CN110272755B - Preparation method of spinning asphalt with high thermal stability and special device thereof - Google Patents
Preparation method of spinning asphalt with high thermal stability and special device thereof Download PDFInfo
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- CN110272755B CN110272755B CN201910392288.4A CN201910392288A CN110272755B CN 110272755 B CN110272755 B CN 110272755B CN 201910392288 A CN201910392288 A CN 201910392288A CN 110272755 B CN110272755 B CN 110272755B
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- 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
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- 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
- C10C3/10—Melting
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- Organic Chemistry (AREA)
- Working-Up Tar And Pitch (AREA)
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Abstract
The invention discloses a preparation method of spinning pitch with high thermal stability and a special device thereof, wherein precursor pitch converted from a mesophase is heated to 350-450 ℃, the stirring speed is 100-1000rpm, 2-40L/kg ∙ min of inert gas bubbles are introduced, the diameter of the introduced bubbles is controlled to be 0.03-0.5mm through a porous plate, and the reaction is carried out for 2-30hr until the softening point is 250-300 ℃. Then the waste gas is pressed and extruded by a filter screen and a hole with the aperture of 0.03-0.5mm, and the generated waste gas is pumped out and decomposed and separated by a vacuum system. And (4) dropping and collecting the asphalt strips, and performing hot melting granulation again to obtain the mesophase asphalt. The reaction device consists of a reaction kettle body with a heating function, a kettle cover, a filter screen, a perforated plate, a receiving kettle bottom cover, a kettle bottom pump, granulation equipment and a vacuum system. The method is suitable for preparing high-viscosity spinning asphalt materials, and can obtain high-quality spinning asphalt with the thermal weight loss of less than 0.4% at 330 ℃.
Description
Technical Field
The invention relates to a preparation method and a device of spinning asphalt, in particular to a method and a special device suitable for preparing high-thermal-stability spinning asphalt from thermosensitive raw materials.
Background
The spinning pitch is mainly applied to preparing pitch-based carbon fibers and is a fused ring aromatic compound with extremely high performance requirements. In order to obtain high-quality carbon fibers, the spinning pitch has extremely high requirements for the content of solid impurities, the content of low-molecular-weight compounds, thermal stability, and the like. Due to the complexity of the source and the molecular structure of the asphalt, not only the thermal polycondensation of the asphalt is required, but also small molecules which cannot participate in the reaction and long fatty chains which are easy to break in the asphalt are required to be removed. In addition, the free radicals generated in the heating process are easy to form a secondary reaction with the asphalt, so that the reaction efficiency and the unstable radical removal effect are greatly reduced, and the thermal stability of the obtained spinning asphalt cannot be effectively improved. In order to improve the thermal stability, the conventional solution improves the high-temperature mass transfer time to different degrees, and under a high-viscosity system, the solution also increases the probability of occurrence of ultra-large molecular infusions and even coking of an asphalt system.
Patent ZL201810233342.6 discloses a method for preparing mesophase pitch, which uses nitrogen bubbling process to perform polymerization and light component separation, and because of using conventional bubbling process, even though stirring is assisted, nitrogen is difficult to be uniformly distributed in a high-viscosity material system, and is easy to be short-circuited, so that the actual contact area of nitrogen and pitch is very small, and the method is particularly remarkable when equipment and process are enlarged. If the problem is simply solved by increasing the nitrogen gas amount, the energy loss is increased, and material droplets are easily taken out of a reaction system to cause material loss and blockage of an auxiliary pipeline.
The negative pressure/vacuum polymerization process is a common polymerization and separation method in the preparation process of the spinning asphalt, is beneficial to discharge small molecules generated by reaction, but has more materials in a reaction kettle, long mass transfer distance of the small molecules and difficult guarantee of efficiency. For example, patent 201510201626.3 uses vacuum to pretreat the spinning pitch prior to spinning, but this method is disadvantageous for spinning continuity and requires a highly thermally stable spinning pitch that can be used directly for continuous spinning.
The film evaporator solves the problem of long mass transfer distance, but has high requirement on equipment and extremely high control difficulty. For example, patent zl201510972599.x and ZL201710362016.0 adopt a film evaporator to remove light components under negative pressure, but in practical application, materials adhered to the inner wall of the device are difficult to effectively renew, the long-time reaction can cause "coking" of the adhered materials, and a filtering device has to be added in the later process of the product to remove generated coking carbon particles.
Disclosure of Invention
The invention mainly aims to overcome the defects of the prior art, is suitable for polymerization and mass transfer separation of high-viscosity and easily-coked materials, and provides a more effective, economical and practical method and a special device for spinning asphalt with high thermal stability.
The above object of the present invention is achieved by the following scheme:
a preparation method of spinning asphalt with high thermal stability comprises the following steps:
(1) precursor asphalt is adopted and heated to the temperature of 350-2Reacting for 2-30hr to make the softening point reach 240-300 deg.C.
