CN105885907A - Preparation method for general-purpose pitch-based carbon fiber spinning pitch - Google Patents
Preparation method for general-purpose pitch-based carbon fiber spinning pitch Download PDFInfo
- Publication number
- CN105885907A CN105885907A CN201610300742.5A CN201610300742A CN105885907A CN 105885907 A CN105885907 A CN 105885907A CN 201610300742 A CN201610300742 A CN 201610300742A CN 105885907 A CN105885907 A CN 105885907A
- Authority
- CN
- China
- Prior art keywords
- colophonium
- asphalt
- preparation
- pitch
- spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
- C10C3/04—Working-up pitch, asphalt, bitumen by chemical means reaction by blowing or oxidising, e.g. air, ozone
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
- C10C3/023—Working-up pitch, asphalt, bitumen by chemical means reaction with inorganic compounds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
- D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
- D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention relates to a preparation method for general-purpose pitch-based carbon fiber spinning pitch. According to the preparation method, spinning pitch is prepared by adopting the combination of oxidation of a liquid oxidant and pyrocondensation polymerization. Compared with a previous air oxidation or pyrocondensation polymerization method, the preparation method disclosed by the invention has the advantages that the reaction temperature is relatively mild and the time is greatly shortened due to the adoption of the liquid oxidant. The spinning pitch prepared by the preparation method has excellent spinnability. The prepared pitch-based carbon fiber has the strength greater than 800MPa.
Description
Technical field
The present invention relates to a kind of preparation method for universal pitch charcoal fibre spinning asphalt, definitely
Say, be use liquid phase oxidation and thermal polycondensation combination spinning asphalt preparation method, use this spinning to drip
Green grass or young crops can prepare superior in quality universal pitch charcoal fibre.
Technical background
Carbon fibe has that density is low, hot strength and the high many advantages of modulus, at military and civilian high-tech
Field is increasingly widely applied.Asphalt carbon fiber is an important kind of Carbon fibe, according to performance
Classification, universal pitch charcoal fibre and Mesophase Pitch-based Carbon Fibers correspond respectively to Colophonium series general performance and
High Property Carbon Fibers kind.The spinning asphalt preparation of universal pitch charcoal fibre generally uses simple thermal polycondensation (king
Cheng Yang et al., number of patent application 201310114647.2 " preparation method of a kind of high softening-point spinning asphalt "),
Air oxidation process (Yan Guilin et al., number of patent application 201210541249.4 " a kind of coal measures general purpose grade Colophonium
The preparation method of Carbon fibe ") or combination (Liu Lang et al., the application number of above two technique
" 200710163857.5 the preparation method of universal pitch charcoal fibre "), achieve preferable spinning asphalt.
In above-mentioned technique, thermal polycondensation is to cause polycondensation reaction, relative to air oxidation process, instead by cracking molecular fragment
Answer speed slower；Air oxidation process is faster than thermal polycondensation, but the time of consuming is the longest.The present invention uses to be had
The liquid instead of air oxidant of oxidisability, owing to Oxygen in Liquid agent oxidisability is relatively strong, and unit bodies hydrops
The molecular number of phase material is far more than air, and oxidant is high with asphaltene molecule contact frequency, so response speed is relatively
Air oxidation process is fast.Owing to Oxygen in Liquid agent is reactive strong, reaction can complete at a lower temperature, compares
Oxidizing process or thermal polycondensation process, reaction temperature can reduce by more than 100 DEG C, and condition is gentleer, controls more to hold
Easily.The modulator approach that the Oxygen in Liquid agent of present invention employing is more conventional can be under relatively mild reaction conditions
Carry out, and the preparation of spinning asphalt can be completed in a relatively short time.
Owing to the bulk properties that spinning asphalt is final is regulated and controled advantageously, so the present invention exists by thermal polycondensation method
It is also adopted by thermal polycondensation after liquid phase oxidation and carries out later stage process.
