CN114164014A - Mesophase pitch and preparation method thereof - Google Patents
Mesophase pitch and preparation method thereof Download PDFInfo
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- CN114164014A CN114164014A CN202111458090.5A CN202111458090A CN114164014A CN 114164014 A CN114164014 A CN 114164014A CN 202111458090 A CN202111458090 A CN 202111458090A CN 114164014 A CN114164014 A CN 114164014A
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- 239000011302 mesophase pitch Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title description 5
- 239000010426 asphalt Substances 0.000 claims abstract description 69
- 239000002028 Biomass Substances 0.000 claims abstract description 47
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 239000012046 mixed solvent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000011317 mixed pitch Substances 0.000 claims description 17
- 239000011295 pitch Substances 0.000 claims description 15
- 239000011294 coal tar pitch Substances 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011331 needle coke Substances 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000003575 carbonaceous material Substances 0.000 abstract description 9
- 230000003287 optical effect Effects 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011280 coal tar Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000000930 thermomechanical effect Effects 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 239000011269 tar Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011300 coal pitch Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002023 wood Substances 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
-
- 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
-
- 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
- C10C3/005—Working-up pitch, asphalt, bitumen by mixing several fractions (also coaltar fractions with petroleum fractions)
-
- 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
- C10C3/007—Working-up pitch, asphalt, bitumen winning and separation of asphalt from mixtures with aggregates, fillers and other products, e.g. winning from natural asphalt and regeneration of waste asphalt
-
- 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
- C10C3/026—Working-up pitch, asphalt, bitumen by chemical means reaction with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/06—Working-up pitch, asphalt, bitumen by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
Provided are mesophase pitch and a method for preparing the same, comprising: centrifuging and filtering biomass asphalt, mixing the biomass asphalt with coal tar asphalt to obtain mixed asphalt, and mixing an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent to obtain a mixed solvent; placing the mixed asphalt and the mixed solvent in a pressure separation kettle, raising the temperature and the pressure, and standing at constant temperature; taking the upper layer solution, and distilling under reduced pressure to obtain refined mixed asphalt; and (3) carrying out co-carbonization thermal polycondensation reaction on the refined mixed asphalt to obtain the mesophase asphalt. The obtained mesophase pitch optical structure is a streamline wide-area structure; the mesophase pitch content is 100%; the softening point is low, the aromaticity is high, the high-temperature viscosity after melting is low, the rheological property is excellent, and the high-temperature-resistant high-viscosity aromatic hydrocarbon can be used as an excellent raw material for preparing carbon materials such as high-quality needle coke, carbon foam and the like.
Description
Technical Field
The invention belongs to the field of asphalt preparation, and particularly relates to a method for preparing mesophase asphalt through co-carbonization.
Background
The biomass asphalt is a carbon product prepared by using biomass tar as a raw material and performing vacuum distillation, and the yield of the biomass asphalt accounts for about 50 percent of the biomass tar. The biomass tar is obtained by pyrolyzing biomass materials at high temperature, wherein the biomass materials comprise wood chips, crop straws and the like, and have the characteristics of reproducibility, low cost, low nitrogen, low sulfur, sufficient global supply and the like. Different biomass materials are used to produce biochar materials for different uses, according to specific requirements. Many studies report the use of various biomass resources to produce storage materials with porous adsorbents and the use of bio-coke produced from biomass materials to produce energy storage electrodes. The electrode is prepared by pyrolyzing the raw materials of biological coke and biological asphalt, and has the conductivity and mechanical properties of the electrode prepared from the traditional carbon material. Biomass asphalt has similar rheological properties to petroleum asphalt and is feasible for road engineering applications. Despite the above uses of biomass materials, the use of biomass pitch for mesophase pitch production has been rarely reported.
Needle coke is a high-quality carbon material developed along with the research of carbonaceous mesophase, and is mainly a carbonized product of coal pitch or petroleum pitch. The needle coke has the advantages of small resistivity, low thermal expansion coefficient, high mechanical strength, good oxidation resistance, larger volume density, real density and the like, and is an indispensable ideal raw material for producing high-power and ultrahigh-power electrodes. Needle coke has been produced industrially for many years, and there are two key factors in the formation of needle coke during the carbonization process: one is that the raw material system has high fluidity, and the other is that the sufficient light component gas escapes to form directional and uniform airflow, so as to realize the airflow coke-drawing and prepare the fine-fiber texture-shaped needle coke with high quality. The biomass pitch has the characteristics of low carbon content, high hydrogen content, low heteroatom content and high light component content, and the method for co-carbonizing the biomass pitch and the coal tar pitch adjusts the composition and the structure of the pitch under the action of certain reaction temperature and pressure, makes up the defect of low hydrogen content in the coal pitch, and can introduce a naphthenic structure. The asphalt containing lower impurity components can also effectively adjust the composition and the structure of the asphalt. Therefore, the method for preparing the mesophase pitch-based needle coke by co-carbonizing the biomass pitch and the coal tar pitch is an economical and feasible method which can improve the properties of the mesophase pitch and the needle coke.
