WO2021232561A1 - Preparation methods for mesophase pitch and high modulus pitch-based carbon fiber - Google Patents

Preparation methods for mesophase pitch and high modulus pitch-based carbon fiber Download PDF

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WO2021232561A1
WO2021232561A1 PCT/CN2020/101358 CN2020101358W WO2021232561A1 WO 2021232561 A1 WO2021232561 A1 WO 2021232561A1 CN 2020101358 W CN2020101358 W CN 2020101358W WO 2021232561 A1 WO2021232561 A1 WO 2021232561A1
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Prior art keywords
mesophase pitch
pitch
mesophase
based carbon
heptane
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PCT/CN2020/101358
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French (fr)
Chinese (zh)
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刘�东
娄斌
于冉
龚鑫
杜辉
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中国石油大学(华东)
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Publication of WO2021232561A1 publication Critical patent/WO2021232561A1/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • 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
    • 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

Definitions

  • the present invention relates to a preparation method of mesophase pitch and high modulus pitch-based carbon fiber, in particular, heavy oil is used as a raw material, and liquid-solid adsorption chromatography and gel permeation chromatography are combined to obtain high mesophase content.
  • a method for preparing high modulus pitch-based carbon fibers through melt spinning, pre-oxidation, carbonization, and graphitization of mesophase pitch belongs to the technical field of preparation of advanced new carbon materials.
  • the mesophase is a liquid crystal substance with optical anisotropy.
  • asphalt molecules condense with each other to form polynuclear fused ring aromatic hydrocarbon macromolecules.
  • macromolecules will adsorb surrounding molecules and accumulate to form small balls.
  • the small balls continue to grow, meet, and merge.
  • the surface tension cannot maintain the spherical state, and the spheres will disintegrate and reform to form an anisotropic phase.
  • the main methods of producing mesophase pitch at this stage include thermal condensation, hydrogenation, co-carbonization, catalytic modification and other methods.
  • Gel Permeation Chromatography is also called size exclusion chromatography (SEC), which is a liquid chromatography that separates molecules based on their size.
  • SEC size exclusion chromatography
  • the filler (gel) of gel permeation chromatography is a porous substance with an inert surface and a certain pore size range. When samples containing molecules of different sizes pass through this type of chromatographic column, some molecules are completely excluded because their size is larger than the pore size of the largest pore of the gel, and they can only pass through the column through the gap between the gel particles. These larger The molecules of can flow out of the column first.
  • Some molecules with a size smaller than the smallest pore size of the gel can penetrate into the pores of the gel and have a long retention time in the column, so they pass through the column the slowest and finally flow out of the column.
  • the middle-sized molecules between the two they can enter a part of the pores of the gel, and the number of pores that can enter is reduced as the size of the molecule increases. This results in that when gel permeation chromatography is used, the larger molecular size flows out first, that is, the molecules flow out in order of their size from large to small, so that they can be separated.
  • LSAC liquid-solid adsorption chromatography
  • HPLC high-performance liquid chromatography
  • GC gas chromatography
  • NMR nuclear magnetic resonance wave Common method
  • Liquid-solid adsorption chromatography is the earliest applied liquid chromatography method. It is based on the interaction between the sample molecule and the adsorbent (such as silica gel, alumina, etc.) surface and the mobile phase liquid. Separated for different roles. The adsorption capacity of various molecules with different polarities in the sample is different on the adsorbent. When separating in this type of chromatograph, the weakest polarity in the sample flows out first, and then in order of polarity from weak to strong. Separate.
  • adsorbent such as silica gel, alumina, etc.
  • the order of polarity is usually: saturated hydrocarbon ⁇ olefin ⁇ aromatic hydrocarbon ⁇ organic halide ⁇ sulfide ⁇ ether ⁇ nitro compound ⁇ ester ⁇ aldehyde ⁇ ketone ⁇ alcohol ⁇ amine ⁇ sulfone ⁇ sulfoxide ⁇ amide ⁇ carboxylic acid. It can be seen that when oil is used as a sample for liquid-solid adsorption chromatographic separation, non-polar saturated hydrocarbons (alkanes and cycloalkanes) flow out first, followed by aromatic hydrocarbons.
  • high-modulus pitch-based carbon fibers requires excellent quality precursor pitch.
  • the preparation of high-quality mesophase pitch with high mesophase content has higher requirements for raw materials, so it should be selected according to the characteristics of the molecular weight distribution and molecular composition of the raw materials. It is modified by favorable separation technology to optimize the composition and structure of raw materials.
  • the purpose of the present invention is to overcome the shortcomings of the prior art, using heavy oil as a raw material, combining liquid-solid adsorption chromatography and gel permeation chromatography to separate and modify the raw materials to obtain a suitable molecular weight distribution and polarity size Suitable modified raw materials are then thermally polycondensed in an autoclave to obtain high-quality mesophase pitch with high mesophase content; then high-modulus pitch-based carbon fibers are prepared.
  • the method has strong raw material compatibility, and the prepared mesophase pitch has a large watershed state optical anisotropic structure and a suitable softening point, which is suitable as an excellent precursor for high modulus pitch-based carbon fibers.
  • the preparation process of the mesophase pitch of the present invention includes the following steps: (1) using heavy oil as raw material; (2) using liquid-solid adsorption chromatography and gel permeation chromatography to sequentially optimize and modify the raw materials, Obtain modified raw materials with appropriate polarity and appropriate relative molecular weight; (3) Heat the modified raw materials at a temperature of 360°C-480°C and a pressure of 0-10MPa for 1-15 hours to prepare high-quality mesophase pitch; 4) The prepared high-quality mesophase pitch is melt-spinned, pre-oxidized, carbonized, and graphitized to obtain high-modulus pitch-based carbon fibers.
  • medium and heavy oil includes petroleum atmospheric residue, vacuum residue or its heavy fraction, medium and low temperature coal tar heavy fraction, high temperature coal tar fraction, catalytic oil slurry, hydrocracking tail oil, ethylene tar One or more of them, the aromatic content is ⁇ 40%, and the number of aromatic rings is mainly 3-4 rings.
  • the selected adsorbent is neutral alumina
  • the mesh number is 100-200 mesh
  • the mobile phase is an equal volume of n-heptane and toluene to obtain n-heptane eluate.
  • the stationary phase of the gel permeation chromatography adopts an organic gel as a filler, and the organic gel is selected from polystyrene, polyethyl acetate gel, cross-linked dextran, cross-linked polypropylene
  • the organic gel is selected from polystyrene, polyethyl acetate gel, cross-linked dextran, cross-linked polypropylene
  • One of the amides, preferably polystyrene, the pore size of the filler is The diameter of the gel column bed is 50-100mm, and the height of the gel column bed is 800-1000mm.
  • Tetrahydrofuran is selected as the mobile phase, and the toluene eluate is separated by gel permeation chromatography to obtain the relative molecular mass of the modified raw oil Is 400-1000.
  • the thermal polycondensation reaction is carried out in an autoclave.
  • the air in the autoclave needs to be replaced before the reaction starts.
  • the mesophase pitch prepared under nitrogen atmosphere and stirring conditions has a mesophase content of ⁇ 97% , The softening point is 170-350°C.
  • the tensile strength of the high modulus pitch-based carbon fiber obtained by melt spinning in the step (4) 1.8-2.2 GPa; tensile modulus: 330-550 GPa.
  • the object of the present invention is also to provide a mesophase pitch prepared by the above method.
  • Another object of the present invention is to provide a method for preparing high-modulus pitch-based carbon fibers.
  • the mesophase pitch prepared by the above method is melt-spun, and the high-modulus pitch-based carbon fibers are obtained through pre-oxidation, carbonization, and graphitization.
  • the invention also provides the application of the mesophase pitch prepared by the above method in preparing high modulus pitch-based carbon fiber.