Summary of the invention
The present invention provides a kind of method that liquid phase oxidation prepares spinning asphalt, and the method has the response time
The advantage that short, reaction condition is gentle, thus method can prepare the spinning asphalt that spinnability is excellent.
The preparation process of the present invention is as follows:
1, by softening point at 50-120 DEG C, the low ash Colophonium of content of ashes ＜ 1.5% and Oxygen in Liquid
Agent mixes according to mass ratio 1: 2-10: 1 ratio, within 1-3 hour, is dripped 50-150 DEG C of reaction
The blue or green mixture with Oxygen in Liquid agent, uses the method for washing to remove oxidant and just obtains initial oxidation drip
Blue or green.
2, initial oxidation Colophonium step 1 obtained, under inert gas shielding, is protected at nitrogen
Under, just obtain the spinning asphalt of softening point 270-290 DEG C in 330-400 DEG C of heat treatment.
Described low ash Colophonium is asphalt or coal tar pitch.
Described Oxygen in Liquid agent is nitric acid, sulphuric acid or the mixture of the two, wherein concentration of nitric acid 10-
50%, sulfuric acid concentration 50-90%.During the two mixing, its ratio is 1: between 5-5: 1.
330-400 DEG C of heat treatment described in step 2 refer at ambient pressure thermal polycondensation after 1-2 hour again very
React 0.3-0.5 hour under dummy status.
Advantages of the present invention is as follows:
(1) response time is short: relatively air oxidation or simple thermal polycondensation process shorten more than 40%.
(2) reaction condition is gentle: liquid phase oxidation temperature is less than air oxidation or thermal polycondensation temperature
About 200 DEG C.
(3) prepared by spinning asphalt prepared by the present invention and simple thermal polycondensation or air oxidation process
Spinning asphalt all has good spinnability, and prepared asphalt carbon fibre property is suitable.
Detailed description of the invention
Embodiment 1
This embodiment is comparative example, is the group technology result of simple air oxidation and thermal polycondensation.Take ash
0.1%, the coal tar pitch of softening point 85 DEG C, 340 DEG C, air oxidation 6 hours, then 360 DEG C of polycondensations
1.5 hours, vacuum polycondensation 0.5 hour, obtain the spinning asphalt of softening point 273 DEG C.This spinning asphalt can connect
Continuous spinning ＞ 1 myriametre, asphalt carbon fibre strength 830MPa of preparation.
Embodiment 2
Take ash 0.1%, the coal tar pitch of softening point 72 DEG C, use the sulphuric acid of 90%, with Colophonium: acid oxidase
Agent=1: the ratio mixing of 1, reacts 1.5 hours at 110 DEG C, obtains the mixture of Colophonium and Oxygen in Liquid agent,
The method using washing is washed to PH to 6-7, is removed by oxidant and obtains initial oxidation Colophonium.By this Colophonium
Under nitrogen protection, in 380 DEG C of polycondensations 1 hour, evacuation 0.5 hour the most at such a temperature, obtain soft
Change the spinning asphalt of point 278 DEG C.This spinning asphalt can continuous spinning ＞ 1 myriametre, the asphalt carbon fiber of preparation is strong
Degree 822MPa.
Embodiment 3
Taking ash 0.1%, 90 DEG C of coal tar pitch of softening point, the nitric acid of employing 30% and 70% sulphuric acid are with 5: 1
Ratio mixes, coal tar pitch and nitration mixture oxidant mass ratio 2: 1, reacts 1.0 hours at 110 DEG C, obtains Colophonium
With the mixture of Oxygen in Liquid agent, use the method for washing to be washed to PH to 6-7, oxidant is removed and obtains
Initial oxidation Colophonium.By this Colophonium under nitrogen protection, in 360 DEG C of polycondensations 1.5 hours, then in this temperature
Lower evacuation 0.3 hour, obtains the spinning asphalt of softening point 279 DEG C.This spinning asphalt can continuous spinning ＞ 1
Myriametre, asphalt carbon fibre strength 850MPa of preparation.
