oxidation polymerization, 280 ℃ of temperature of reaction, reaction times 5h, air flow quantity 0.16m
3/ h obtains oxidized bitumen.
The 3rd step: identical with the step of the 3rd in the case study on implementation 1.
The 4th step: identical with the step of the 4th in the case study on implementation 1.
The spinning property pitch that obtains is carried out spinning evaluation, good spinning property.Process thomel through overstabilization and charing processing, each item index is shown in table 1 and table 2.
Embodiment 5
The first step: identical with the first step in the case study on implementation 1, the kerosene, diesel oil and the heavy wash oil mixed solvent that just add 0.5: 0.5: 1 ratio of mass ratio are total to 500g.
Second step: refined asphaltic bitumen is carried out heat of oxidation aggregation processing, 280 ℃ of temperature of reaction controls, reaction times 6h, air flow quantity 0.16m
3/ h obtains oxidized bitumen.
The 3rd step: identical with the step of the 3rd in the case study on implementation 1.
The 4th step: identical with the step of the 4th in the case study on implementation 1.
The spinning property pitch that obtains is carried out the spinning evaluation, and spinning property is better.Process thomel through overstabilization and charing processing, each item index is shown in table 1 and table 2.
Table 1 refined asphaltic bitumen and universal coal measures spinning property asphaltic nature
Annotate: percentage all is a quality percentage in the table.
The character of the common carbon fiber that each case of table 2 makes
Claims (1)
1. a SX, heat of oxidation polymerization prepare universal coal measures spinning property bituminous method, it is characterized in that this method comprises the following steps:
A. be raw material with the coal tar soft asphalt, carry out extracting and separating with the mixed solvent of aliphatic hydrocarbon and aromatic hydrocarbon, aliphatic solvents comprises: sherwood oil, kerosene, diesel oil, Yellow Protopet 2A, the wherein a kind of or arbitrary proportion arbitrary combination with them; Aromatic hydrocarbon solvent comprises: benzene,toluene,xylene, heavy aromatics, lightweight washing oil, heavy wash oil, methylnaphthalene, a carbolineum; Their wherein a kind of or arbitrary proportion arbitrary combination; The quality of mixed solvent is 1.2～0.5 times of coal tar soft asphalt quality; In 1: 1.5～0.4 scope, the extracting and separating temperature is controlled at 80 ℃～150 ℃ to the quality of aliphatic solvents and aromatic hydrocarbon solvent than ratio control in the mixed solvent, and the extracting and separating time was controlled at 0.5～5 hour; The extraction phase distillation that obtains is removed solvent, obtain the refined asphaltic bitumen of quinoline insolubles quality percentage content＜0.1%;
B. be raw material with the refined asphaltic bitumen that obtains, in stainless steel cauldron, carry out heat of oxidation polymerization, 200～450 ℃ of treatment temps, 2～10 hours treatment times, air flow quantity 0.08～0.20m
3/ h;
C. after the heat of oxidation finishing polymerization, under 200～350 ℃ of temperature, carry out flash distillation, flash distillation vacuum tightness is 0.02～0.08Mpa, and the treatment time is 0.1～1 hour, obtains universal coal measures spinning property pitch.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103014919A (en) * | 2012-12-28 | 2013-04-03 | 陕西师范大学 | Preparation method of general purpose pitch-based carbon fiber |
| CN103361096A (en) * | 2012-04-10 | 2013-10-23 | 上海宝钢化工有限公司 | Preparation method of high-softening-point asphalt for producing general-grade carbon fibers |
| CN104004537A (en) * | 2014-04-11 | 2014-08-27 | 郑州大学 | Comprehensive utilization technology for coal pitch refined carbon material raw materials |
| CN104004538A (en) * | 2014-04-11 | 2014-08-27 | 郑州大学 | Comprehensive utilization process for refining raw material of carbon material by coal tar |
| CN107488456A (en) * | 2017-07-31 | 2017-12-19 | 江苏天诺环境工程技术开发有限公司 | A kind of preparation method of high β resin modified asphalts |
| CN109181732A (en) * | 2018-09-30 | 2019-01-11 | 中国科学院山西煤炭化学研究所 | A kind of method that coal tar preparation can spin pitch |
| CN109181733A (en) * | 2018-09-30 | 2019-01-11 | 中国科学院山西煤炭化学研究所 | A kind of method that coal tar pitch preparation can spin pitch |
| CN109402784A (en) * | 2018-09-30 | 2019-03-01 | 中国科学院山西煤炭化学研究所 | A kind of method of low temperature coal tar pitch during hydrogenated styrene-butadiene block copolymer is modified |