  • the invention combines the two chromatographic separation methods and combines the advantages of the two chromatographic separation methods to obtain modified raw materials.
  • the mobile phase is: n-heptane 150mL, toluene 150mL, and then n-heptane eluate and toluene eluate are obtained; then the collected toluene eluate is collected Evaporate the solvent in an oil bath, constant weight, dry, and measure the refractive index to obtain modified raw materials with appropriate polarity;
  • n-heptane-insoluble toluene soluble toluene extract obtained by liquid-solid adsorption chromatography was separated by gel permeation chromatography, polystyrene was used as the stationary phase, and tetrahydrofuran was used as the mobile phase, and finally a modified molecular weight of 400-1000 was obtained.
  • Sexual feedstock oil obtained by liquid-solid adsorption chromatography
  • the raw materials modified by the above two chromatographic methods are placed in an autoclave at a reaction temperature of 360-480°C, and under the protection of nitrogen, the reaction pressure is 0-10MPa, and the content of the mesophase prepared by the reaction for 1-15h is ⁇ 97%, a high-quality mesophase pitch with a softening point of 170-350°C, which has a large watershed state optical anisotropic structure and good spinnability.
  • the high modulus pitch-based carbon fiber with a tensile modulus of 330-550GPa and a tensile strength of 1.8-2.2GPa is prepared by melt-spinning, pre-oxidation, carbonization, and graphitization.
  • the present invention adopts a combination process of two chromatographic separation methods to improve the composition and polarity of the raw materials, obtains the dissolution of suitable polarity by liquid-solid adsorption chromatography, and then applies gel permeation chromatography to determine the relative molecular weight. The distribution is adjusted to obtain a modified raw material with a relatively narrow molecular weight distribution.
  • a high-quality mesophase pitch (with a mesophase content ⁇ 97%, and a softening point of 170-350°C) is obtained through thermal polycondensation reaction, which is suitable as a high modulus asphalt base
  • the precursor of carbon fiber pitch is obtained through thermal polycondensation reaction, which is suitable as a high modulus asphalt base.
  • n-heptane Immediately add the above-mentioned n-heptane to dissolve and dilute the sample to be tested, and use a small amount of n-heptane to continuously rinse the conical flask 3-5 times, add the rinse solution to the column, observe the infiltration of the sample, and wait until the sample solution is completely infiltrated and oxidized After aluminum, weigh 2g of alumina to cover, and then wash the sample with solvent in the elution sequence of 150ml of n-heptane and 150ml of toluene, control the liquid flow rate to 1-2ml/min, and use an Erlenmeyer flask under the column.
  • the modified raw materials are subjected to thermal polycondensation reaction in an autoclave, the reaction temperature is 430°C, the reaction pressure is 3MPa under nitrogen atmosphere and stirring conditions, and the reaction is 8 hours to obtain a high-quality intermediate with a mesophase content of 98% and a softening point of 235°C Phase pitch, which has a large watershed state optical anisotropic structure and good spinnability.
  • a high modulus pitch-based carbon fiber with a tensile modulus of 410 GPa and a tensile strength of 2.2 GPa was prepared by melt spinning.
  • the modified raw materials are subjected to thermal polycondensation reaction in an autoclave at a reaction temperature of 450°C, under a nitrogen atmosphere and stirring conditions, a reaction pressure of 6MPa, and a reaction for 10 hours to obtain a mesophase content of 100% and a softening point of 255°C.
  • the high-quality mesophase pitch has a large watershed state optical anisotropic structure and good spinnability.
  • a high modulus pitch-based carbon fiber with a tensile modulus of 480 GPa and a tensile strength of 1.9 GPa was prepared by melt spinning.
  • the modified raw materials were subjected to thermal polycondensation reaction in an autoclave at a reaction temperature of 430°C, under a nitrogen atmosphere and stirring conditions, a reaction pressure of 3MPa, and a reaction for 8 hours to obtain a mesophase content of 97% and a softening point of 240°C.
  • the high-quality mesophase pitch has a large watershed state optical anisotropic structure and good spinnability.
  • a high modulus pitch-based carbon fiber with a tensile modulus of 420 GPa and a tensile strength of 2 GPa was prepared by melt spinning.
  • the modified raw materials were connected in an autoclave for thermal polycondensation reaction.
  • the reaction temperature was 450°C. Under nitrogen atmosphere and stirring conditions, the reaction pressure was 6MPa. After 10 hours of reaction, the mesophase content was 100% and the softening point was 260°C.
  • the high-quality mesophase pitch has a large watershed state optical anisotropic structure and good spinnability.
  • a high modulus pitch-based carbon fiber with a tensile modulus of 460 GPa and a tensile strength of 2.0 GPa was prepared by melt spinning.

Abstract

The present invention relates to the technical field of the preparation of advanced novel carbon materials. Provided are preparation methods for mesophase pitch and a high modulus pitch-based carbon fiber. The present methods comprise: treating heavy oil by means of liquid-solid adsorption chromatography (LSAC) and gel permeation chromatography (GPC) to obtain a modified raw material having a proper molecular weight and polarity; then performing thermal polycondensation on the modified raw material for 1-15 hours at the reaction temperature of 360-480°С and under the reaction pressure of 0-10 MPa to prepare high-quality mesophase pitch; and performing melt spinning on the mesophase pitch, and performing pre-oxidation, carbonization and graphitization treatment to obtain the high modulus pitch-based carbon fiber. The methods of the present invention are strong in raw material compatibility; the obtained mesophase pitch is excellent in quality, the mesophase content of the mesophase pitch is greater than or equal to 97%, and the softening point of the mesophase pitch is 170-350°С; the mesophase pitch has a large-area wide-area streamline optically anisotropic structure, and is good in spinnability and suitable for preparing a high modulus mesophase pitch-based carbon fiber.

Description

一种中间相沥青与高模量沥青基碳纤维的制备方法Preparation method of mesophase pitch and high modulus pitch-based carbon fiber 技术领域Technical field
本发明涉及一种中间相沥青与高模量沥青基碳纤维的制备方法，具体是以重质油为原料，经过液固吸附色谱法和凝胶渗透色谱法相组合的技术制备得到高中间相含量的中间相沥青，通过熔融纺丝，预氧化，碳化，石墨化制备得到高模量的沥青基碳纤维的方法，属于高级新型碳材料的制备技术领域。The present invention relates to a preparation method of mesophase pitch and high modulus pitch-based carbon fiber, in particular, heavy oil is used as a raw material, and liquid-solid adsorption chromatography and gel permeation chromatography are combined to obtain high mesophase content. A method for preparing high modulus pitch-based carbon fibers through melt spinning, pre-oxidation, carbonization, and graphitization of mesophase pitch belongs to the technical field of preparation of advanced new carbon materials.
背景技术Background technique
中间相是一种具有光学各向异性的液晶态物质。沥青分子在高温条件下，分子彼此之间发生缩合形成多核稠环芳烃大分子，在多核大分子的形成过程中，大分子会吸附周围的分子，堆积形成小球。小球不断长大、相遇、融并，当小球融并到足够大时，表面张力无法维持球形状态，球体就会发生解体和重整，从而形成各向异性相。现阶段生产中间相沥青的方法主要有热缩聚法、加氢法、共炭化法、催化改性法等方法，由于重质油中含有各种烃类及其多种异构体、稠环芳烃，原料相对分子质量分布较宽、结构及化学性质非常复杂，在进行高压釜内反应操作前都需要对原料进行预处理及调制，反应过程中还要求高压条件，需要加入催化剂促进反应。应充分重视和开发重质油的分离技术，对重质油进行精制从而得到优质的反应原料，优化反应条件。凝胶渗透色谱法作为一种新型分离方法，由于其独特的分离机理，为重油及其重组分的分离研究提供有力的手段。The mesophase is a liquid crystal substance with optical anisotropy. Under high temperature conditions, asphalt molecules condense with each other to form polynuclear fused ring aromatic hydrocarbon macromolecules. During the formation of polynuclear macromolecules, macromolecules will adsorb surrounding molecules and accumulate to form small balls. The small balls continue to grow, meet, and merge. When the small balls merge to a large enough size, the surface tension cannot maintain the spherical state, and the spheres will disintegrate and reform to form an anisotropic phase. The main methods of producing mesophase pitch at this stage include thermal condensation, hydrogenation, co-carbonization, catalytic modification and other methods. Because heavy oil contains various hydrocarbons and their various isomers, and fused ring aromatics. , The relative molecular mass distribution of the raw materials is wide, and the structure and chemical properties are very complex. The raw materials need to be pretreated and prepared before the reaction operation in the autoclave. High pressure conditions are required during the reaction process, and a catalyst needs to be added to promote the reaction. We should pay full attention to and develop the separation technology of heavy oil, refine the heavy oil to obtain high-quality reaction raw materials, and optimize the reaction conditions. As a new type of separation method, gel permeation chromatography provides a powerful means for the separation of heavy oil and its heavy components due to its unique separation mechanism.
