CN108264915B - Preparation method of spinnable mesophase pitch - Google Patents
Preparation method of spinnable mesophase pitch Download PDFInfo
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- CN108264915B CN108264915B CN201810233342.6A CN201810233342A CN108264915B CN 108264915 B CN108264915 B CN 108264915B CN 201810233342 A CN201810233342 A CN 201810233342A CN 108264915 B CN108264915 B CN 108264915B
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- asphalt
- mesophase pitch
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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
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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
- C10C3/02—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
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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
- C10C3/06—Working-up pitch, asphalt, bitumen by distillation
Abstract
The invention discloses a preparation method of spinnable mesophase pitch. The invention mainly comprises the following steps: taking catalytic cracking slurry oil as a raw material, taking catalytic synthesized naphthalene oligomerization asphalt as a co-carbonization agent and a hydrogen supply reagent, carrying out co-carbonization pressurized polymerization reaction for 3-12 h at the temperature of 380-450 ℃ and under the pressure of 0.5-6 MPa, and then unloading to normal pressure to obtain co-carbonization polymerization asphalt; then carrying out nitrogen bubbling purging on the co-carbonized polymerized asphalt at the temperature of 370-440 ℃ under the conditions of normal pressure and 3-10L/(min-Kg) for 1-20 h, and cooling to room temperature after the reaction is finished to obtain high-quality spinnable mesophase asphalt; the mesophase pitch is used as a raw material, and continuous spinning with 500 holes more than 5000m can be realized through melt spinning. The invention has the characteristics of simple process and equipment, mild reaction condition, low softening point of the prepared mesophase pitch, good spinnability, low cost, easy realization of industrial production and the like.
Description
Technical Field
The invention belongs to the technical field of preparation methods of raw materials for high-performance asphalt-based carbon fiber spinning, and particularly relates to a preparation method of spinnable mesophase asphalt.
Background
The mesophase pitch is an excellent precursor for preparing high-grade carbon materials such as high-performance pitch carbon fiber, needle coke, C/C composite materials and the like. As a high-performance carbonaceous precursor, mesophase pitch is generally required to have the characteristics of less heteroatoms, low ash content, high aromaticity, low degree of condensation, regular molecular arrangement, high carbon yield, good fluidity and the like. And the precursor mesophase pitch for preparing the high-performance pitch-based carbon fiber has higher requirements on the rheological property and the purity of the precursor mesophase pitch.
Researches show that the short alkyl branched chain and the naphthenic structure in the molecular structure of the mesophase pitch can effectively improve the solubility of the mesophase pitch and improve the rheological property of the mesophase pitch, thereby having better spinnability.
The catalytic cracking slurry oil is a common raw material for preparing the oil-based mesophase pitch, and in the process of preparing the mesophase pitch by separately carrying out thermal polymerization, with the progress of polymerization reaction and the removal of alkyl branched chains, the H/C molar ratio in the pitch is greatly reduced, so that the prepared mesophase pitch has a relatively high softening point, and therefore, hydrotreating is often required in the process of preparing the mesophase pitch by taking the catalytic cracking slurry oil as a raw material, and the main approaches comprise two types of high-pressure hydrotreating and reagent hydrotreating. Mochida et al prepared 100% mesophase pitch from catalytically cracked slurry pitch by a two-step process of pressure polymerization and vacuum purge and spun at higher temperatures. Chaqing and the like take aromatic hydrocarbon-rich components of catalytic cracking slurry oil as raw materials, and prepare spinnable mesophase pitch by solvent cutting and thermal polymerization processes. The chinese patent CN106544758A uses catalytic slurry oil as a raw material, and after obtaining a mesophase product through high-pressure hydrogenation pretreatment and two-step polycondensation and staged carbonization, the high-modulus pitch-based carbon fiber is prepared through melt spinning. Chinese patent CN105238430A produced high quality mesophase pitch with a lower softening point by a two-step process of hydroisomerization and thermal polycondensation. In general, mesophase pitch prepared by a single thermal polycondensation method has a low H/C, a high softening point and harsh spinning conditions. Although the solvent cutting and hydrogenation-thermal polymerization processes can prepare mesophase pitch with a lower softening point, the preparation processes have higher production cost and limit further popularization and application of the mesophase pitch.
