CN116536070A - Method for preparing mesophase pitch by hydrogenating coal tar pitch components - Google Patents
Method for preparing mesophase pitch by hydrogenating coal tar pitch components Download PDFInfo
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- CN116536070A CN116536070A CN202310544069.XA CN202310544069A CN116536070A CN 116536070 A CN116536070 A CN 116536070A CN 202310544069 A CN202310544069 A CN 202310544069A CN 116536070 A CN116536070 A CN 116536070A
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- coal tar
- tar pitch
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000011294 coal tar pitch Substances 0.000 title claims abstract description 40
- 239000011302 mesophase pitch Substances 0.000 title claims abstract description 33
- 239000010426 asphalt Substances 0.000 claims abstract description 31
- 238000000605 extraction Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 230000003287 optical effect Effects 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000012643 polycondensation polymerization Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 21
- 239000006228 supernatant Substances 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 5
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- PJDWNSYGMXODTB-UHFFFAOYSA-N 1,2,3,4,4a,4b,5,6-octahydrophenanthrene Chemical compound C1=CCCC2C(CCCC3)C3=CC=C21 PJDWNSYGMXODTB-UHFFFAOYSA-N 0.000 claims description 2
- PUNXVEAWLAVABA-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene;1,2,5,6-tetrahydroanthracene Chemical compound C1=CC=C2C=C(CCCC3)C3=CC2=C1.C1=CCCC2=C1C=C1CCC=CC1=C2 PUNXVEAWLAVABA-UHFFFAOYSA-N 0.000 claims description 2
- KEIFWROAQVVDBN-UHFFFAOYSA-N 1,2-dihydronaphthalene Chemical compound C1=CC=C2C=CCCC2=C1 KEIFWROAQVVDBN-UHFFFAOYSA-N 0.000 claims description 2
- UUSUFQUCLACDTA-UHFFFAOYSA-N 1,2-dihydropyrene Chemical compound C1=CC=C2C=CC3=CCCC4=CC=C1C2=C43 UUSUFQUCLACDTA-UHFFFAOYSA-N 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- -1 dihydroanthracene Chemical compound 0.000 claims description 2
- XXPBFNVKTVJZKF-UHFFFAOYSA-N dihydrophenanthrene Natural products C1=CC=C2CCC3=CC=CC=C3C2=C1 XXPBFNVKTVJZKF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 2
- 239000004917 carbon fiber Substances 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000011331 needle coke Substances 0.000 abstract 1
- 230000000750 progressive effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 13
- 239000012071 phase Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
- C10C3/023—Working-up pitch, asphalt, bitumen by chemical means reaction with inorganic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
The invention discloses a method for preparing mesophase pitch by hydrogenating coal tar pitch components, which comprises the steps of sequentially obtaining A, B and C components or A, B, C and D components or A, B, C, D and E components from coal tar pitch by adopting a progressive extraction method; adding a hydrogen-supplying solvent and a catalyst into the heavy components separated from the coal tar pitch, and carrying out hydrotreatment to obtain hydrogenated heavy components; mixing the hydrogenated heavy component and the unhydrogenated component according to a certain proportion to obtain modified asphalt; and performing thermal condensation polymerization on the modified asphalt to obtain mesophase asphalt. The modified asphalt provided by the invention has a molecular composition suitable for preparing mesophase asphalt, the molecular weight range is reasonable, the distribution is concentrated, the anisotropic content in the prepared mesophase asphalt is high, the optical structure is good, the modified asphalt is rich in a wide-area streamline structure, and the modified asphalt is a high-quality precursor for preparing carbon materials such as carbon fibers, needle coke and the like.
Description
Technical Field
The invention belongs to the field of deep processing of coal tar pitch, and particularly relates to a method for preparing mesophase pitch by hydrogenating a coal tar pitch component.
Background
The heavy aromatic compound can form mesophase pitch through liquid phase carbonization, and has anisotropic optical properties and a certain rheological property. The planar aromatic macromolecules which are regularly arranged in the mesophase pitch are easy to be piled up and arranged according to the structure of graphite under the high-temperature heat treatment condition, so that the mesophase pitch-based carbon material has a plurality of excellent performances. Therefore, the mesophase pitch is an excellent precursor for preparing high-elasticity carbon fibers, high-specific-surface-area activated carbon, ultra-high-power graphite electrodes and other advanced functional materials.