凝胶渗透色谱法(gel permeation chromatography，简称GPC)又称为体积排阻法(size exclusion chromatography，简称SEC)，它是一种按分子体积大小进行分离的液相色谱法。凝胶渗透色谱的填充物(凝胶)是一种表面惰性的、具有一定孔径范围的多孔物质。当含有不同尺寸分子的样品通过此类色谱柱时，有些分子由于其尺寸大于凝胶最大孔的孔径，它们就完全被排斥在外，只能经凝胶颗粒之间的空隙通过柱子，这些较大的分子便能首先从色谱柱中流出。而一些尺寸小于凝胶最小的孔径的分子则可以渗透进入凝胶的孔内，在柱中的保留时间长，因此他们通过柱子的速度最慢，最后从色谱柱中流出。至于介于两 者之间的中等尺寸分子，它们可以进入凝胶的一部分孔中，而能进入的孔的数量是随分子的尺寸增大而减少的。这就导致在用凝胶渗透色谱法时，分子尺寸较大的先流出，即分子按其尺寸从大到小的顺序先后流出，从而得以分离。目前，研究者们将凝胶渗透色谱法用作预分离手段，与其他测试方法如液固吸附色谱法(LSAC)、高效液相色谱法(HPLC)、气相色谱法(GC)、核磁共振波普法(NMR)等结合使用从而得到重质油组成及结构按分子大小递变的信息。Gel Permeation Chromatography (GPC) is also called size exclusion chromatography (SEC), which is a liquid chromatography that separates molecules based on their size. The filler (gel) of gel permeation chromatography is a porous substance with an inert surface and a certain pore size range. When samples containing molecules of different sizes pass through this type of chromatographic column, some molecules are completely excluded because their size is larger than the pore size of the largest pore of the gel, and they can only pass through the column through the gap between the gel particles. These larger The molecules of can flow out of the column first. Some molecules with a size smaller than the smallest pore size of the gel can penetrate into the pores of the gel and have a long retention time in the column, so they pass through the column the slowest and finally flow out of the column. As for the middle-sized molecules between the two, they can enter a part of the pores of the gel, and the number of pores that can enter is reduced as the size of the molecule increases. This results in that when gel permeation chromatography is used, the larger molecular size flows out first, that is, the molecules flow out in order of their size from large to small, so that they can be separated. At present, researchers use gel permeation chromatography as a means of pre-separation, and other test methods such as liquid-solid adsorption chromatography (LSAC), high-performance liquid chromatography (HPLC), gas chromatography (GC), nuclear magnetic resonance wave Common method (NMR), etc. are used in combination to obtain information on the composition and structure of heavy oils according to molecular size.
液固吸附色谱法(liquid-solid adsorption chromatography，简称LSAC)是最早应用的一种液相色谱法，它是基于样品分子与吸附剂(如硅胶、氧化铝等)表面和流动相液体之间相互作用的不同而进行分离的。样品中各类极性不同的分子在吸附剂上的吸附能力强弱程度是不同，在此类色谱仪中分离时，样品中极性最弱的先行流出，随后按极性由弱到强依次分离。其极性大小顺序通常为：饱和烃＜烯烃＜芳香烃≈有机卤化物＜硫化物＜醚＜硝基化合物＜酯≈醛≈酮＜醇≈胺＜砜＜亚砜＜酰胺＜羧酸。可见，以油品作为样品进行液固吸附色谱分离时，最先流出的是非极性的饱和烃(烷烃及环烷烃)，接着是芳香烃。Liquid-solid adsorption chromatography (LSAC) is the earliest applied liquid chromatography method. It is based on the interaction between the sample molecule and the adsorbent (such as silica gel, alumina, etc.) surface and the mobile phase liquid. Separated for different roles. The adsorption capacity of various molecules with different polarities in the sample is different on the adsorbent. When separating in this type of chromatograph, the weakest polarity in the sample flows out first, and then in order of polarity from weak to strong. Separate. The order of polarity is usually: saturated hydrocarbon <olefin <aromatic hydrocarbon ≈ organic halide <sulfide <ether <nitro compound <ester ≈ aldehyde ≈ ketone <alcohol ≈ amine <sulfone <sulfoxide <amide <carboxylic acid. It can be seen that when oil is used as a sample for liquid-solid adsorption chromatographic separation, non-polar saturated hydrocarbons (alkanes and cycloalkanes) flow out first, followed by aromatic hydrocarbons.
要制得高模量的沥青基碳纤维需要品质优异的前驱体沥青，制备高中间相含量的优质中间相沥青对于原料的要求较高，所以应针对原料的分子量分布及分子组成的特点选择合适而有利的分离技术对其进行改性，优化原料的组成和结构。To prepare high-modulus pitch-based carbon fibers requires excellent quality precursor pitch. The preparation of high-quality mesophase pitch with high mesophase content has higher requirements for raw materials, so it should be selected according to the characteristics of the molecular weight distribution and molecular composition of the raw materials. It is modified by favorable separation technology to optimize the composition and structure of raw materials.
发明内容Summary of the invention
本发明的目的在于克服现有技术的不足，以重质油为原料，将液固吸附色谱法和凝胶渗透色谱法相结合，对原料进行分离和改性得到相对分子质量分布合适、极性大小适宜的改性原料，再于高压釜内进行热缩聚得到高中间相含量的优质中间相沥青；继而制得高模量沥青基碳纤维。该方法原料兼容性强，制得的中间相沥青具有大片流域态光学各向异性结构，软化点合适，适宜作为高模量沥青基碳纤维的优良前驱体。The purpose of the present invention is to overcome the shortcomings of the prior art, using heavy oil as a raw material, combining liquid-solid adsorption chromatography and gel permeation chromatography to separate and modify the raw materials to obtain a suitable molecular weight distribution and polarity size Suitable modified raw materials are then thermally polycondensed in an autoclave to obtain high-quality mesophase pitch with high mesophase content; then high-modulus pitch-based carbon fibers are prepared. The method has strong raw material compatibility, and the prepared mesophase pitch has a large watershed state optical anisotropic structure and a suitable softening point, which is suitable as an excellent precursor for high modulus pitch-based carbon fibers.
本发明所述的中间相沥青的制备过程包括以下几个步骤：(1)以重质油为原料；(2)运用液固吸附色谱法和凝胶渗透色谱法依次对原料进行优化改性， 得到极性大小适宜、相对分子质量合适的改性原料；(3)将改性原料在温度360℃-480℃，压力0-10MPa下热缩聚反应1-15h，制得优质中间相沥青；(4)将制得的优质中间相沥青进行熔融纺丝，预氧化，碳化，石墨化得到高模量沥青基碳纤维。The preparation process of the mesophase pitch of the present invention includes the following steps: (1) using heavy oil as raw material; (2) using liquid-solid adsorption chromatography and gel permeation chromatography to sequentially optimize and modify the raw materials, Obtain modified raw materials with appropriate polarity and appropriate relative molecular weight; (3) Heat the modified raw materials at a temperature of 360°C-480°C and a pressure of 0-10MPa for 1-15 hours to prepare high-quality mesophase pitch; 4) The prepared high-quality mesophase pitch is melt-spinned, pre-oxidized, carbonized, and graphitized to obtain high-modulus pitch-based carbon fibers.