The commonly used co-charring reagents at present are divided into two categories. The first kind is naphthalene, tetrahydronaphthalene, decahydronaphthalene and other pure substances, the co-carbonization reagent has obvious hydrogenation effect, can effectively reduce the mesophase softening point, but can obviously reduce the mesophase pitch yield, and simultaneously has the problems of large consumption of the co-carbonization agent, high hydrogenation reaction pressure, difficult separation of the co-carbonization reagent and the like. Another co-carbonization reagent is a petroleum industry byproduct with more complex components, and I.Mochida takes catalytic cracking slurry oil and vacuum residue as raw materials to prepare needle coke by a co-carbonization process. Li academic force and the like research the co-carbonization behavior of the aromatic hydrocarbon-rich fraction of the catalytic cracking slurry oil and the ethylene tar and prepare a wide-area streamline mesophase, thereby preparing the needle coke. The Wangliang of China Petroleum university uses catalytic cracking slurry oil and coal tar pitch as raw materials to carry out co-carbonization under normal pressure to prepare mesophase pitch and needle coke. In conclusion, the vacuum residue, the ethylene tar and the coal tar have complex components, and although the optical characteristics and the coking performance of the catalytic cracking slurry oil mesophase pitch can be effectively improved through the co-carbonization process, the spinning mesophase pitch is difficult to prepare. Compared with other co-charring agents, the molecular structure of the naphthalene oligomerization asphalt as the catalytic polymerization asphalt is relatively controllable, and the existence of transferable hydrogen in the naphthalene oligomerization asphalt can change the liquid phase carbonization reaction rate of catalytic cracking slurry oil and the structural composition of a mesophase; the transferable hydrogen in the naphthalene oligomerization asphalt in the co-carbonization reaction process carries out hydrogenation reduction on the catalytic cracking oil slurry to form a hydrogenated aromatic hydrocarbon and naphthenic structure, thereby effectively improving the H/C molar ratio of the mesophase asphalt, reducing the softening point of the mesophase asphalt and improving the solubility and rheological property of the mesophase asphalt.
Disclosure of Invention
The invention mainly aims to solve the problems of complex process, high equipment requirement, higher softening point of the mesophase pitch, unstable spinning and the like of the existing method for preparing the mesophase pitch by taking catalytic cracking slurry oil as a raw material and aims to develop a novel method for preparing high-quality spinnable mesophase pitch by taking the catalytic cracking slurry oil as a main raw material and the naphthalene oligomerization pitch as an auxiliary material. The method realizes that the prepared mesophase pitch has lower softening point and higher H/C molar ratio through a co-carbonization polymerization process, a thermal polymerization process and different proportions of two co-carbonization raw materials, and can realize continuous melt spinning for more than 5000 meters.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing spinnable mesophase pitch mainly comprises the following steps: adopting catalytic cracking slurry oil as a raw material, adding catalytic synthesized naphthalene oligomerization asphalt as a co-carbonization agent and a hydrogen supply reagent, carrying out co-carbonization pressurized polymerization reaction for 3-12 h at the temperature of 360-450 ℃ and under the pressure of 0.5-6 MPa, and then discharging to normal pressure to obtain co-carbonization polymerization asphalt; and then carrying out nitrogen bubbling blowing or reduced pressure distillation on the co-carbonized polymerized asphalt at the air flow of 3-10L/(min-Kg) under the conditions of normal pressure and the temperature of 350-440 ℃ for 1-20H, and cooling to room temperature after the reaction is finished to obtain the high-quality spinnable mesophase asphalt with lower softening point and higher H/C molar ratio.
The mole H/C of the catalytic cracking oil slurry is 0.80-1.6.
The softening point of the catalytic synthesized naphthalene oligomerization asphalt is 40-180 ℃, and the molar H/C is 0.60-0.79.
The catalytic synthesis naphthalene oligomerization asphalt is 0.05-1 time of catalytic cracking slurry oil in mass.
The reduced pressure distillation pressure is-0.1-0 MPa.
The softening point of the mesophase pitch prepared by the method is 250-290 ℃, the content of the mesophase is 95-100%, the mole fraction ratio of H to C is 0.50-0.65, the content of quinoline insoluble substances is less than 26wt%, continuous filaments with the diameter of more than 5000m can be prepared through melt spinning, and the filament diameter can reach 10-15 μm.