The coal tar pitch has high yield, low cost and high aromatic hydrocarbon content, and is widely applied to preparing mesophase pitch. However, coal tar pitch has a complex composition, high impurity content, and contains quinoline insoluble or highly reactive components, which are susceptible to excessive polycondensation during carbonization, which is detrimental to the formation of mesophase pitch molecules.
At present, in order to improve the hydrogen-carbon ratio, remove quinoline insoluble substances (QI) and adjust molecular composition, a method for preparing an intermediate phase aiming at modifying a coal tar pitch raw material is mainly hydrogenation modification. For example, patent CN110699107a discloses a method for preparing mesophase pitch by using coal pitch as raw material and through hydro-catalysis-hydrogen supply treatment, the method has moderate softening point and high content of mesophase pitch, but the preparation method needs secondary hydrogenation of raw material, has complex process and uses a large amount of hydrogen supply solvent, is not easy to control hydrogenation depth, and has higher preparation cost.
In the hydrogenation reaction process, because the molecular composition distribution of the coal tar pitch is wider, light components are easy to excessively hydrogenate, and the hydrogenation depth of heavy components is insufficient, the problems of low yield of an intermediate phase, non-ideal optical structure and the like are caused. The patent on the aspects of accurately adjusting the raw material composition, preventing excessive hydrogenation and the like for coal tar pitch hydrogenation is rarely related.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a method for preparing mesophase pitch by hydrogenating coal tar pitch components, which is characterized in that the components with different properties are obtained by gradually extracting the coal tar pitch, wherein heavy components are mixed with unhydrogenated components according to a certain proportion after hydrogenation, so that the molecular composition of the pitch is changed, the molecular weight distribution is proper, a naphthenic structure and an aliphatic side chain are added, stable growth and fusion of mesophase pellets are promoted, and the prepared mesophase pitch has high anisotropic phase content and is mainly of a wide-area streamline structure.
In order to solve the technical problems, the invention provides the following technical scheme: a method for preparing mesophase pitch by hydrogenating a coal tar pitch component comprises,
step-by-step extraction is carried out on the coal tar pitch by using different extractants to obtain A, B and C three components or A, B, C and D four components or A, B, C, D and E five components;
adding hydrogen-supplying solvent into one or more of B, C, D or E components, mixing with a catalyst, and obtaining hydrogenated heavy components after hydrogenation treatment;
mixing the hydrogenated heavy component and the unhydrogenated component to obtain a modified asphalt;
and performing thermal condensation polymerization on the modified asphalt to obtain the mesophase pitch.
As a preferred embodiment of the method according to the invention, wherein: the step-by-step extraction of the coal tar pitch with different extractant comprises,
adding an extractant a into the coal tar pitch, standing after extraction, and separating raffinate 1 and supernatant to obtain an extract, and recovering the extractant a through reduced pressure distillation to obtain a component A;
vacuum drying the raffinate 1 to constant weight, mixing with the extractant B, standing after extraction, separating the raffinate 2 and supernatant to obtain an extract, and recovering the extractant B through reduced pressure distillation to obtain a component B;
and (3) vacuum drying the raffinate 2 to constant weight, mixing with the extractant C, standing after extraction, separating the raffinate and the supernatant to obtain an extract, and recovering the extractant C through reduced pressure distillation to obtain the component C.
In the step, four extraction agents are adopted in the step-by-step extraction process to sequentially obtain A, B, C and D four components; five extractants are adopted to sequentially obtain A, B, C, D and E five components.
As a preferred embodiment of the method according to the invention, wherein: the extractant is selected from n-hexane, n-heptane, toluene, pyridine, chloroform, acetone, tetrahydrofuran, quinoline, anthracene oil, wash oil and naphthalene oil.
As a preferred embodiment of the method according to the invention, wherein: the step-by-step extraction is carried out, wherein the mass ratio of the extractant to the asphalt is 5:1-20:1, and the extraction conditions are as follows: stirring at 50-120 deg.c for 50-90 min.