所述步骤(1)中重质油包括石油常压渣油、减压渣油或其重馏分、中低温煤焦油重馏分、高温煤焦油馏分、催化油浆、加氢裂化尾油、乙烯焦油中的一种或几种，其芳烃含量为≥40％，芳香环数主要为3-4环。The step (1) medium and heavy oil includes petroleum atmospheric residue, vacuum residue or its heavy fraction, medium and low temperature coal tar heavy fraction, high temperature coal tar fraction, catalytic oil slurry, hydrocracking tail oil, ethylene tar One or more of them, the aromatic content is ≥40%, and the number of aromatic rings is mainly 3-4 rings.
所述步骤(2)液固吸附色谱法中，选用的吸附剂为中性氧化铝，目数为100-200目，流动相依次为等体积的正庚烷、甲苯，得到正庚烷溶出物和甲苯溶出物；所述凝胶渗透色谱法的固定相采用有机凝胶作为填料，所述有机凝胶选自聚苯乙烯、聚乙酸乙酯凝胶、交联葡聚糖、交联聚丙烯酰胺中的一种，优选为聚苯乙烯，填料的孔径在
Figure PCTCN2020101358-appb-000001
之间，凝胶柱床直径为50-100mm，凝胶柱床高度为800-1000mm，选择四氢呋喃作为流动相，将甲苯溶出物经凝胶渗透色谱分离，得到的改性原料油的相对分子质量为400-1000。 In the step (2) liquid-solid adsorption chromatography, the selected adsorbent is neutral alumina, the mesh number is 100-200 mesh, and the mobile phase is an equal volume of n-heptane and toluene to obtain n-heptane eluate. And toluene eluate; the stationary phase of the gel permeation chromatography adopts an organic gel as a filler, and the organic gel is selected from polystyrene, polyethyl acetate gel, cross-linked dextran, cross-linked polypropylene One of the amides, preferably polystyrene, the pore size of the filler is
Figure PCTCN2020101358-appb-000001
The diameter of the gel column bed is 50-100mm, and the height of the gel column bed is 800-1000mm. Tetrahydrofuran is selected as the mobile phase, and the toluene eluate is separated by gel permeation chromatography to obtain the relative molecular mass of the modified raw oil Is 400-1000.
所述步骤(3)中热缩聚反应在高压反应釜中进行，反应开始前需将高压反应釜内的空气置换，在氮气气氛和搅拌条件下制得的中间相沥青的中间相含量≥97％，软化点为170-350℃。In the step (3), the thermal polycondensation reaction is carried out in an autoclave. The air in the autoclave needs to be replaced before the reaction starts. The mesophase pitch prepared under nitrogen atmosphere and stirring conditions has a mesophase content of ≥97% , The softening point is 170-350℃.
所述步骤(4)中熔融纺丝得到的高模量沥青基碳纤维的拉伸强度：1.8-2.2GPa；拉伸模量：330-550GPa。The tensile strength of the high modulus pitch-based carbon fiber obtained by melt spinning in the step (4): 1.8-2.2 GPa; tensile modulus: 330-550 GPa.
本发明的目的还在于提供一种采用上述方法制备得到的中间相沥青。The object of the present invention is also to provide a mesophase pitch prepared by the above method.
本发明的另一目的在于提供一种高模量沥青基碳纤维的制备方法，将上述方法制得的中间相沥青进行熔融纺丝，经预氧化、碳化、石墨化得到高模量沥青基碳纤维。Another object of the present invention is to provide a method for preparing high-modulus pitch-based carbon fibers. The mesophase pitch prepared by the above method is melt-spun, and the high-modulus pitch-based carbon fibers are obtained through pre-oxidation, carbonization, and graphitization.
本发明还提供了上述方法制备得到的中间相沥青在制备高模量沥青基碳纤维中的应用。The invention also provides the application of the mesophase pitch prepared by the above method in preparing high modulus pitch-based carbon fiber.
本发明将两种色谱分离方法组合使用，结合两种色谱分离方法的优点，得到改性的原料。首先应用液固吸附色谱法，以中性氧化铝作为吸附剂，流动相先后为：正庚烷150mL、甲苯150mL，依次得到正庚烷溶出物、甲苯溶出物； 然后将收集到的甲苯溶出物在油浴锅中蒸干溶剂，恒重、干燥，测定折射率，从而得到极性大小适宜的改性原料；The invention combines the two chromatographic separation methods and combines the advantages of the two chromatographic separation methods to obtain modified raw materials. First apply liquid-solid adsorption chromatography with neutral alumina as the adsorbent. The mobile phase is: n-heptane 150mL, toluene 150mL, and then n-heptane eluate and toluene eluate are obtained; then the collected toluene eluate is collected Evaporate the solvent in an oil bath, constant weight, dry, and measure the refractive index to obtain modified raw materials with appropriate polarity;
将液固吸附色谱法得到的正庚烷不溶甲苯可溶的甲苯溶出物通过凝胶渗透色谱法分离，以聚苯乙烯作为固定相，以四氢呋喃作为流动相，最后得到分子量为400-1000的改性原料油。接着将经过上述两种色谱法改性后的原料置于高压反应釜内，反应温度为360-480℃，在氮气保护下，反应压力为0-10MPa，反应1-15h制得中间相含量≥97％，软化点范围170-350℃的优质中间相沥青，其具有大片流域态光学各向异性结构，可纺性好。以此作为前驱体沥青，通过熔融纺丝法，经预氧化、炭化、石墨化处理后制备得到拉伸模量为330-550GPa，拉伸强度为1.8-2.2GPa的高模量沥青基碳纤维。The n-heptane-insoluble toluene soluble toluene extract obtained by liquid-solid adsorption chromatography was separated by gel permeation chromatography, polystyrene was used as the stationary phase, and tetrahydrofuran was used as the mobile phase, and finally a modified molecular weight of 400-1000 was obtained. Sexual feedstock oil. Then, the raw materials modified by the above two chromatographic methods are placed in an autoclave at a reaction temperature of 360-480℃, and under the protection of nitrogen, the reaction pressure is 0-10MPa, and the content of the mesophase prepared by the reaction for 1-15h is ≥ 97%, a high-quality mesophase pitch with a softening point of 170-350℃, which has a large watershed state optical anisotropic structure and good spinnability. Using this as the precursor pitch, the high modulus pitch-based carbon fiber with a tensile modulus of 330-550GPa and a tensile strength of 1.8-2.2GPa is prepared by melt-spinning, pre-oxidation, carbonization, and graphitization.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
(1)本发明涉及的原料来源广泛，价格低廉，实验方法安全可靠，流程合理。(1) The raw materials involved in the present invention have a wide range of sources, low prices, safe and reliable experimental methods, and reasonable processes.
(2)本发明是采用两种色谱分离方法的组合工艺改善原料的组成和极性大小，通过液固吸附色谱法得到极性大小合适的溶出物，再应用凝胶渗透色谱法对相对分子量的分布进行调整，得到相对分子量分布较窄的改性原料，通过热缩聚反应得到品质优良的中间相沥青(其中间相含量≥97％，软化点170-350℃)，适合作为高模量沥青基碳纤维的前驱体沥青。(2) The present invention adopts a combination process of two chromatographic separation methods to improve the composition and polarity of the raw materials, obtains the dissolution of suitable polarity by liquid-solid adsorption chromatography, and then applies gel permeation chromatography to determine the relative molecular weight. The distribution is adjusted to obtain a modified raw material with a relatively narrow molecular weight distribution. A high-quality mesophase pitch (with a mesophase content ≥97%, and a softening point of 170-350℃) is obtained through thermal polycondensation reaction, which is suitable as a high modulus asphalt base The precursor of carbon fiber pitch.
