CN110628449B - Method for preparing spinning-grade synthetic mesophase pitch - Google Patents
Method for preparing spinning-grade synthetic mesophase pitch Download PDFInfo
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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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- 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
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Abstract
The invention relates to a preparation method of spinning-grade synthetic mesophase pitch, which comprises the following steps: (1) adding a catalyst into a pure aromatic compound, and stirring and reacting for 2-5 hours at the temperature of 200-280 ℃ under the reaction pressure of 0.6MPa to prepare an aromatic oligomer; (2) carrying out thermal polycondensation and reduced pressure polycondensation on the low polymer of the aromatic hydrocarbon to prepare spinning-grade synthetic mesophase pitch; the invention discloses the addition of ZrCl into aromatic compounds for the first time4The catalyst is used in polymerization reaction to prepare intermediate phase asphalt. Due to ZrCl4The aromatic rings in the aromatic hydrocarbon oligomer of the polymerization product are arranged in a chain shape under the directional catalysis action, so that the large plane molecular structure of the finally formed mesophase pitch is ensured. At the same time due to ZrCl4The catalyst has less consumption, simple and convenient removal and low requirements on the pressure resistance, the air tightness and the corrosion resistance of equipment, saves the equipment cost, and the prepared mesophase pitch meets the requirements for preparing carbon fibers.
Description
Technical Field
The invention relates to a method for preparing spinning-grade synthetic mesophase pitch, and belongs to the technical field of catalytic synthesis for preparing mesophase pitch.
Background
The mesophase pitch is an important raw material for preparing high-performance carbon materials such as high-performance carbon fibers, needle coke, carbon/carbon composite materials, lithium ion secondary battery cathode materials, mesophase pitch-based foam carbon and the like. In particular, the high-performance carbon fiber prepared by using the mesophase pitch has the unique properties of high heat conduction, high modulus, high strength and the like, and is obviously superior to polyacrylonitrile-based carbon fiber, so that mesophase pitch-based carbon fiber material products are widely applied to the advanced fields of aviation, aerospace, national defense and military industry, novel energy storage devices, atomic energy industry (nuclear reactors) and the like. The high-performance carbon fiber has very strict requirements on raw material spinning-grade mesophase pitch, and has the characteristics of less heteroatoms, low ash content, high aromaticity, low degree of condensation, orderly arrangement of aromatic macromolecules, high carbon yield, good fluidity, good spinnability and the like. However, the mesophase pitch is usually prepared from coal tar or petroleum residue as a raw material by a thermal polycondensation method, due to the influence of factors such as the complexity of geological conditions in the formation process of coal and petroleum and residues in the refining process, the components of the coal tar and the petroleum residue are complex and unstable, and the components containing trace impurities are not easy to remove, so that the properties of the mesophase pitch are directly influenced. At present, spinning-grade mesophase pitch is not commercialized in China.
In order to overcome the inherent defects of coal tar pitch and petroleum residual oil pitch, researchers develop synthetic mesophase pitch, and prepare the mesophase pitch by using pure aromatic compounds (naphthalene and anthracene) as raw materials and adopting a catalytic method, so that the problems of impurities and the like of the coal tar and petroleum residual oil raw materials are solved. In addition, the preparation of the mesophase pitch by using the pure aromatic hydrocarbon compound has the characteristics of high raw material purity, regular molecular structure, narrow molecular weight distribution and the like, the reaction process is effectively controlled under the action of catalysts such as Lewis acid and the like, the formation of overlarge infusible pitch molecules is avoided, long-chain aromatic hydrocarbon molecules with regular molecular weight and high molecular flatness can be obtained, meanwhile, a pitch macromolecule chain contains short alkyl and naphthenic structures, so that the mesophase pitch has extremely high rheological property, and the characteristics are particularly important for the spinning performance of the synthesized mesophase pitch.
After the eighties of the twentieth century, the process for synthesizing mesophase pitch has gradually developed and has gone through different synthetic process routes, and Japanese patent laid-open No. 61-83317 discloses a process for synthesizing mesophase pitch by using AlCl3A process for synthesizing the low-softening-point mesophase asphalt by catalytic reaction of naphthalene-series arylhydrocarbon compounds. However, in this method, AlCl is used as a catalyst3The separation and recovery of the catalyst and the asphalt become difficult, the catalyst has high Al ion residue which is difficult to remove mainly due to high Al ion activity, and the residue has great influence on the performance of the final carbon material prepared from the mesophase asphalt.