As a preferred embodiment of the method according to the invention, wherein: the hydrogen-supplying solvent is one or more than two of dihydropyrene, dihydroanthracene, tetrahydroanthracene, dihydronaphthalene, tetrahydronaphthalene, dihydrophenanthrene, octahydrophenanthrene, tetrahydroquinoline and coal direct liquefaction hydrogen-supplying solvent and coal tar distillate hydrogenation products;
the catalyst is Fe 2 O 3 、FeS 2 、ZnO、ZnCl 2 、SnO 2 One or a mixture of more than two of Co, mo and Ni catalysts.
As a preferred embodiment of the method according to the invention, wherein: the hydrogen supply solvent accounts for 5-60 wt% of the mass of the heavy components;
the hydrotreating is carried out under the condition of hydrogen or nitrogen of 2 MPa-8 MPa, and the temperature is 340 ℃ to 440 ℃.
As a preferred embodiment of the method according to the invention, wherein: mixing the hydrogenated heavy component and the unhydrogenated component, wherein,
when the coal tar pitch is extracted into 3 components, the mass ratio of the unhydrogenated components to the hydrogenated heavy components is 10-20 percent, 20-50 percent and 10-40 percent;
when the coal tar pitch is extracted into 4 components, the mass ratio of the unhydrogenated components to the hydrogenated heavy components is 10% -20%, 20% -50%, 10% -30% and 10% -20%;
when the coal tar pitch is extracted into 5 components, the mass ratio of the unhydrogenated component to the hydrogenated heavy component is 10% -20%, 20% -50%, 10% -30%, 10% -20% and 10% -20%.
As a preferred embodiment of the method according to the invention, wherein: the thermal polycondensation process is to heat up to 320-480 ℃ at a heating rate of 0.5-5 ℃/min, and the heat preservation time is 3-15 h.
As a preferred embodiment of the method according to the invention, wherein: the modified asphalt is subjected to thermal polycondensation, wherein the stirring speed is 50-500 r/min, and the initial pressure of nitrogen is 0.1-5 MPa.
As a preferred embodiment of the method according to the invention, wherein: the intermediate phase asphalt product is intermediate phase asphalt with anisotropic phase content more than or equal to 80%, wide area streamline optical texture content more than or equal to 60% and softening point of 120-380 ℃.
The invention has the beneficial effects that:
(1) The invention provides a method for preparing high-quality mesophase pitch by taking coal tar pitch as a raw material, extracting and separating components by a solvent, hydrogenating heavy components, mixing and modifying the components to adjust the composition of the raw material; the prepared mesophase pitch has proper softening point, high anisotropic phase content, rich ideal optical structure and simple and feasible method.
(2) According to the invention, components with different properties are obtained by extracting the coal tar pitch with an organic solvent and separating, so that impurities and high-reactivity substances in raw materials can be reduced, the thermal polycondensation reaction can be smoothly carried out, coking is inhibited, and the thermal stability of a system is improved.
(3) According to the invention, hydrogenation is carried out on heavy components of coal tar pitch to obtain hydrogenated heavy components, a naphthene structure and an alkyl side chain are introduced, active hydrogen is released in a thermal polycondensation reaction, excessive polycondensation of aromatic hydrocarbon molecules is effectively inhibited, mesophase pellets stably grow, and wide-area mesophase formation is facilitated.
(4) According to the invention, the modified asphalt is obtained after the unhydrogenated component and the hydrogenated heavy component are mixed, the molecular weight distribution of the modified asphalt is regulated, and a naphthene structure and an alkyl side chain are introduced, so that the thermal polycondensation reaction rate is regulated, the generation and development of a mesophase are promoted, and the content of the mesophase is promoted and the optical texture is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a polarizing microscopic morphology of mesophase pitch prepared in example 1 of the present invention.
FIG. 2 is a polarizing microscopic morphology of mesophase pitch prepared in example 2 of the present invention.
FIG. 3 is a polarizing microscopic morphology of mesophase pitch prepared in example 3 of the present invention.