具体实施方式Detailed ways
下面结合实施例进一步叙述本发明所提供的以重质油为原料通过液固吸附色谱法和凝胶渗透色谱法两种色谱方法的组合对原料油进行改性后制备中间相沥青与高模量沥青基碳纤维的方法。The following examples further describe the preparation of mesophase pitch and high modulus after modifying the feedstock oil by the combination of two chromatographic methods, liquid-solid adsorption chromatography and gel permeation chromatography, provided by the present invention with heavy oil as the raw material. Pitch-based carbon fiber method.
实施例1：Example 1:
称取60g待分离常压渣油样品溶于正庚烷，可以适当提高温度促进溶解，待到溶液呈透明；Weigh 60g sample of atmospheric residue to be separated and dissolve it in n-heptane. The temperature can be appropriately increased to promote the dissolution, until the solution becomes transparent;
取少许脱脂棉塞在吸附柱下部，不宜塞的过分紧实，将100-200目的氧化铝在500℃下活化6h后，取50g活化后的氧化铝填入色谱柱，填入的过程中用包有橡皮的细棒轻敲吸附柱以使氧化铝均匀、紧实，然后迅速加入150ml正庚烷 预湿吸附剂，观察溶剂液面下降情况，待到加入的正庚烷全部渗入氧化铝后，立即加入上述正庚烷溶解稀释的待测样品，并用正庚烷少量连续润洗锥形瓶3-5次，将润洗液也加入柱中，观察样品的渗入情况，待样品溶液完全渗入氧化铝后再称取2g氧化铝用以覆盖，然后以正庚烷150ml，甲苯150ml的洗脱顺序对测定样品进行溶剂冲洗，控制液体流速为1-2ml/min，在柱下用锥形瓶盛接溶液，依次得到正庚烷溶出物、甲苯溶出物；然后将锥形瓶中收集到的甲苯溶出物在油浴锅中蒸干溶剂，恒重；Take a small amount of absorbent cotton plug in the lower part of the adsorption column. It is not suitable to be too tightly packed. After activating the 100-200 mesh alumina at 500°C for 6 hours, take 50g of the activated alumina and fill the chromatographic column. Tap the adsorption column with a thin rubber rod to make the alumina uniform and compact. Then quickly add 150ml of n-heptane pre-wet adsorbent, observe the drop of the solvent level, and wait until the added n-heptane has penetrated into the alumina. Immediately add the above-mentioned n-heptane to dissolve and dilute the sample to be tested, and use a small amount of n-heptane to continuously rinse the conical flask 3-5 times, add the rinse solution to the column, observe the infiltration of the sample, and wait until the sample solution is completely infiltrated and oxidized After aluminum, weigh 2g of alumina to cover, and then wash the sample with solvent in the elution sequence of 150ml of n-heptane and 150ml of toluene, control the liquid flow rate to 1-2ml/min, and use an Erlenmeyer flask under the column. Connect the solution to obtain the n-heptane eluate and the toluene eluate in sequence; then, the toluene eluate collected in the conical flask is evaporated to dry the solvent in an oil bath, and the weight is constant;
取上述经过液固吸附色谱法分离得到的甲苯溶出物，采用四氢呋喃作为溶剂配成5％(质量分数)的溶液，将此溶液加入到装有聚苯乙烯填料的色谱柱中，凝胶柱床直径为50mm，柱床高度为800mm，聚苯乙烯填料孔径为
Figure PCTCN2020101358-appb-000002
用激光小角衍射仪分子量检测器测量分子量，最后得到分子量为400-1000的改性原料； Take the above-mentioned toluene eluate separated by liquid-solid adsorption chromatography, use tetrahydrofuran as the solvent to prepare a 5% (mass fraction) solution, and add this solution to a chromatographic column equipped with polystyrene packing. The diameter is 50mm, the height of the column bed is 800mm, and the aperture of the polystyrene packing is
Figure PCTCN2020101358-appb-000002
Measure the molecular weight with the molecular weight detector of the laser small-angle diffractometer, and finally obtain the modified raw material with a molecular weight of 400-1000;
将改性原料于高压反应釜进行热缩聚反应，反应温度为430℃，在氮气气氛和搅拌条件下，反应压力为3MPa，反应8h制得中间相含量98％，软化点为235℃的优质中间相沥青，其具有大片的流域态光学各向异性结构，可纺性好。以此作为前驱体沥青，通过熔融纺丝法，制备得到拉伸模量为410GPa，拉伸强度为2.2GPa的高模量沥青基碳纤维。The modified raw materials are subjected to thermal polycondensation reaction in an autoclave, the reaction temperature is 430℃, the reaction pressure is 3MPa under nitrogen atmosphere and stirring conditions, and the reaction is 8 hours to obtain a high-quality intermediate with a mesophase content of 98% and a softening point of 235℃ Phase pitch, which has a large watershed state optical anisotropic structure and good spinnability. Using this as the precursor pitch, a high modulus pitch-based carbon fiber with a tensile modulus of 410 GPa and a tensile strength of 2.2 GPa was prepared by melt spinning.
实施例2：Example 2:
称取60g待分离催化油浆样品溶于正庚烷，可以适当提高温度促进溶解，待到溶液呈透明；Weigh 60g of the catalytic oil slurry sample to be separated and dissolve it in n-heptane. The temperature can be appropriately increased to promote the dissolution, until the solution becomes transparent;
取少许脱脂棉塞在吸附柱下部，不宜塞的过分紧实，将100-200目的氧化铝在500℃下活化6h后，取50g活化后的氧化铝填入色谱柱，填入的过程中用包有橡皮的细棒轻敲吸附柱以使氧化铝均匀、紧实，然后迅速加入150ml正庚烷预湿吸附剂，观察溶剂液面下降情况，待到加入的正庚烷全部渗入氧化铝后，立即加入上述正庚烷溶解稀释的待测样品，并用正庚烷少量连续润洗锥形瓶3-5次，将润洗液也加入柱中，观察样品的渗入情况，待样品溶液完全渗入氧化铝后再称取2g氧化铝用以覆盖，然后以正庚烷150ml，甲苯150ml的洗脱顺序对测定样品进行溶剂冲洗，控制液体流速为1-2ml/min，在柱下用250ml锥形瓶盛 接溶液，依次得到正庚烷溶出物、甲苯溶出物。然后将锥形瓶中的收集到的甲苯溶出物在油浴锅中蒸干溶剂，恒重；Take a small amount of absorbent cotton plug in the lower part of the adsorption column. It is not suitable to be too tightly packed. After activating the 100-200 mesh alumina at 500°C for 6 hours, take 50g of the activated alumina and fill the chromatographic column. Tap the adsorption column with a thin rubber rod to make the alumina uniform and compact. Then quickly add 150ml of n-heptane pre-wet adsorbent, observe the drop of the solvent level, and wait until the added n-heptane has penetrated into the alumina. Immediately add the above-mentioned n-heptane to dissolve and dilute the sample to be tested, and use a small amount of n-heptane to continuously rinse the conical flask 3-5 times, add the rinse solution to the column, observe the infiltration of the sample, and wait until the sample solution is completely infiltrated and oxidized After aluminum, weigh 2g of alumina to cover, then wash the sample with solvent in the elution sequence of 150ml of n-heptane and 150ml of toluene, control the liquid flow rate to 1-2ml/min, and use a 250ml Erlenmeyer flask under the column After receiving the solution, the n-heptane eluate and the toluene eluate are successively obtained. Then, evaporate the solvent from the collected toluene extract in the conical flask in an oil bath to a constant weight;
取上述经过液固吸附色谱法分离得到的甲苯溶出物，采用四氢呋喃作为溶剂配成5％(质量分数)的溶液，将此溶液加入到装有聚苯乙烯填料的色谱柱中，凝胶柱床直径为60mm，柱床高度为1000mm，聚苯乙烯填料的孔径为
Figure PCTCN2020101358-appb-000003
用激光小角衍射仪分子量检测器测量分子量，最后得到分子量为400-1000的改性原料； Take the above-mentioned toluene eluate separated by liquid-solid adsorption chromatography, use tetrahydrofuran as the solvent to prepare a 5% (mass fraction) solution, and add this solution to a chromatographic column equipped with polystyrene packing. The diameter is 60mm, the height of the column bed is 1000mm, and the pore size of the polystyrene packing is
Figure PCTCN2020101358-appb-000003
Measure the molecular weight with the molecular weight detector of the laser small-angle diffractometer, and finally obtain the modified raw material with a molecular weight of 400-1000;
将改性后的原料于高压反应釜进行热缩聚反应，反应温度为450℃，在氮气气氛和搅拌条件下，反应压力为6MPa，反应10h制得中间相含量100％，软化点为255℃的优质中间相沥青，其具有大片的流域态光学各向异性结构，可纺性好。以此作为前驱体沥青，通过熔融纺丝法，制备得到拉伸模量为480GPa，拉伸强度为1.9GPa的高模量沥青基碳纤维。The modified raw materials are subjected to thermal polycondensation reaction in an autoclave at a reaction temperature of 450°C, under a nitrogen atmosphere and stirring conditions, a reaction pressure of 6MPa, and a reaction for 10 hours to obtain a mesophase content of 100% and a softening point of 255°C. The high-quality mesophase pitch has a large watershed state optical anisotropic structure and good spinnability. Using this as the precursor pitch, a high modulus pitch-based carbon fiber with a tensile modulus of 480 GPa and a tensile strength of 1.9 GPa was prepared by melt spinning.