Mochida, Japan reports the use of HF/BF3The process for synthesizing mesophase pitch by using catalyst avoids AlCl3The problem of catalyst residue. Japanese patent laid-open Nos. Hei 1-139621 and Hei 1-254796 adopt HF/BF3The aromatic hydrocarbon compound is catalyzed to prepare the spinning mesophase pitch with low softening point and high mesophase content, the reaction temperature is 200-400 ℃, the pressure reaches dozens of MPa, and particularly, a large amount of HF/BF is3The corrosion to equipment is serious, and the problems of operation safety protection, environmental protection, human body toxicity and the like exist, so that the process has difficulty in realizing industrialization in China.
In recent years, researchers haveFor HF/BF3A series of improvements were made to the catalytic reaction system, Zhengjiaming et al (proceedings of Tianjin university, 1995, vol.28, 2 nd), Luchun et al (novel carbon material, 1999, vol.14, 3 rd) and Japanese patent laid-open No. Sho 63-146920, which were milder, but had strict requirements for the material of the equipment. Chinese patent document CN104152168A (application No. 201410394762.4) discloses a mesophase pitch raw material with excellent spinnability and a preparation method thereof, wherein a naphthalene compound is used as a raw material, and a polymerization reaction is carried out in the presence of hydrogen fluoride and boron trifluoride as catalysts, wherein the amount of hydrogen fluoride is 0.5 to 15 times the molar number of the raw material, and the amount of boron trifluoride is 0.2 to 1.0 times the molar number of the raw material; the polymerization temperature is 250-300 ℃, and after the polymerization reaction is finished, the catalyst HF-BF is removed3And carrying out reduced pressure distillation on the obtained product at the temperature of 400 ℃ and under the pressure of less than 1KPa, and separating out a low-boiling-point product to obtain a mesophase pitch raw material product. The technology takes naphthalene compounds as raw materials to prepare the mesophase pitch raw materials, so that the raw material cost is high, and the carbon fibers prepared from the raw materials still cannot meet the industrial requirements. In addition, chinese patent documents CN106350088A and CN106497591A both propose different improvements, and also require the equipment to maintain high air tightness.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing spinning-grade synthetic mesophase pitch; the method can solve the problems of high impurity content, difficult removal, high requirements on equipment materials, low yield and product performance and the like of the mesophase pitch produced by the conventional method in China.
The technical scheme of the application is as follows:
a method of preparing a spinning grade synthetic mesophase pitch comprising the steps of:
(1) catalyst ZrCl4Adding ZrCl into pure aromatic compound (naphthalene or anthracene)4The mixing ratio of the aromatic hydrocarbon compound and the pure aromatic hydrocarbon compound is 0.5-2: 100, the obtained mixture is stirred and reacted for 2-5 hours in a reaction kettle at the temperature of 200-280 ℃, the reaction pressure is 0.6MPa, and the reaction is carried out under the condition of N2The preparation method comprises the following steps of (1) performing under an atmosphere to obtain a solid-liquid mixed product;
(2) mixing the product prepared in the step (1) with solvent pyridine with the volume 5 times that of the product, uniformly stirring, and then separating and removing ZrCl in the product through medium-speed qualitative filter paper4The obtained liquid component is distilled to remove pyridine solvent and unpolymerized aromatic hydrocarbon compound to obtain polycyclic aromatic hydrocarbon oligomer;
(3) subjecting the polycyclic aromatic hydrocarbon oligomer prepared in the step (2) to reaction at a reaction temperature of 390-420 ℃, a reaction time of 3-20 hours and a pressure N of normal pressure-2 MPa2And carrying out thermal polycondensation reaction under the conditions of atmosphere and the like to prepare the compound of the mesophase pitch.
(4) Adjusting the content of the intermediate phase of the product prepared in the step (3), reacting at the temperature of 390 ℃ and 420 ℃ for 0.5 hour under the negative pressure of 0.1MPa, and removing the small molecular compound to obtain the spinning-grade synthesized intermediate phase asphalt, wherein the content of the intermediate phase is more than or equal to 90 percent.