FIG. 4 is a process flow diagram of a method for preparing mesophase pitch by hydrogenating a coal tar pitch component in an embodiment of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
The embodiment provides a method for preparing mesophase pitch by hydrogenating a coal tar pitch component, the process flow chart is shown in fig. 4, and the method comprises the following steps:
(1) Placing 100g of coal tar pitch and 500g of n-heptane into a beaker, stirring for 50min at the temperature of 40 ℃ in a water bath, standing, separating raffinate 1 and supernatant, and distilling the obtained extract under reduced pressure to remove an organic solvent to obtain a component A;
placing the raffinate 1 and 400g of toluene after vacuum drying for 24 hours into a beaker, stirring for 60 minutes at the water bath temperature of 60 ℃, standing, separating the raffinate 2 and the supernatant, and removing the organic solvent after the obtained extract is distilled under reduced pressure to obtain a component B;
placing the extract 2 dried in vacuum for 24 hours and 200g of tetrahydrofuran in a beaker, stirring for 60 minutes at the temperature of 70 ℃ in a water bath, standing, separating raffinate 3 and supernatant, and removing organic solvent after reduced pressure distillation of the obtained extract to obtain a component C;
placing extract 3 dried in vacuum for 24h and 200g of quinoline in a beaker, stirring for 60min at 70 ℃ in water bath, standing, separating raffinate 4 and supernatant, distilling the obtained extract under reduced pressure, removing organic solvent to obtain component D, and drying raffinate 4 in vacuum for 24h to obtain component E;
(2) 40g of component D,6g of tetrahydronaphthalene and 0.04g of cobalt-molybdenum catalyst are placed in a reaction kettle, the initial pressure of hydrogen is 4MPa, the stirring speed is 100 revolutions per minute, the temperature is raised to 390 ℃ at the heating rate of 1.5 ℃/min, and the mixture is cooled to room temperature after being kept at the constant temperature for 1 hour, so as to obtain hydrogenated component D1;
putting 40g of component E,4g of tetrahydronaphthalene and 0.03g of cobalt-molybdenum catalyst into a reaction kettle, wherein the initial pressure of hydrogen is 4MPa, the stirring speed is 100 revolutions per minute, heating to 410 ℃ at the heating rate of 1.5 ℃/min, keeping the temperature for 1h, and cooling to room temperature to obtain a hydrogenated component E1;
(3) Placing 5g of component A, 12.5g of component B, 15g of component C, 10g of hydrogenated component D1 and 7.5g of hydrogenated component E1 in a beaker, stirring by strong magnetic force for 30min at the temperature of 90 ℃ in a water bath, and cooling to room temperature to obtain modified asphalt;
(4) And (3) placing the modified asphalt into a reaction kettle, wherein the initial pressure of nitrogen is 0.5MPa, heating to 375 ℃ at the heating rate of 1.5 ℃/min, and keeping the temperature for 8 hours to obtain the mesophase asphalt.
The polarizing microscopic morphology of the prepared mesophase pitch is shown in fig. 1, and the measurement results of the anisotropic phase content and the optical structure composition are shown in table 1.