实施例3：Example 3:
称取60g待分离催化油浆样品溶于正庚烷，可以适当提高温度促进溶解，待到溶液呈透明；Weigh 60g of the catalytic oil slurry sample to be separated and dissolve it in n-heptane. The temperature can be appropriately increased to promote the dissolution, until the solution becomes transparent;
取少许脱脂棉塞在吸附柱下部，不宜塞的过分紧实，将100-200目的氧化铝在500℃下活化6h后，取50g活化后的氧化铝填入色谱柱，填入的过程中用包有橡皮的细棒轻敲吸附柱以使氧化铝均匀、紧实，然后迅速加入150ml正庚烷预湿吸附剂，观察溶剂液面下降情况，待到加入的正庚烷全部渗入氧化铝后，立即加入上述正庚烷溶解稀释的待测样品，并用正庚烷少量连续润洗锥形瓶3-5次，将润洗液也加入柱中，观察样品的渗入情况，待样品溶液完全渗入氧化铝后再称取2g氧化铝用以覆盖，然后以正庚烷150ml，甲苯150ml的洗脱顺序对测定样品进行溶剂冲洗，控制液体流速为1-2ml/min，在柱下用250ml锥形瓶盛接溶液，依次得到正庚烷溶出物、甲苯溶出物。然后将锥形瓶中的收集到的甲苯溶出物在油浴锅中蒸干溶剂，恒重；Take a small amount of absorbent cotton plug in the lower part of the adsorption column. It is not suitable to be too tightly packed. After activating the 100-200 mesh alumina at 500°C for 6 hours, take 50g of the activated alumina and fill the chromatographic column. Tap the adsorption column with a thin rubber rod to make the alumina uniform and compact. Then quickly add 150ml of n-heptane pre-wet adsorbent, observe the drop of the solvent level, and wait until the added n-heptane has penetrated into the alumina. Immediately add the above-mentioned n-heptane to dissolve and dilute the sample to be tested, and use a small amount of n-heptane to continuously rinse the conical flask 3-5 times, add the rinse solution to the column, observe the infiltration of the sample, and wait until the sample solution is completely infiltrated and oxidized After aluminum, weigh 2g of alumina to cover, then wash the sample with solvent in the elution sequence of 150ml of n-heptane and 150ml of toluene, control the liquid flow rate to 1-2ml/min, and use a 250ml Erlenmeyer flask under the column After receiving the solution, the n-heptane eluate and the toluene eluate are successively obtained. Then, evaporate the solvent from the collected toluene extract in the conical flask in an oil bath to a constant weight;
取上述经过液固吸附色谱法分离得到的甲苯溶出物，采用四氢呋喃作为溶剂配成5％(质量分数)的溶液，将此溶液加入到装有聚苯乙烯填料的色谱柱中，凝胶柱床直径为70mm，柱床高度为900mm，聚苯乙烯填料的孔径为
Figure PCTCN2020101358-appb-000004
用激光小角衍射仪分子量检测器测量分子量，最后得到分子量为400-1000的改性原料； Take the above-mentioned toluene eluate separated by liquid-solid adsorption chromatography, use tetrahydrofuran as the solvent to prepare a 5% (mass fraction) solution, and add this solution to a chromatographic column equipped with polystyrene packing. The diameter is 70mm, the height of the column bed is 900mm, and the pore size of the polystyrene packing is
Figure PCTCN2020101358-appb-000004
Measure the molecular weight with the molecular weight detector of the laser small-angle diffractometer, and finally obtain the modified raw material with a molecular weight of 400-1000;
将改性后的原料于高压反应釜进行热缩聚反应，反应温度为430℃，在氮气气氛和搅拌条件下，反应压力为3MPa，反应8h制得中间相含量97％，软化点范围240℃的优质中间相沥青，其具有大片的流域态光学各向异性结构，可纺性好。以此作为前驱体沥青，通过熔融纺丝法，制备得到拉伸模量为420GPa，拉伸强度为2GPa的高模量沥青基碳纤维。The modified raw materials were subjected to thermal polycondensation reaction in an autoclave at a reaction temperature of 430°C, under a nitrogen atmosphere and stirring conditions, a reaction pressure of 3MPa, and a reaction for 8 hours to obtain a mesophase content of 97% and a softening point of 240°C. The high-quality mesophase pitch has a large watershed state optical anisotropic structure and good spinnability. Using this as the precursor pitch, a high modulus pitch-based carbon fiber with a tensile modulus of 420 GPa and a tensile strength of 2 GPa was prepared by melt spinning.