According to the invention, in the step (1), the catalyst for the reaction is ZrCl4，ZrCl4ZrCl having a water content of 04Content (wt.)>98％。
According to the invention, in the step (1), the reaction raw material, namely the pure aromatic hydrocarbon compound is one or a mixture of more of naphthalene and anthracene compounds, the water content of the pure aromatic hydrocarbon compound is 0, and the content of the pure aromatic hydrocarbon compound is more than or equal to 99.5%.
Preferably, in the step (1), the ZrCl is used4The addition amount is 0.5, 1, 1.5 and 2mol of ZrCl per 100 mol of pure aromatic compound4Or any range therebetween.
Preferably, in the step (1), the reaction temperature is 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃ or a range between any two of them.
Preferably, in step (1), the reaction time is 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours or a range between any two of them.
According to the invention, in the step (1), the reaction product is mainly formed by the dimer, trimer and tetramer of the pure arene as the raw material, contains 4-10 benzene ring structures, 1-3 naphthenic structures and contains 1-5 methyl and 1-5 methylene side chains.
The process principle of the invention is as follows:
the reaction mainly comprises two stages, namely, a pressure catalysis reaction and a thermal polycondensation reaction;
the first stage of the reaction is a pressure-catalyzed reaction by adding ZrCl to a pure aromatic compound4As a catalyst for cationic polymerization of a high molecular compound, the aromatic hydrocarbon compound is promoted to undergo cationic polymerization reaction, and the formed reaction product is mainly dimer, trimer and tetramer of a pure aromatic hydrocarbon compound and contains a cycloalkane structure, a methyl group and a methylene side chain. The molecules in mesophase pitch easily formed by the compound are more regularly and orderly arranged.
The second stage of the reaction is normal pressure or pressurized thermal polycondensation reaction, in the reaction process, the condensed ring aromatic hydrocarbon macromolecules are condensed to form larger aromatic hydrocarbon molecules, and the aromatic hydrocarbon molecules are arranged orderly and have certain orientation to form anisotropic liquid crystal phase, namely mesophase pitch. By ZrCl4The polycyclic aromatic hydrocarbon macromolecular structure contained in the catalytic mesophase pitch is consistent, has certain orientation and is beneficial to the chain molecular structure of aromatic rings.
The final step of the second reaction is decompression polycondensation reaction, which includes extracting the small molecular compound produced in the first catalytic reaction and the compound without intermediate phase, raising the intermediate phase content of the product, controlling the softening point of the intermediate phase asphalt and preparing intermediate phase asphalt suitable for spinning.
Advantageous effects
The invention discloses adding ZrCl into pure aromatic compound4The catalyst is used for reaction to prepare mesophase pitch. Compared with the prior art, the method has the following beneficial effects:
(1)ZrCl4the molecular structure arrangement of the aromatic hydrocarbon oligomer generated by the catalytic reaction is regular: due to ZrCl4The directional catalysis of the aromatic ring is carried out in an attomoto condensation mode and is longitudinally arranged in the process of polycondensation of aromatic hydrocarbon compounds into macromolecules, so that the large plane molecular structure of finally formed mesophase asphalt is ensuredThe prepared mesophase pitch has low softening point and meets the requirement of preparing high-performance carbon fiber by spinning.
(2)ZrCl4The catalyst consumption is less, and the removal is simple and convenient: ZrCl4The molar ratio of the catalyst to the pure aromatic compound is 0.5-5: 100, compared with other catalysts for catalytically synthesizing mesophase pitch, the catalyst is less in use. The reaction product is a solid-liquid mixture, the aromatic hydrocarbon oligomer is in a liquid state, ZrCl4The catalyst is solid, after the reaction is finished, the catalyst can be directly removed, the catalyst can be directly filtered and separated, the obtained aromatic hydrocarbon oligomer almost does not contain impurities such as the catalyst, and the performance of the finally prepared mesophase pitch is superior to that of petroleum mesophase pitch and coal mesophase pitch.
(3)ZrCl4The catalytic reaction operation is easy to control, and the requirement on equipment is low: ZrCl4The catalyst is solid powder, the operation process is easy to control, the reaction process has low requirements on the air tightness, the pressure resistance and the corrosion resistance of equipment, and the equipment cost is saved.
Drawings
FIG. 1 is a polarizing microscope image of mesophase pitch prepared in example 1;
FIG. 2 is a polarizing microscope photograph of mesophase pitch prepared in example 2;
FIG. 3 is a polarizing microscope photograph of mesophase pitch prepared in example 3;
FIG. 4 is a polarization microscope photograph of mesophase pitch prepared in comparative example 1;
Detailed Description
The technical solutions of the present invention are further described below with reference to the following embodiments and the accompanying drawings, but the scope of the present invention is not limited thereto.