Example 2
The embodiment provides a method for preparing mesophase pitch by hydrogenating a coal tar pitch component, which comprises the following steps:
(1) Placing 100g of coal tar pitch and 500g of n-hexane in a beaker, stirring for 40min at the water bath temperature, standing, separating raffinate 1 and supernatant, and distilling the obtained extract under reduced pressure to remove an organic solvent to obtain a component A;
placing the raffinate 1 and 400g of toluene in a beaker, stirring for 40min at the water bath temperature of 60 ℃, standing, separating the raffinate 2 and the supernatant, and removing the organic solvent from the obtained extract after reduced pressure distillation to obtain a component B;
placing the raffinate 2 and 300g of chloroform into a beaker, stirring for 40min at the temperature of 65 ℃ in a water bath, standing, separating the raffinate 3 and the supernatant, and removing the organic solvent from the obtained extract after reduced pressure distillation to obtain a component C;
placing the extract 3 and 200g of pyridine into a beaker, stirring for 50min at the temperature of 70 ℃ in a water bath, standing, separating raffinate 4 and supernatant, distilling the obtained extract under reduced pressure, removing organic solvent to obtain a component D, and vacuum drying the raffinate 4 for 24h to obtain a component E;
(2) 40g of component E,2g of dihydroanthracene and 0.03g of Fe are taken 2 O 3 Placing the catalyst in a reaction kettle, wherein the initial pressure of hydrogen is 3MPa, the stirring speed is 100 revolutions per minute, the temperature is increased to 400 ℃ at the heating rate of 1.5 ℃/min, and the catalyst is cooled to room temperature after being kept at the constant temperature for 1h to obtain a hydrogenation component E1;
(3) 7.5g of component A, 10g of component B, 15g of component C, 10g of component D and 7.5g of hydrogenated component E1 are taken and placed in a beaker, and are stirred by strong magnetic force for 30min at the water bath of 90 ℃, and cooled to room temperature, so as to obtain modified asphalt;
(4) And (3) placing the modified asphalt into a reaction kettle, wherein the initial pressure of nitrogen is 0.5MPa, heating to 375 ℃ at the heating rate of 1.5 ℃/min, and keeping the temperature for 8 hours to obtain the mesophase asphalt.
The polarizing microscopic morphology of the obtained mesophase pitch is shown in fig. 2, and the measurement results of the anisotropic phase content and the optical structure composition are shown in table 1.
Example 3
The embodiment provides a method for preparing mesophase pitch by hydrogenating a coal tar pitch component, which comprises the following steps:
(1) Placing 100g of coal tar pitch and 500g of n-hexane in a beaker, stirring for 40min at the water bath temperature, standing, separating raffinate 1 and supernatant, and distilling the obtained extract under reduced pressure to remove an organic solvent to obtain a component A;
placing the raffinate 1 and 400g of toluene in a beaker, stirring for 40min at the water bath temperature of 60 ℃, standing, separating the raffinate 2 and the supernatant, and removing the organic solvent from the obtained extract after reduced pressure distillation to obtain a component B;
placing the raffinate 2 and 300g of chloroform into a beaker, stirring for 40min at the temperature of 65 ℃ in a water bath, standing, separating the raffinate 3 and the supernatant, and removing the organic solvent from the obtained extract after reduced pressure distillation to obtain a component C;
placing the extract 3 and 200g of quinoline into a beaker, stirring for 50min at the temperature of 70 ℃ in a water bath, standing, separating raffinate 4 and supernatant, distilling the obtained extract under reduced pressure, removing organic solvent to obtain a component D, and vacuum drying the raffinate 4 for 24h to obtain a component E;
(2) Putting 40g of component D, 4g of tetrahydronaphthalene and 0.02g of cobalt-molybdenum catalyst into a reaction kettle, wherein the initial pressure of hydrogen is 5MPa, the stirring speed is 100 revolutions per minute, heating to 400 ℃ at the heating rate of 1.5 ℃/min, keeping the temperature for 1h, and cooling to room temperature to obtain a hydrogenated component D1;
(3) 10g of component A, 17.5g of component B, 15g of component C and 11.5g of hydrogenated component D1 are taken and placed in a beaker, and are stirred by strong magnetic force for 15min at the water bath of 90 ℃, and cooled to room temperature, so as to obtain modified asphalt;
(4) And (3) placing the modified asphalt into a reaction kettle, wherein the initial pressure of nitrogen is 0.5MPa, heating to 375 ℃ at the heating rate of 1.5 ℃/min, and keeping the temperature for 7 hours to obtain the mesophase asphalt.
The polarizing microscopic morphology of the obtained mesophase pitch is shown in fig. 3, and the measurement results of the anisotropic phase content and the optical structure composition are shown in table 1.
TABLE 1 mesophase pitch content and optical structural composition prepared in examples 1 to 3
According to the method for preparing the mesophase pitch by hydrogenating the coal tar pitch components, disclosed by the invention, a controllable new path is provided for preparing the mesophase pitch with high added value by gradually extracting the coal tar pitch and hydrogenating the heavy components to a proper depth.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, and it should be covered in the scope of the present invention.