实施例4：Example 4:
称取60g待分离加氢裂化尾油样品溶于正庚烷，可以适当提高温度促进溶解，待到溶液呈透明；Weigh 60g of the hydrocracking tail oil sample to be separated and dissolve it in n-heptane. The temperature can be appropriately increased to promote the dissolution. When the solution becomes transparent;
取少许脱脂棉塞在吸附柱下部，不宜塞的过分紧实，将100-200目的氧化铝在500℃下活化6h后，取50g活化后的氧化铝填入色谱柱，填入的过程中用包有橡皮的细棒轻敲吸附柱以使氧化铝均匀、紧实，然后迅速加入150ml正庚烷预湿吸附剂，观察溶剂液面下降情况，待到加入的正庚烷全部渗入氧化铝后，立即加入上述正庚烷溶解稀释的待测样品，并用正庚烷少量连续润洗锥形瓶3-5次，将润洗液也加入柱中，观察样品的渗入情况，待样品溶液完全渗入氧化铝后再称取2g氧化铝用以覆盖，然后以正庚烷150ml，甲苯150ml的洗脱顺序对测定样品进行溶剂冲洗，控制液体流速为1-2ml/min，在柱下用250ml锥形瓶盛接溶液，依次得到正庚烷溶出物、甲苯溶出物。然后将锥形瓶中的收集到的甲苯溶出物在油浴锅中蒸干溶剂，恒重；Take a small amount of absorbent cotton plug in the lower part of the adsorption column. It is not suitable to be too tightly packed. After activating 100-200 mesh alumina at 500°C for 6 hours, take 50g of activated alumina and fill the chromatographic column. Tap the adsorption column with a thin rubber rod to make the alumina uniform and compact. Then quickly add 150ml of n-heptane pre-wet adsorbent, observe the drop of the solvent level, and wait until the added n-heptane has penetrated into the alumina. Immediately add the above-mentioned n-heptane to dissolve and dilute the sample to be tested, and use a small amount of n-heptane to continuously rinse the conical flask 3-5 times, add the rinse solution to the column, observe the infiltration of the sample, and wait until the sample solution is completely infiltrated and oxidized After aluminum, weigh 2g of alumina to cover, then wash the sample with solvent in the elution sequence of 150ml of n-heptane and 150ml of toluene, control the liquid flow rate to 1-2ml/min, and use a 250ml Erlenmeyer flask under the column After receiving the solution, the n-heptane eluate and the toluene eluate are successively obtained. Then, evaporate the solvent from the collected toluene extract in the conical flask in an oil bath to a constant weight;
取上述经过液固吸附色谱法分离得到的甲苯溶出物，采用四氢呋喃作为溶剂配成5％(质量分数)的溶液，将此溶液加入到装有聚苯乙烯填料的色谱柱中，凝胶柱床直径为80mm，柱床高度为1000mm，聚苯乙烯填料的孔径为
Figure PCTCN2020101358-appb-000005
用激光小角衍射仪分子量检测器测量分子量，最后得到分子量为400-1000的改性原料； Take the above-mentioned toluene eluate separated by liquid-solid adsorption chromatography, use tetrahydrofuran as the solvent to prepare a 5% (mass fraction) solution, and add this solution to a chromatographic column equipped with polystyrene packing. The diameter is 80mm, the height of the column bed is 1000mm, and the pore size of the polystyrene packing is
Figure PCTCN2020101358-appb-000005
Measure the molecular weight with the molecular weight detector of the laser small-angle diffractometer, and finally obtain the modified raw material with a molecular weight of 400-1000;
将改性后的原料于高压反应釜接进行热缩聚反应，反应温度为450℃，在氮气气氛和搅拌条件下，反应压力为6MPa，反应10h制得中间相含量100％，软化点为260℃的优质中间相沥青，其具有大片的流域态光学各向异性结构，可纺 性好。以此作为前驱体沥青，通过熔融纺丝法，制备得到拉伸模量为460GPa，拉伸强度为2.0GPa的高模量沥青基碳纤维。The modified raw materials were connected in an autoclave for thermal polycondensation reaction. The reaction temperature was 450°C. Under nitrogen atmosphere and stirring conditions, the reaction pressure was 6MPa. After 10 hours of reaction, the mesophase content was 100% and the softening point was 260°C. The high-quality mesophase pitch has a large watershed state optical anisotropic structure and good spinnability. Using this as the precursor pitch, a high modulus pitch-based carbon fiber with a tensile modulus of 460 GPa and a tensile strength of 2.0 GPa was prepared by melt spinning.
对比例1：Comparative example 1:
称取60g待分离加氢裂化尾油样品溶于正庚烷，可以适当提高温度促进溶解，待到溶液呈透明；Weigh 60g of the hydrocracking tail oil sample to be separated and dissolve it in n-heptane. The temperature can be appropriately increased to promote the dissolution. When the solution becomes transparent;
取少许脱脂棉塞在吸附柱下部，不宜塞的过分紧实，将100-200目的氧化铝在500℃下活化6h后，取50g活化后的氧化铝填入色谱柱，填入的过程中用包有橡皮的细棒轻敲吸附柱以使氧化铝均匀、紧实，然后迅速加入150ml正庚烷预湿吸附剂，观察溶剂液面下降情况，待到加入的正庚烷全部渗入氧化铝后，立即加入上述正庚烷溶解稀释的待测样品，并用正庚烷少量连续润洗锥形瓶3-5次，将润洗液也加入柱中，观察样品的渗入情况，待样品溶液完全渗入氧化铝后再称取2g氧化铝用以覆盖，然后以正庚烷150ml，甲苯150ml的洗脱顺序对测定样品进行溶剂冲洗，控制液体流速为1-2ml/min，在柱下用250ml锥形瓶盛接溶液，依次得到正庚烷溶出物、甲苯溶出物；然后将锥形瓶中的收集到的甲苯溶出物在油浴锅中蒸干溶剂，恒重；Take a small amount of absorbent cotton plug in the lower part of the adsorption column. It is not suitable to be too tightly packed. After activating the 100-200 mesh alumina at 500°C for 6 hours, take 50g of the activated alumina and fill the chromatographic column. Tap the adsorption column with a thin rubber rod to make the alumina uniform and compact. Then quickly add 150ml of n-heptane pre-wet adsorbent, observe the drop of the solvent level, and wait until the added n-heptane has penetrated into the alumina. Immediately add the above-mentioned n-heptane to dissolve and dilute the sample to be tested, and use a small amount of n-heptane to continuously rinse the conical flask 3-5 times, add the rinse solution to the column, observe the infiltration of the sample, and wait until the sample solution is completely infiltrated and oxidized After aluminum, weigh 2g of alumina to cover, then wash the sample with solvent in the elution sequence of 150ml of n-heptane and 150ml of toluene, control the liquid flow rate to 1-2ml/min, and use a 250ml Erlenmeyer flask under the column Hold the solution to obtain the n-heptane eluate and the toluene eluate in sequence; then evaporate the solvent from the toluene eluate collected in the Erlenmeyer flask in an oil bath to a constant weight;
取上述经过液固吸附色谱法分离得到的甲苯溶出物作为原料，在高压反应釜中进行热缩聚反应，反应温度为430℃，在氮气气氛和搅拌条件下，反应压力为3MPa，反应8h制得中间相含量90％，软化点为220℃的中间相沥青，以此作为前驱体沥青，通过熔融纺丝法，制备得到拉伸模量为390GPa，拉伸强度为1.7GPa的沥青基碳纤维。Take the above-mentioned toluene eluate separated by liquid-solid adsorption chromatography as a raw material, and conduct thermal polycondensation reaction in an autoclave at a reaction temperature of 430°C. Under a nitrogen atmosphere and stirring conditions, the reaction pressure is 3MPa and the reaction time is 8 hours. A mesophase pitch with a mesophase content of 90% and a softening point of 220°C was used as a precursor pitch to prepare pitch-based carbon fibers with a tensile modulus of 390 GPa and a tensile strength of 1.7 GPa through the melt spinning method.