Compared with the prior preparation method, the invention has the beneficial effects that:
the catalytic cracking slurry oil is used as a main raw material, the naphthalene oligomerization asphalt is used as a co-carbonization agent, the yield of the mesophase asphalt prepared by co-carbonization of the two is higher than that of the linear combination of the mesophase asphalt prepared by single polymerization of the two, and the degree of polymerization of the mesophase asphalt molecules prepared in the co-carbonization process is relatively higher.
The naphthalene oligomerization asphalt containing a naphthenic structure is added as a hydrogen donor, so that the composition structure of a reaction system is improved, the rheological property of the system is improved, the molecular structure of a product is easy to regulate and control, and the preparation of high-quality spinnable mesophase asphalt is facilitated.
The softening point of the mesophase pitch is as low as 250-290 ℃, the H/C molar ratio is higher, the solubility is good, the viscosity is low, and the subsequent melt spinning is facilitated.
The invention has simple production process, mild reaction condition, low requirement on equipment and easy popularization and realization of industrialization.
Detailed Description
The method for preparing spinnable mesophase pitch using catalytic cracking slurry oil as main raw material provided by the present invention is further described with reference to the following examples, but the scope of the present invention is not limited to the ranges described in the examples, and the specific examples show that "parts", "contents" and the like of the amounts indicate mass fractions.
Example 1
80 parts of catalytic cracking slurry oil with the H/C molar ratio of 1.0 and the toluene soluble content of 100 percent and 20 parts of naphthalene oligomerization asphalt with the softening point of 85 ℃ and the H/C molar ratio of 0.73 of catalytic synthesis are taken to be stirred and mixed in a common high-pressure reaction kettle, nitrogen is introduced to purge the air in the kettle, the temperature is raised to 420 ℃ at the rate of 5 ℃/min and is kept for 6 hours, the system pressure in the heat preservation process is 2.2MPa, the temperature is naturally reduced after the heat preservation is finished, and the system pressure is discharged to normal pressure, so that the co-carbonization polymerization asphalt is obtained.
And blowing the co-carbonized polymeric asphalt in an inert atmosphere at 400 ℃ under normal pressure by bubbling to remove light components, wherein the gas flow is 3L/(min.Kg), continuously stirring in the blowing process, and reacting for 10 hours to obtain the mesophase asphalt with the softening point of 260 ℃, the carbon residue rate of 87.3%, the H/C of 0.574, the quinoline insoluble content of 20.5% and the anisotropic component content of 98%.
Example 2
50 parts of catalytic cracking slurry oil with the H/C molar ratio of 1.0 and the toluene soluble content of 100 percent and 50 parts of naphthalene oligomerization asphalt with the softening point of 85 ℃ and the H/C molar ratio of 0.73 of catalytic synthesis are taken to be stirred and mixed in a common high-pressure reaction kettle, nitrogen is introduced to purge the air in the kettle, the temperature is raised to 420 ℃ at the rate of 5 ℃/min and is kept for 6 hours, the system pressure in the heat preservation process is 1.8MPa, the temperature is naturally reduced after the heat preservation is finished, and the system pressure is discharged to the normal pressure, so that the co-carbonization polymerization asphalt is obtained.
And (3) carrying out reduced pressure distillation and blowing on the co-carbonized polymeric asphalt at 400 ℃ under an inert atmosphere, wherein the gas flow is 3L/(min.Kg) under the pressure of-0.05 MPa, continuously stirring in the blowing process, and reacting for 10 hours to obtain the mesophase asphalt with the softening point of 252 ℃, the carbon residue rate of 85.7%, the H/C of 0.600, the quinoline insoluble content of 18.4% and the anisotropic component content of 100%.
Example 3
80 parts of catalytic cracking slurry oil with the H/C molar ratio of 1.2 and the toluene soluble content of 100 percent and 20 parts of catalytic synthesis naphthalene oligomerization asphalt with the softening point of 93 ℃ and the H/C molar ratio of 0.76 are taken to be stirred and mixed in a common high-pressure reaction kettle, nitrogen is introduced to pressurize to 2MPa, the temperature is raised to 430 ℃ at the rate of 5 ℃/min and is kept for 3 hours, the system pressure in the heat preservation process is 5.3MPa, the temperature is naturally reduced after the heat preservation is finished, and the system pressure is discharged to the normal pressure, so that the co-carbonization polymerization asphalt is obtained.