Embodiment 4
Take ash 0.1%, the coal tar pitch of softening point 95 DEG C, use the nitric acid of 10%, with Colophonium: acid oxidase
Agent=3: the ratio mixing of 1, react 3 hours at 130 DEG C, obtain the mixture of Colophonium and Oxygen in Liquid agent, adopt
The method washed with water is washed to PH to 6-7, is removed by oxidant and obtains initial oxidation Colophonium.This Colophonium is existed
Under nitrogen protection, in 350 DEG C of polycondensations 1 hour, evacuation 0.3 hour, is softened the most at such a temperature
The spinning asphalt of point 270 DEG C.This spinning asphalt can continuous spinning ＞ 1 myriametre, the asphalt carbon fibre strength of preparation
861MPa。
Embodiment 5
Take ash 0.1%, the coal tar pitch of softening point 50 DEG C, use the nitric acid of 50%, with Colophonium: acid oxidase
Agent=10: the ratio mixing of 1, react 1.5 hours at 50 DEG C, obtain the mixture of Colophonium and Oxygen in Liquid agent,
The method using washing is washed to PH to 6-7, is removed by oxidant and obtains initial oxidation Colophonium.By this Colophonium
Under nitrogen protection, in 330 DEG C of polycondensations 1 hour, evacuation 0.3 hour the most at such a temperature, obtain soft
Change the spinning asphalt of point 286 DEG C.This spinning asphalt can continuous spinning ＞ 1 myriametre, the asphalt carbon fiber of preparation is strong
Degree 856MPa.
Embodiment 6
Take ash 0.1%, the coal tar pitch of softening point 112 DEG C, use the sulphuric acid of 50%, with Colophonium: acid oxidase
Agent=1: the ratio mixing of 2, reacts 3 hours at 150 DEG C, obtains the mixture of Colophonium and Oxygen in Liquid agent, adopt
The method washed with water is washed to PH to 6-7, is removed by oxidant and obtains initial oxidation Colophonium.This Colophonium is existed
Under nitrogen protection, in 400 DEG C of polycondensations 1 hour, evacuation 0.3 hour, is softened the most at such a temperature
The spinning asphalt of point 290 DEG C.This spinning asphalt can continuous spinning ＞ 1 myriametre, the asphalt carbon fibre strength of preparation
817MPa。
Embodiment 7
Take ash 0.15%, the asphalt of softening point 120 DEG C, use 40% nitric acid and 80% sulphuric acid with
The ratio mixing of 1: 5, coal tar pitch and nitration mixture oxidant mass ratio 2: 1, react 2.0 hours at 90 DEG C, obtain
Colophonium and the mixture of Oxygen in Liquid agent, use the method for washing to be washed to PH to 6-7, removed by oxidant
Obtain initial oxidation Colophonium.By this Colophonium under nitrogen protection, in 330 DEG C of polycondensations 2 hours, then in this temperature
The lower evacuation of degree 0.3 hour, obtains the spinning asphalt of softening point 285 DEG C.This spinning asphalt can continuous spinning ＞
1 myriametre, asphalt carbon fibre strength 805MPa of preparation.
Embodiment 8
Take ash 0.15%, the asphalt of softening point 85 DEG C, use the nitric acid of 30%, with Colophonium: acid oxygen
Agent=5: the ratio mixing of 1, react 1.5 hours at 70 DEG C, obtain the mixture of Colophonium and Oxygen in Liquid agent,
The method using washing is washed to PH to 6-7, is removed by oxidant and obtains initial oxidation Colophonium.By this Colophonium
Under nitrogen protection, in 330 DEG C of polycondensations 1 hour, evacuation 0.3 hour the most at such a temperature, obtain soft
Change the spinning asphalt of point 278 DEG C.This spinning asphalt can continuous spinning ＞ 1 myriametre, the asphalt carbon fiber of preparation is strong
Degree 825MPa.