| CN111363577A (en) * | 2020-03-12 | 2020-07-03 | 中国科学院山西煤炭化学研究所 | Spinnable asphalt for coal-based general-grade asphalt carbon fibers and preparation method thereof |
| CN111925818A (en) * | 2020-08-14 | 2020-11-13 | 辽宁信德新材料科技股份有限公司 | Carbon fiber spinnable asphalt and preparation method and application thereof |
| CN112300821A (en) * | 2019-07-23 | 2021-02-02 | Oci有限公司 | Preparation method of petroleum-based high-softening-point asphalt |
| CN113061452A (en) * | 2021-01-06 | 2021-07-02 | 洛阳金达石化有限责任公司 | Coal tar pitch quinoline insoluble extractant and extraction method thereof |
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| CN101289624A (en) * | 2008-06-03 | 2008-10-22 | 山西宏特煤化工有限公司 | Process for producing moderate temperature modified bitumen by continuously pressurizing and hot-polymerizing at two stages connected in series |
| CN201433191Y (en) * | 2009-06-21 | 2010-03-31 | 中国矿业大学 | Kettle-type asphalt air oxidation device |
| CN101824329A (en) * | 2010-05-17 | 2010-09-08 | 朱兴建 | Novel process for eliminating quinoline insoluble substances in coal tar medium temperature pitch |
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| CN101289624A (en) * | 2008-06-03 | 2008-10-22 | 山西宏特煤化工有限公司 | Process for producing moderate temperature modified bitumen by continuously pressurizing and hot-polymerizing at two stages connected in series |
| CN201433191Y (en) * | 2009-06-21 | 2010-03-31 | 中国矿业大学 | Kettle-type asphalt air oxidation device |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361096A (en) * | 2012-04-10 | 2013-10-23 | 上海宝钢化工有限公司 | Preparation method of high-softening-point asphalt for producing general-grade carbon fibers |
| CN103361096B (en) * | 2012-04-10 | 2014-12-03 | 上海宝钢化工有限公司 | Preparation method of high-softening-point asphalt for producing general-grade carbon fibers |
| CN103014919A (en) * | 2012-12-28 | 2013-04-03 | 陕西师范大学 | Preparation method of general purpose pitch-based carbon fiber |
| CN103014919B (en) * | 2012-12-28 | 2014-09-10 | 陕西师范大学 | Preparation method of general purpose pitch-based carbon fiber |
| CN104004537A (en) * | 2014-04-11 | 2014-08-27 | 郑州大学 | Comprehensive utilization technology for coal pitch refined carbon material raw materials |
| CN104004538A (en) * | 2014-04-11 | 2014-08-27 | 郑州大学 | Comprehensive utilization process for refining raw material of carbon material by coal tar |
| CN104004537B (en) * | 2014-04-11 | 2015-11-04 | 郑州大学 | Coal-tar pitch refines the comprehensive utilization process of Carbon Materials raw material |
| CN104004538B (en) * | 2014-04-11 | 2015-11-11 | 郑州大学 | The comprehensive utilization process of coal tar refining Carbon Materials raw material |
| CN107488456A (en) * | 2017-07-31 | 2017-12-19 | 江苏天诺环境工程技术开发有限公司 | A kind of preparation method of high β resin modified asphalts |
| CN109181732A (en) * | 2018-09-30 | 2019-01-11 | 中国科学院山西煤炭化学研究所 | A kind of method that coal tar preparation can spin pitch |
| CN109181733A (en) * | 2018-09-30 | 2019-01-11 | 中国科学院山西煤炭化学研究所 | A kind of method that coal tar pitch preparation can spin pitch |
| CN109402784A (en) * | 2018-09-30 | 2019-03-01 | 中国科学院山西煤炭化学研究所 | A kind of method of low temperature coal tar pitch during hydrogenated styrene-butadiene block copolymer is modified |
| CN109181733B (en) * | 2018-09-30 | 2020-11-27 | 中国科学院山西煤炭化学研究所 | Method for preparing spinnable asphalt from coal tar pitch |
| CN109402784B (en) * | 2018-09-30 | 2020-12-01 | 中国科学院山西煤炭化学研究所 | Method for modifying medium-low temperature coal pitch by hydrogenated styrene-butadiene block copolymer |
| CN112300821A (en) * | 2019-07-23 | 2021-02-02 | Oci有限公司 | Preparation method of petroleum-based high-softening-point asphalt |
| CN111363577A (en) * | 2020-03-12 | 2020-07-03 | 中国科学院山西煤炭化学研究所 | Spinnable asphalt for coal-based general-grade asphalt carbon fibers and preparation method thereof |
| CN111363577B (en) * | 2020-03-12 | 2021-09-21 | 中国科学院山西煤炭化学研究所 | Spinnable asphalt for coal-based general-grade asphalt carbon fibers and preparation method thereof |
| CN111925818A (en) * | 2020-08-14 | 2020-11-13 | 辽宁信德新材料科技股份有限公司 | Carbon fiber spinnable asphalt and preparation method and application thereof |
| CN113061452A (en) * | 2021-01-06 | 2021-07-02 | 洛阳金达石化有限责任公司 | Coal tar pitch quinoline insoluble extractant and extraction method thereof |
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Application publication date: 20120404 |