And blowing the co-carbonized polymeric asphalt in an inert atmosphere at 410 ℃ under normal pressure by bubbling to remove light components, wherein the gas flow is 3L/(min.Kg), continuously stirring in the blowing process, and reacting for 3 hours to obtain the mesophase asphalt with the softening point of 262 ℃, the carbon residue rate of 86.0%, the H/C of 0.610, the quinoline insoluble content of 20.0% and the anisotropic component content of 100%.
Example 4
80 parts of catalytic cracking slurry oil with the molar ratio of H to C being 0.8 and the content of toluene soluble substances being 100 percent and 50 parts of naphthalene oligomerization asphalt with the softening point of 150 ℃ and the molar ratio of H to C being 0.72 are taken to be stirred and mixed in a common high-pressure reaction kettle, nitrogen is introduced to pressurize to 2MPa, the temperature is raised to 410 ℃ at the rate of 5 ℃/min and is kept for 9 hours, the system pressure in the heat preservation process is 5.0MPa, the temperature is naturally reduced after the heat preservation is finished, and the system pressure is discharged to the normal pressure, so that the co-carbonization polymerization asphalt is obtained.
And blowing the co-carbonized polymeric asphalt in an inert atmosphere at 395 ℃ under normal pressure by bubbling to remove light components, wherein the gas flow is 10L/(min.Kg), continuously stirring in the blowing process, and reacting for 14 hours to obtain the mesophase asphalt with the softening point of 280 ℃, the carbon residue rate of 87.7%, the H/C of 0.558, the quinoline insoluble content of 24.3% and the anisotropic component content of 100%.
Example 5
80 parts of catalytic cracking slurry oil with the molar ratio of H to C being 0.8 and the content of toluene soluble substances being 100 percent and 50 parts of naphthalene oligomerization asphalt with the softening point of 150 ℃ and the molar ratio of H to C being 0.68 are taken to be stirred and mixed in a common high-pressure reaction kettle, nitrogen is introduced to pressurize to 2MPa, the temperature is raised to 410 ℃ at the rate of 5 ℃/min and is kept for 9 hours, the system pressure in the heat preservation process is 5.0MPa, the temperature is naturally reduced after the heat preservation is finished, and the system pressure is discharged to the normal pressure, so that the co-carbonization polymerization asphalt is obtained.
And (3) carrying out reduced pressure distillation purging on the co-carbonized polymerized asphalt at 395 ℃ under an inert atmosphere, wherein the pressure is-0.09 MPa, the gas flow is 10L/(min.Kg), continuously stirring in the purging process, and reacting for 3 hours to obtain the mesophase asphalt with the softening point of 280 ℃, the carbon residue rate of 88.2%, the H/C of 0.540, the quinoline insoluble content of 25.0% and the anisotropic component content of 100%.
Claims (7)
1. A method for preparing spinnable mesophase pitch is characterized by comprising the following steps:
step (1): adopting catalytic cracking slurry oil as a raw material, adding catalytic synthesized naphthalene oligomerization asphalt as a co-carbonization agent and a hydrogen supply agent, carrying out co-carbonization pressurized polymerization reaction for 3-12 h at the temperature of 380-450 ℃ and under the pressure of 0.5-6 MPa, and then discharging to normal pressure to obtain co-carbonization polymerization asphalt;
step (2): and then carrying out nitrogen bubbling blowing or reduced pressure distillation on the co-carbonized polymerized asphalt at the temperature of 370-440 ℃ for 1-20 h in the amount of 3-10L/(min-Kg), and cooling to room temperature after the reaction is finished to obtain the spinnable mesophase asphalt.
2. A process for preparing a spinnable mesophase pitch according to claim 1, characterized in that: the catalytic cracking oil slurry in the step (1) is purified oil slurry, the H/C molar ratio is 0.7-1.6, and the molecular weight distribution is 250-1500.