对比例2：Comparative example 2:
称取60g待分离加氢裂化尾油样品溶于正庚烷，可以适当提高温度促进溶解，待到溶液呈透明；Weigh 60g of the hydrocracking tail oil sample to be separated and dissolve it in n-heptane. The temperature can be appropriately increased to promote the dissolution. When the solution becomes transparent;
取少许脱脂棉塞在吸附柱下部，不宜塞的过分紧实，将100-200目的氧化铝在500℃下活化6h后，取50g活化后的氧化铝填入色谱柱，填入的过程中用包有橡皮的细棒轻敲吸附柱以使氧化铝均匀、紧实，然后迅速加入150ml正庚烷预湿吸附剂，观察溶剂液面下降情况，待到加入的正庚烷全部渗入氧化铝后，立即加入上述正庚烷溶解稀释的待测样品，并用正庚烷少量连续润洗锥形瓶3-5 次，将润洗液也加入柱中，观察样品的渗入情况，待样品溶液完全渗入氧化铝后再称取2g氧化铝用以覆盖，然后以正庚烷150ml，甲苯150ml的洗脱顺序对测定样品进行溶剂冲洗，控制液体流速为1-2ml/min，在柱下用250ml锥形瓶盛接溶液，依次得到正庚烷溶出物、甲苯溶出物；然后将锥形瓶中的收集到的甲苯溶出物在油浴锅中蒸干溶剂，恒重；Take a small amount of absorbent cotton plug in the lower part of the adsorption column. It is not suitable to be too tightly packed. After activating the 100-200 mesh alumina at 500°C for 6 hours, take 50g of the activated alumina and fill the chromatographic column. Tap the adsorption column with a thin rubber rod to make the alumina uniform and compact. Then quickly add 150ml of n-heptane pre-wet adsorbent, observe the drop of the solvent level, and wait until the added n-heptane has penetrated into the alumina. Immediately add the above-mentioned n-heptane to dissolve and dilute the sample to be tested, and use a small amount of n-heptane to continuously rinse the conical flask 3-5 times, add the rinse solution to the column, observe the infiltration of the sample, and wait until the sample solution is completely infiltrated and oxidized After aluminum, weigh 2g of alumina to cover, then wash the sample with solvent in the elution sequence of 150ml of n-heptane and 150ml of toluene, control the liquid flow rate to 1-2ml/min, and use a 250ml Erlenmeyer flask under the column Hold the solution to obtain the n-heptane eluate and the toluene eluate in sequence; then evaporate the solvent from the toluene eluate collected in the Erlenmeyer flask in an oil bath to a constant weight;
取上述经过液固吸附色谱法分离得到的甲苯溶出物作为原料，在高压反应釜中进行热缩聚反应，反应温度为450℃，在氮气气氛和搅拌条件下，反应压力为6MPa，反应10h制得中间相含量92％，软化点为235℃的中间相沥青，以此作为前驱体沥青，通过熔融纺丝法，制备得到拉伸模量为410GPa，拉伸强度为1.8GPa的沥青基碳纤维。Take the above-mentioned toluene eluate separated by liquid-solid adsorption chromatography as a raw material, and conduct thermal polycondensation reaction in an autoclave at a reaction temperature of 450°C, under a nitrogen atmosphere and stirring conditions, a reaction pressure of 6 MPa, and a reaction time of 10 hours. A mesophase pitch with a mesophase content of 92% and a softening point of 235°C is used as a precursor pitch to prepare pitch-based carbon fibers with a tensile modulus of 410 GPa and a tensile strength of 1.8 GPa through a melt spinning method.

Claims (9)

  1. 一种中间相沥青的制备方法，其特征在于，包括以下步骤：(1)以重质油为原料，组合使用液固吸附色谱法和凝胶渗透色谱法对原料进行预处理，得到极性大小适宜和相对分子质量合适的改性原料；所述改性原料为相对分子质量为400-1000范围内的正庚烷不溶甲苯可溶的甲苯溶出物；(2)将改性原料加入到高压反应釜中，氮气气氛，在搅拌条件下，反应温度为360-480℃，反应压力为0-10MPa，反应1-15h热缩聚得到高中间相含量的优质中间相沥青。A method for preparing mesophase pitch, which is characterized in that it comprises the following steps: (1) Using heavy oil as a raw material, a combination of liquid-solid adsorption chromatography and gel permeation chromatography is used to pretreat the raw material to obtain the polarity size Modified raw materials with suitable and appropriate relative molecular mass; the modified raw materials are n-heptane insoluble toluene soluble toluene eluates with a relative molecular mass in the range of 400-1000; (2) adding the modified raw materials to the high-pressure reaction In the kettle, in a nitrogen atmosphere, under stirring conditions, the reaction temperature is 360-480°C, the reaction pressure is 0-10 MPa, and the reaction is 1-15 hours to obtain high-quality mesophase pitch with high mesophase content by thermal polycondensation.
  2. 根据权利要求1所述的一种中间相沥青的制备方法，其特征在于：所述步骤(1)中的重质油选自石油常压渣油、石油减压渣油、石油重馏分、中低温煤焦油重馏分、高温煤焦油馏分、催化油浆、加氢裂化尾油、乙烯焦油中的一种或几种。The method for preparing mesophase pitch according to claim 1, wherein the heavy oil in the step (1) is selected from petroleum atmospheric residue, petroleum vacuum residue, petroleum heavy fraction, medium One or more of low-temperature coal tar heavy fraction, high-temperature coal tar fraction, catalytic oil slurry, hydrocracking tail oil, and ethylene tar.
  3. 根据权利要求1所述的一种中间相沥青的制备方法，其特征在于：所述步骤(1)的液固吸附色谱法使用的吸附剂为中性氧化铝，流动相依次为等体积的正庚烷和甲苯。A method for preparing mesophase pitch according to claim 1, characterized in that the adsorbent used in the liquid-solid adsorption chromatography of step (1) is neutral alumina, and the mobile phase is an equal volume of positive Heptane and toluene.
  4. 根据权利要求1所述的一种中间相沥青的制备方法，其特征在于：所述步骤(1)的凝胶渗透色谱法的固定相采用有机凝胶作为填料，所述有机凝胶选自聚苯乙烯、聚乙酸乙酯凝胶、交联葡聚糖、交联聚丙烯酰胺中的一种，优选为聚苯乙烯，填料孔径为
    Figure PCTCN2020101358-appb-100001
    凝胶柱床直径为50-100mm，凝胶柱床高度为800-1000mm，洗脱剂为四氢呋喃。     The method for preparing mesophase pitch according to claim 1, wherein the stationary phase of the gel permeation chromatography in step (1) uses organic gel as a filler, and the organic gel is selected from poly One of styrene, polyethyl acetate gel, cross-linked dextran, and cross-linked polyacrylamide, preferably polystyrene, and the pore size of the filler is
    Figure PCTCN2020101358-appb-100001
    The diameter of the gel column bed is 50-100mm, the height of the gel column bed is 800-1000mm, and the eluent is tetrahydrofuran.
  5. 根据权利要求1所述的一种中间相沥青的制备方法，其特征在于：所述的预处理方法是先将原料经过液固吸附色谱法处理得到不溶于正庚烷的甲苯溶出物；再将所述甲苯溶出物通过凝胶渗透色谱法分离，得到相对分子质量为400-1000的改性原料。The method for preparing mesophase pitch according to claim 1, characterized in that: the pretreatment method is to first process the raw materials through liquid-solid adsorption chromatography to obtain the toluene eluate that is insoluble in n-heptane; The toluene eluate is separated by gel permeation chromatography to obtain a modified raw material with a relative molecular mass of 400-1000.
  6. 根据权利要求1所述的一种中间相沥青的制备方法，其特征在于：所述中间相沥青的中间相含量≥97％，软化点范围170-350℃，具有大片流域态光学各向异性结构。The method for preparing mesophase pitch according to claim 1, characterized in that the mesophase content of the mesophase pitch is ≥97%, the softening point range is 170-350℃, and the mesophase pitch has a large watershed state optical anisotropic structure .
  7. 一种高模量沥青基碳纤维的制备方法，其特征在于：将权利要求1-6任一所述的方法制备得到的中间相沥青经熔融纺丝、预氧化、碳化、石墨化制得，所述高模量沥青基碳纤维的拉伸强度为：2-3.5GPa，拉伸模量为：330-550GPa。A method for preparing high modulus pitch-based carbon fiber, characterized in that: the mesophase pitch prepared by the method of any one of claims 1-6 is prepared by melt spinning, pre-oxidation, carbonization, and graphitization. The tensile strength of the high modulus pitch-based carbon fiber is: 2-3.5 GPa, and the tensile modulus is: 330-550 GPa.
  8. 一种采用权利要求1-6任一所述的方法制备得到的中间相沥青。A mesophase pitch prepared by the method of any one of claims 1-6.
  9. 权利要求1-6任一所述的方法制备得到的中间相沥青在制备高模量沥青 基碳纤维中的应用。Use of the mesophase pitch prepared by the method of any one of claims 1 to 6 in the preparation of high modulus pitch-based carbon fibers.
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