(2) Keeping the temperature of 280-360 ℃ for the asphalt obtained in the step (1), and extruding the asphalt through a filter screen with 60-3000 meshes and holes with the aperture of 0.03-0.5mm under pressure, wherein the number of the extruded holes is 1-10 holes/cm2The extrusion pressure is 0.1-0.5MPa, the extruded asphalt filament is kept at the temperature of 280-320 ℃, and the generated waste gas is extracted and decomposed and separated through a vacuum system.
(3) The asphalt strips fall down and are collected and melted again for granulation, and the temperature is controlled below 320 ℃.
The precursor asphalt is purified hydrogenated coal tar asphalt, purified hydrogenated petroleum asphalt or pure aromatic polymerized asphalt with the softening point of 60-180 ℃.
The preparation method of the high-thermal-stability spinning asphalt comprises the following steps of: comprises a reaction kettle cover, a reaction kettle body, a filter screen, a porous plate, a receiving kettle bottom cover, a kettle bottom pump, a vacuum system and granulation equipment. The upper part of the reaction kettle body is provided with a kettle cover, the middle part of the reaction kettle body is provided with a filter screen and a porous plate, the bottom of the reaction kettle body is provided with a receiving kettle bottom cover, the receiving kettle bottom cover is connected with a kettle bottom pump, the kettle bottom pump is connected with granulation equipment, the kettle cover is provided with a feed valve, an air outlet valve and stirring, and the lower part of the porous plate at the middle part of the reaction kettle body is provided with an air inlet pipe valve and an air exhaust pipe valve and is.
The invention has the following beneficial effects:
1. the mass transfer efficiency in the thermal polymerization process is greatly improved through the bubbling mass transfer of the superfine bubbles, and the reaction temperature and time are effectively reduced.
2. Through the extrusion filamentation of the asphalt and the negative pressure separation, the problem that the decomposition products generated in the preparation process of the prior spinning asphalt can be discharged immediately is solved, the content of the fatty side chain in the asphalt system is greatly reduced, and the thermal stability of the asphalt is further improved.
3. The use of high-cost complex equipment is avoided, and the effect of more efficient mass transfer separation is achieved by adopting simple structure equipment.
Drawings
FIG. 1 is a schematic structural diagram of the special apparatus of the present invention.
Wherein, the reaction kettle comprises 1-a kettle cover, 2-a reaction kettle body, 3-a filter screen and a porous plate, 4-a receiving kettle bottom cover, 5-a kettle bottom pump, 6-a vacuum system, 7-granulation equipment, 1-1-a feed valve, 1-2-an air outlet valve, 1-3-stirring, 2-1-an air inlet pipe valve and 2-2-an air exhaust pipe valve.
Detailed Description
Example 1
The preparation method of the spinning asphalt with high thermal stability adopts a special device which comprises a reaction kettle cover 1, a reaction kettle body 2, a filter screen and a porous plate 3, a receiving kettle bottom cover 4, a kettle bottom pump 5, a vacuum system 6 and granulation equipment 7. The upper part of the reaction kettle body 2 is provided with a kettle cover 1, the middle part of the reaction kettle body is provided with a filter screen and a porous plate 3, the bottom part is provided with a receiving kettle bottom cover 4, the receiving kettle bottom cover 4 is connected with a kettle bottom pump 5, the kettle bottom pump 5 is connected with a granulation device 7, the kettle cover 1 is provided with a feed valve 1-1, an air outlet valve 1-2 and a stirring valve 1-3, the lower part of the porous plate of the reaction kettle body 2 is provided with an air inlet pipe valve 2-1 and an air exhaust pipe valve 2-2, and the porous plate is connected with a vacuum system.
600 meshes of filter screen, 800mm of diameter of porous plate, 0.05mm of aperture and 4 holes/cm of hole number2The holes are uniformly distributed.
Asphalt (HF/BF) polymerized by catalysis of naphthalene with softening point of 80 DEG C3Catalytic preparation) 300kg, melting, adding into a special device through a feed valve 1-1, heating to 420 ℃,introducing 5L/kg ∙ min (1500L/min) nitrogen from gas inlet pipe valve 2-1, introducing nitrogen into the material via porous plate 3, stirring at 600rpm, extracting waste gas from gas outlet valve 1-2 under micro-negative pressure, and reacting for 8hr to obtain asphalt with softening point of 270 deg.C.
(2) And (3) cooling and keeping the temperature of the reaction kettle body 2 at 300 ℃, closing the air outlet valve 1-2 and the air inlet pipe valve 2-1, opening the air exhaust pipe valve 2-2, adjusting the vacuum system 6 to 1000Pa, pressurizing to 0.2MPa through the feed valve 1-1, and slowly dropping the asphalt to form asphalt strands with the diameter of 16-30 mu m.
(3) And (3) dropping and collecting asphalt filaments, controlling the temperature of the receiving kettle bottom cover 4 and the kettle bottom pump 5 to be 300 ℃, and directly conveying the asphalt filaments to granulation equipment 7 to prepare the granular spinning asphalt.
Example 2
A filter screen with 3000 meshes, a perforated plate with the diameter of 800mm, the aperture of 0.05mm and the number of holes of 4 holes/cm2The holes are uniformly distributed.