Claims (10)
1. A method for preparing mesophase pitch by hydrogenating a coal tar pitch component is characterized by comprising the following steps: comprising the steps of (a) a step of,
step-by-step extraction is carried out on the coal tar pitch by using different extractants to obtain A, B and C three components or A, B, C and D four components or A, B, C, D and E five components;
adding hydrogen-supplying solvent into one or more of B, C, D or E components, mixing with a catalyst, and obtaining hydrogenated heavy components after hydrogenation treatment;
mixing the hydrogenated heavy component and the unhydrogenated component to obtain a modified asphalt;
and performing thermal condensation polymerization on the modified asphalt to obtain the mesophase pitch.
2. The method of claim 1, wherein: the step-by-step extraction of the coal tar pitch with different extractant comprises,
adding an extractant a into the coal tar pitch, standing after extraction, and separating raffinate 1 and supernatant to obtain an extract, and recovering the extractant a through reduced pressure distillation to obtain a component A;
vacuum drying the raffinate 1 to constant weight, mixing with the extractant B, standing after extraction, separating the raffinate 2 and supernatant to obtain an extract, and recovering the extractant B through reduced pressure distillation to obtain a component B;
and (3) vacuum drying the raffinate 2 to constant weight, mixing with the extractant C, standing after extraction, separating the raffinate and the supernatant to obtain an extract, and recovering the extractant C through reduced pressure distillation to obtain the component C.
In the steps, A, B, C and D components are sequentially obtained when four extracting agents are adopted in the step-by-step extraction process; when five extractants are used, A, B, C, D and E five components are obtained in sequence.
3. The method of claim 2, wherein: the extractant is selected from n-hexane, n-heptane, toluene, pyridine, chloroform, acetone, tetrahydrofuran, quinoline, anthracene oil, wash oil, naphthalene oil, and the like.
4. A method according to claim 2 or 3, wherein: the step-by-step extraction is carried out, wherein the mass ratio of the extractant to the asphalt is 5:1-20:1, and the extraction conditions are as follows: stirring at 50-120 deg.c for 50-90 min.
5. The method of claim 1, wherein: the hydrogen-supplying solvent is one or a mixture of more than two of dihydropyrene, dihydroanthracene, tetrahydroanthracene, dihydronaphthalene, tetrahydronaphthalene, dihydrophenanthrene, octahydrophenanthrene, tetrahydroquinoline and coal direct liquefaction hydrogen-supplying solvent and coal tar distillate hydrogenation products;
the catalyst is Fe 2 O 3 、FeS 2 、ZnO、ZnCl 2 、SnO 2 One or a mixture of two or more of Co, mo, ni and other catalysts.
6. The method of claim 5, wherein: the hydrogen supply solvent accounts for 5-60 wt% of the mass of the heavy components;
the hydrotreating is carried out under the condition of hydrogen or nitrogen of 2 MPa-8 MPa, and the temperature is 340 ℃ to 440 ℃.
7. The method of claim 1, wherein: mixing the hydrogenated heavy component and the unhydrogenated component, wherein,
when the coal tar pitch is separated into 3 components, the mass ratio of the unhydrogenated component to the hydrogenated heavy component is 10-20 percent, 20-50 percent and 10-40 percent;
when the coal tar pitch is separated into 4 components, the mass ratio of the unhydrogenated component to the hydrogenated heavy component is 10% -20%, 20% -50%, 10% -30% and 10% -20%;
when the coal tar pitch is separated into 5 components, the mass ratio of the unhydrogenated component to the hydrogenated heavy component is 10% -20%, 20% -50%, 10% -30%, 10% -20% and 10% -20%.
8. The method of claim 1, wherein: the thermal polycondensation process is to heat up to 320-480 ℃ at a heating rate of 0.5-5 ℃/min, and the heat preservation time is 3-15 h.
9. The method of claim 1, wherein: the modified asphalt is subjected to thermal polycondensation, wherein the stirring speed is 50-500 r/min, and the initial pressure of nitrogen is 0.1-5 MPa.
10. The method of claim 1, wherein: the intermediate phase asphalt product is intermediate phase asphalt with anisotropic phase content more than or equal to 80%, wide area streamline optical texture content more than or equal to 60% and softening point of 120-380 ℃.
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