3. A process for preparing a spinnable mesophase pitch according to claim 1, characterized in that: the softening point of the catalytic synthesized naphthalene oligomerization asphalt in the step (1) is 40-180 ℃, and the H/C molar ratio is 0.60-0.79.
4. A process for preparing a spinnable mesophase pitch according to claim 1, characterized in that: the catalytic synthesis naphthalene oligomerization asphalt in the step (1) has the use mass of 0.05-1 time of that of catalytic cracking slurry oil.
5. A process for preparing a spinnable mesophase pitch according to claim 1, characterized in that: and (3) the reduced pressure distillation pressure in the step (2) is-0.1-0 MPa.
6. A process for preparing a spinnable mesophase pitch according to claim 1, characterized in that: the softening point of the spinnable mesophase pitch prepared in the step (2) is 250-300 ℃, the content of the mesophase is 95-100%, the H/C mole fraction ratio is 0.50-0.65, and the content of quinoline insoluble substances is less than 26 wt%.
7. A process for preparing a spinnable mesophase pitch according to claim 1, characterized in that: the spinnable mesophase pitch prepared in the step (2) can be continuously spun with 500 holes more than 5000m through melt spinning, and the filament diameter reaches 10-15 mu m.
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| CN110272755B (en) * | 2019-05-13 | 2021-02-23 | 湖南东映碳材料科技有限公司 | Preparation method of spinning asphalt with high thermal stability and special device thereof |
| CN111439741B (en) * | 2020-05-29 | 2021-11-12 | 中国石油大学(华东) | Method for improving atmospheric pyrolysis carbonization carbon formation rate of ethylene tar and application thereof |
| CN113621130A (en) * | 2021-08-02 | 2021-11-09 | 武汉科技大学 | Preparation method of high-quality spinning asphalt, product and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS62277491A (en) * | 1986-05-26 | 1987-12-02 | Maruzen Petrochem Co Ltd | Production of meso-phase pitch |
| JPH0832886B2 (en) * | 1987-01-07 | 1996-03-29 | 株式会社ペトカ | Method for producing 100% mesophase pitch for spinning |
| JPH06248274A (en) * | 1993-02-22 | 1994-09-06 | Shozo Watabe | Production of mesophase pitch for production of high-strength ultrahigh elastic modulus carbon fiber using h. component stable to heat and q.s. component stable to heat as raw material and for production of matrix for carbon-carbon composite material |
| CN1053001C (en) * | 1996-12-20 | 2000-05-31 | 中国科学院山西煤炭化学研究所 | Process for preparing middle phase asphalt |
| CN1091425C (en) * | 1998-08-18 | 2002-09-25 | 中国石油化工集团公司 | Process for preparing spinning asphalt used for high-performance carbon fibre |
| US7723556B2 (en) * | 2005-12-20 | 2010-05-25 | Chevron U.S.A. Inc. | Process to make base oil from thermally cracked waxy feed using ionic liquid catalyst |
| 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 |
| CN105778057A (en) * | 2014-12-26 | 2016-07-20 | 北京化工大学常州先进材料研究院 | Method for preparing mesophase pitch through co-carbonization |
| CN105238430B (en) * | 2015-10-22 | 2017-08-11 | 中国石油大学(华东) | A kind of method that catalytic cracked oil pulp hydroisomerizing thermal polycondensation prepares mesophase pitch |
| CN106435840B (en) * | 2016-10-21 | 2018-09-11 | 中国石油大学(华东) | A kind of preparation method of asphalt base carbon fiber |
| CN106497591B (en) * | 2016-10-21 | 2019-05-07 | 湖南东映碳材料科技有限公司 | A kind of preparation method catalyzing and synthesizing mesophase pitch |
| CN106544758B (en) * | 2016-10-21 | 2018-09-11 | 中国石油大学(华东) | A kind of preparation method of high modulus pitch-based carbon fiber |
| CN107189802A (en) * | 2017-07-17 | 2017-09-22 | 青岛科技大学 | A kind of method that FCC slurry hydro-upgrading segmentation thermal polycondensation prepares mesophase pitch |
| CN107474866B (en) * | 2017-09-25 | 2019-08-06 | 上海高强高模新材料科技有限公司 | A kind of preparation method of high-quality mesophase pitch |
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