250kg of coal tar pitch with a softening point of 120 ℃ is adopted, the melted coal tar pitch is added into a special device through a feed valve 1-1, the mixture is heated to 410 ℃, 10L/kg ∙ min (2500L/min) of nitrogen is introduced from a gas inlet pipe valve 2-1, the nitrogen enters the material through a porous plate 3, the stirring speed is 800rpm, waste gas is pumped out through a gas outlet valve 1-2 under the micro negative pressure, and the reaction is carried out for 15 hours, so that pitch with a softening point of 290 ℃ is obtained.
(2) And (3) cooling and keeping the temperature of the reaction kettle body 2 at 330 ℃, closing the air outlet valve 1-2 and the air inlet pipe valve 2-1, opening the air exhaust pipe valve 2-2, adjusting the vacuum system 6 to 1000Pa, pressurizing to 0.4MPa through the feed valve 1-1, and slowly dropping the asphalt to form asphalt strands with the diameter of 15-28 mu m.
(3) And (3) dropping and collecting asphalt filaments, controlling the temperature of the receiving kettle bottom cover 4 and the kettle bottom pump 5 to be 320 ℃, and directly conveying the asphalt filaments to a granulation device 7 to prepare the granular spinning asphalt.
Claims (2)
1. The preparation method of the spinning asphalt with high thermal stability is characterized by comprising the following steps:
(1) precursor asphalt is adopted and heated to 350-450 ℃ in a polymerization reaction kettle with a stirrer, inert gas enters the materials through a porous plate at the bottom of the polymerization reaction kettle, and the stirring speed is 100-1000rpm, ventilation capacity of 2-40L/kg ∙ min, perforated plate aperture of 0.03-0.5mm, and hole number of 1-10 holes/cm2Reacting for 2-30 hr; the reaction kettle consists of a kettle cover (1), a reaction kettle body (2), a filter screen and a porous plate (3), a receiving kettle bottom cover (4), a kettle bottom pump (5), a vacuum system (6) and granulation equipment (7), the upper part of the reaction kettle body (2) is provided with a kettle cover (1), the middle inside the reaction kettle body is provided with a filter screen and a porous plate (3), the bottom part is provided with a receiving kettle bottom cover (4), the receiving kettle bottom cover (4) is connected with a kettle bottom pump (5), the kettle bottom pump (5) is connected with granulation equipment (7), the kettle cover (1) is provided with a feed valve (1-1), an air outlet valve (1-2) and a stirring valve (1-3), the lower part of the filter screen and the porous plate (3) in the middle of the reaction kettle body (2) is provided with an air inlet pipe valve (2-1) and an air exhaust pipe valve (2-2), and the reaction kettle body (2) is connected with a vacuum system (6) through the air;
(2) keeping the temperature of the precursor asphalt treated in the step (1) at 280-360 ℃, and extruding the precursor asphalt through a filter screen with 60-3000 meshes and holes with the aperture of 0.03-0.5mm under pressure, wherein the number of the holes is 1-10 holes/cm2The extrusion pressure is 0.1-0.5MPa, the extruded asphalt strand is kept at the temperature of 280-320 ℃, and the waste gas generated by decomposition and separation is pumped out through a vacuum system;
(3) and (3) dropping and collecting the asphalt filaments and re-melting and granulating, wherein the temperature of the hot melting and granulating is controlled to be above the softening point of the asphalt and below 320 ℃.
2. The method for preparing spinning pitch with high thermal stability according to claim 1, wherein the precursor pitch in step (1) is purified hydrogenated coal tar pitch, purified hydrogenated petroleum pitch or pure aromatic polymerized pitch with a softening point of 60-180 ℃.
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| CN114292660B (en) * | 2021-12-07 | 2023-07-18 | 西安近代化学研究所 | Asphalt forming feeder device and process method |
| CN116613299B (en) * | 2023-07-17 | 2023-11-24 | 浙江锂宸新材料科技有限公司 | Preparation method of silicon-carbon anode material and product thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242878A (en) * | 2013-05-07 | 2013-08-14 | 中海油（青岛）重质油加工工程技术研究中心有限公司 | Asphalt bubble removing device and defoaming method thereof |
| CN108264915A (en) * | 2018-03-21 | 2018-07-10 | 湖南大学 | A kind of preparation method for spinning mesophase pitch |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242878A (en) * | 2013-05-07 | 2013-08-14 | 中海油（青岛）重质油加工工程技术研究中心有限公司 | Asphalt bubble removing device and defoaming method thereof |
| CN108264915A (en) * | 2018-03-21 | 2018-07-10 | 湖南大学 | A kind of preparation method for spinning mesophase pitch |
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Address after: Room 2202, building F1, Lugu Yuyuan, No.27 Wenxuan Road, high tech Development Zone, Changsha City, Hunan Province Patentee after: Hunan Dongying Carbon Materials Technology Co.,Ltd. Address before: Room 2202, building F1, Lugu Yuyuan, No.27 Wenxuan Road, high tech Development Zone, Changsha City, Hunan Province Patentee before: HUNAN DONGYING CARBON MATERIAL TECHNOLOGY CO.,LTD. |