The raw material sources are as follows:
ZrCl4purchased from Bailingwei chemical reagent company, analytically pure,>98%, moisture: none. (ii) a
Refined naphthalene is sold in the ordinary market, and the technical indexes are as follows: c10H8>99.5%, moisture: none;
the methylnaphthalene is sold in the ordinary market, and the technical indexes are as follows: c11H10>99.5%, moisture: none.
Example 1
A method of preparing a spinning grade synthetic mesophase pitch comprising the steps of:
(1) catalyst ZrCl4Adding into refined naphthalene, ZrCl4The mixing ratio of the refined naphthalene and the refined naphthalene is 1: 100, the obtained mixture is stirred and reacted for 5 hours in a reaction kettle at the temperature of 280 ℃, the reaction pressure is 0.6MPa, and the reaction is carried out under the condition of N2The preparation method comprises the following steps of (1) performing under an atmosphere to obtain a solid-liquid mixed product;
(2) mixing the product prepared in the step (1) with 5 times volume of solvent pyridine, separating liquid and solid components in the product through medium-speed qualitative filter paper, and distilling to remove the pyridine solvent in the liquid component to obtain polycyclic aromatic hydrocarbon oligomer;
(3) the polycyclic aromatic hydrocarbon oligomer prepared in the step (2) is reacted for 15 hours at the reaction temperature of 420 ℃ and under the normal pressure of N2And carrying out thermal polycondensation reaction under the conditions of atmosphere and the like to prepare the compound of the mesophase pitch.
(4) Adjusting the content of the intermediate phase of the product prepared in the step (3), reacting for 0.5 hour at 420 ℃ under the negative pressure of 0.01MPa, removing small molecular compounds to obtain synthetic intermediate phase asphalt with the softening point of 265 ℃, the content of the intermediate phase of 100 percent, the ash content of 40ppm and good spinning performance, wherein a polarizing microscope image of the product is shown in figure 1.
Example 2
A method of preparing a spinning grade synthetic mesophase pitch comprising the steps of:
(1) catalyst ZrCl4Adding into refined naphthalene, ZrCl4The mixing ratio of the refined naphthalene and the refined naphthalene is 2: 100, the obtained mixture is stirred and reacted for 2 hours in a reaction kettle at the temperature of 270 ℃, the reaction pressure is 0.6MPa, and the reaction is carried out under the condition of N2The preparation method comprises the following steps of (1) performing under an atmosphere to obtain a solid-liquid mixed product;
(2) mixing the product prepared in the step (1) with 5 times volume of solvent pyridine, separating liquid and solid components in the product through medium-speed qualitative filter paper, and distilling to remove the pyridine solvent in the liquid component to obtain polycyclic aromatic hydrocarbon oligomer;
(3) the polycyclic aromatic hydrocarbon oligomer prepared in the step (2) is reacted at the reaction temperature of 420℃,Reaction time 15 hours, normal pressure N2And carrying out thermal polycondensation reaction under the conditions of atmosphere and the like to prepare the compound of the mesophase pitch.
(4) Adjusting the content of the intermediate phase of the product prepared in the step (3), reacting for 0.5 hour at 420 ℃ under the negative pressure of 0.01MPa, removing small molecular compounds to obtain the synthetic intermediate phase asphalt with the softening point of 250 ℃, the content of the intermediate phase of 100 percent, the ash content of 45ppm and good spinning performance, wherein the polarized light microscope image of the product is shown in figure 2.
Example 3
A method of preparing a spinning grade synthetic mesophase pitch comprising the steps of:
(1) catalyst ZrCl4Adding into methylnaphthalene, ZrCl4The mixing ratio of the refined naphthalene and the refined naphthalene is 1.5: 100, the obtained mixture is stirred and reacted for 3 hours in a reaction kettle at the temperature of 280 ℃, the reaction pressure is 0.6MPa, and the reaction is carried out under the condition of N2The preparation method comprises the following steps of (1) performing under an atmosphere to obtain a solid-liquid mixed product;
(2) mixing the product prepared in the step (1) with 5 times volume of solvent pyridine, separating liquid and solid components in the product through medium-speed qualitative filter paper, and distilling to remove the pyridine solvent in the liquid component to obtain polycyclic aromatic hydrocarbon oligomer;
(3) the polycyclic aromatic hydrocarbon oligomer prepared in the step (2) is reacted for 18 hours at the reaction temperature of 420 ℃ and under normal pressure N2And carrying out thermal polycondensation reaction under the conditions of atmosphere and the like to prepare the compound of the mesophase pitch.