The result of above-described embodiment collects and see table.
Claims (4)
1. the preparation method of a universal pitch charcoal fibre spinning asphalt, it is characterised in that use Oxygen in Liquid agent
Aoxidizing low ash, low softening point asphalt at a certain temperature, after having aoxidized, washing just removes oxidant
Obtain initial oxidation Colophonium；This initial oxidation Colophonium is just obtained spinning asphalt through thermal polycondensation.
2. the initial oxidation Colophonium described in claim 1, its preparation method is as follows: by low ash Colophonium and liquid phase oxidation
Agent mixes according to mass ratio 1: 2-10: 1 ratio, within 1-3 hour, obtains Colophonium and liquid phase 50-150 DEG C of reaction
The mixture of oxidant.The method that this mixture uses washing removes oxidant and just obtains initial oxidation Colophonium.
3. low ash, low softening point asphalt described in claim 2 refer to that softening point is at 50-120 DEG C, content of ashes
Asphalt less than 0.15% or coal tar pitch；Oxygen in Liquid agent is nitric acid or sulphuric acid or the mixture of the two,
Wherein concentration of nitric acid 10-50%, sulfuric acid concentration 50-90%.During the two mixing, its ratio is 1: 5-5: 1
Between.
4. the spinning asphalt described in claim 1 is that initial oxidation Colophonium claim 2 obtained is protected at nitrogen
Under, process after 1-2 hour in 330-400 DEG C, then reaction obtained after 0.3-0.5 hour under vacuum conditions
The asphaltic products of softening point 270-290 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610300742.5A CN105885907A (en) | 2016-05-05 | 2016-05-05 | Preparation method for general-purpose pitch-based carbon fiber spinning pitch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610300742.5A CN105885907A (en) | 2016-05-05 | 2016-05-05 | Preparation method for general-purpose pitch-based carbon fiber spinning pitch |
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| Publication Number | Publication Date |
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| CN105885907A true CN105885907A (en) | 2016-08-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610300742.5A Pending CN105885907A (en) | 2016-05-05 | 2016-05-05 | Preparation method for general-purpose pitch-based carbon fiber spinning pitch |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108486688A (en) * | 2018-03-27 | 2018-09-04 | 天津工业大学 | A kind of quick infusible method in asphalt-based carbon fiber preparation process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5308599A (en) * | 1991-07-18 | 1994-05-03 | Petoca, Ltd. | Process for producing pitch-based carbon fiber |
| CN1395988A (en) * | 2001-07-12 | 2003-02-12 | 中国科学院山西煤炭化学研究所 | Process for preparing carbon aerogel |
| CN101135074A (en) * | 2007-10-10 | 2008-03-05 | 新疆创越投资有限责任公司 | Method for preparing universal pitch charcoal fibre |
-
2016
- 2016-05-05 CN CN201610300742.5A patent/CN105885907A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5308599A (en) * | 1991-07-18 | 1994-05-03 | Petoca, Ltd. | Process for producing pitch-based carbon fiber |
| CN1395988A (en) * | 2001-07-12 | 2003-02-12 | 中国科学院山西煤炭化学研究所 | Process for preparing carbon aerogel |
| CN101135074A (en) * | 2007-10-10 | 2008-03-05 | 新疆创越投资有限责任公司 | Method for preparing universal pitch charcoal fibre |
Non-Patent Citations (2)
| Title |
|---|
| 于宝军: "氧化-缩聚两步法制备煤沥青基纺丝沥青及其性能研究", 《万方数据知识服务平台》 * |
| 刘小军等: "HNO3液相氧化沥青球的初步研究", 《第20届炭•石墨材料学术会议》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108486688A (en) * | 2018-03-27 | 2018-09-04 | 天津工业大学 | A kind of quick infusible method in asphalt-based carbon fiber preparation process |
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Application publication date: 20160824 |
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