(4) Adjusting the content of the intermediate phase of the product prepared in the step (3), reacting for 0.5 hour at 420 ℃ under the negative pressure of 0.01MPa, removing small molecular compounds to obtain the synthetic intermediate phase asphalt with the softening point of 260 ℃, the content of the intermediate phase of 100 percent, the ash content of 45ppm and good spinning performance, wherein a polarizing microscope image of the product is shown in figure 3.
Comparative example 1
(1) The purified petroleum residual oil is reacted for 10 hours at the reaction temperature of 420 ℃ and under the pressure of 0.2MPa N2And carrying out thermal polycondensation reaction under the conditions of atmosphere and the like to prepare the compound of the mesophase pitch.
(2) Adjusting the content of the intermediate phase of the product prepared in the step (1), reacting for 0.5 hour at 420 ℃ under the negative pressure of 0.01MPa, removing small molecular compounds to obtain intermediate phase asphalt with the softening point of 320 ℃, the content of the intermediate phase of 95 percent and the ash content of 75ppm, wherein a polarizing microscope image of the product is shown in figure 4.
The invention is based on the research of the long-term system theory of the inventor, develops a new way, and finds a new way to adopt ZrCl in a complex system for polymerizing polycyclic aromatic hydrocarbon4The route of catalytic production of mesophase pitch, through proper process adjustment, the mesophase pitch prepared by the method, whether from the catalyst dosage or the requirement on equipment, has great improvement compared with other methods, and reaches the application level of spinning grade. The large-scale production of the product can upgrade and upgrade the products in related fields of China, and plays an important role in promoting.
Claims (2)
1. A method of preparing a spinning grade synthetic mesophase pitch comprising the steps of:
(1) catalyst ZrCl4Adding into naphthalene or anthracene which are pure aromatic compounds, wherein ZrCl is contained4The molar ratio of the pure aromatic hydrocarbon compound to the pure aromatic hydrocarbon compound is 0.5-2: 100, the obtained mixture is stirred and reacts for 2-5 hours in a reaction kettle at the temperature of 200-280 ℃, the reaction pressure is 0.6MPa, a solid-liquid mixed product is prepared, and a catalyst ZrCl in the product is removed4And a poorly soluble solid component to obtain polycyclic aromatic hydrocarbon oligomer;
(2) subjecting the polycyclic aromatic hydrocarbon oligomer prepared in the step (1) to a reaction at a reaction temperature of 390-420 ℃, a reaction time of 10-20 hours and a normal pressure of N2Carrying out thermal polycondensation reaction under the atmosphere condition to prepare a compound of mesophase pitch;
(3) increasing the content of the intermediate phase of the product prepared in the step (2), reacting for 0.5 hour at the temperature of 390-;
the pure aromatic hydrocarbon compound is one or a mixture of more of naphthalene and anthracene compounds, the water content of the pure aromatic hydrocarbon compound is 0, and the content of the pure aromatic hydrocarbon compound is more than or equal to 99.5 percent;
the polycyclic aromatic hydrocarbon oligomer mainly comprises dimers, trimers and tetramers of pure aromatic hydrocarbon, contains 4-10 benzene ring structures, 1-3 naphthenic structures, and contains 1-5 methyl and 1-5 methylene side chains.
2. The process of claim 1, wherein the mesophase pitch has a mesophase content of 90% or more.
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| 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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| US3839190A (en) * | 1969-10-25 | 1974-10-01 | Huels Chemische Werke Ag | Process for the production of bitumen or bitumen-containing mixtures with improved properties |
| JPS60132644A (en) * | 1983-12-22 | 1985-07-15 | Kureha Chem Ind Co Ltd | Adsorbent and its preparation |
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| CN105838409A (en) * | 2015-01-12 | 2016-08-10 | 神华集团有限责任公司 | Method for preparing mesophase pitch from residues of coal liquefaction and prepared mesophase pitch |
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