Disclosure of Invention
Therefore, the invention aims to provide a method for preparing mesophase pitch by co-carbonizing biomass pitch and medium-temperature coal tar pitch, the prepared mesophase pitch has a better tissue structure, can be used as an excellent raw material for preparing carbon materials such as high-quality needle coke, carbon foam and the like, and simultaneously provides a feasible method for the application of the biomass pitch.
The invention provides a preparation method of mesophase pitch, which comprises the following steps:
(1) placing the biomass asphalt in a centrifugal filter for centrifugal filtration to obtain filtered biomass asphalt;
(2) preparing a mixed solvent: mixing an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent according to a certain weight ratio to prepare a mixed solvent;
(3) preparing mixed asphalt, mixing the filtered biomass asphalt obtained in the step (1) with coal tar asphalt according to a certain weight ratio to prepare mixed asphalt;
(4) mixing the mixed asphalt obtained in the step (3) and the mixed solvent obtained in the step (2) according to a certain weight ratio, and placing the mixture in a pressure separation kettle;
(5) introducing inert gas into the pressure separation kettle for purging, keeping the pressure of the inert gas atmosphere increased to 0.5-1Mpa, heating to 120-;
(6) taking out the upper layer solution after standing and settling in the pressurized polymerization kettle, placing the upper layer solution in a reduced pressure distillation device for reduced pressure distillation, and recovering the solvent to obtain refined mixed asphalt;
(7) and (4) placing the refined mixed asphalt obtained in the step (6) into a pressurized polymerization kettle, raising the pressure and the temperature under the inert gas atmosphere, and keeping the temperature and the pressure constant for a period of time to perform a co-carbonization thermal polycondensation reaction to obtain the mesophase asphalt.
Wherein, in the step (1), the rotation speed of the centrifugal filter is 4000-.
And (2) in the step (1), putting the biomass asphalt into a centrifuge tube with filter cloth, and carrying out centrifugal filtration in a centrifugal filter.
Wherein, in the step (1), a centrifugal filter is used for filtering and removing large impurities in the biomass asphalt, such as small branches and leaves, straws and the like.
Wherein in the step (2), the aromatic hydrocarbon solvent is wash oil, and the aliphatic hydrocarbon solvent is kerosene.
Wherein, in the step (2), the weight ratio of the aromatic hydrocarbon solvent to the aliphatic hydrocarbon solvent is 0.2-0.4: 1.
Wherein in the step (3), the weight ratio of the biomass pitch to the coal tar pitch is 0.1-0.2: 1.
Wherein in the step (4), the weight ratio of the mixed asphalt to the mixed solvent is 1: 2-4.
Wherein, in the step (5), the constant temperature standing time is 1-3h (preferably 2 h).
Wherein, in the step (6), the reduced pressure distillation is carried out at a pressure of-0.90 to-0.98 MPa.
Wherein, in the step (6), the solvent distilled out under reduced pressure is recovered for recycling.
Wherein, in the step (6), the removal of the quinoline insolubles is to remove the quinoline insolubles by using a pressurized separation kettle to prepare the refined mixed asphalt, wherein the extraction pressure is 0.5-1MPa, and the extraction temperature is 120-.
Wherein the quinoline insoluble content in the refined mixed asphalt obtained in the step (6) is not more than 0.1 wt%.
Wherein, in the step (7), the refined mixed asphalt is placed into a pressurized polymerization kettle, inert gas is firstly introduced for purging, then the inert gas atmosphere is maintained, the pressure is increased to 0.5-1Mpa, the temperature is increased to 400-.
Wherein, in the step (7), the temperature rise is gradient temperature rise, and includes: the temperature is raised from room temperature to 300 ℃ at a temperature raising rate of 4-6 ℃/min (preferably 5 ℃/min), and then from 300 ℃ to 400-440 ℃ at a temperature raising rate of 1-2 ℃/min.
Wherein, in the step (7), the stirring is started when the asphalt is heated to more than 100 ℃, and the stirring speed is 100-150 rmp.
Wherein, in the step (5) or (7), the inert gas is selected from one or more of nitrogen, helium and argon.
The invention provides the mesophase pitch prepared by the preparation method of the mesophase pitch.
Wherein the mesophase pitch optical structure is a streamline wide-area structure; the mesophase pitch content is 100%; the softening point is lower and is 300-320 ℃; the aromatic degree is higher, the high-temperature viscosity after melting is low, the rheological property is excellent, and the aromatic polycarbonate can be used as an excellent raw material for preparing carbon materials such as high-quality needle coke, carbon foam and the like.
The invention has the following beneficial technical effects:
1. the invention utilizes biomass asphalt mixed with coal tar asphalt as a raw material to prepare mesophase asphalt, the biomass asphalt is residue obtained by pyrolyzing biomass materials at high temperature, the biomass materials comprise tree sawdust, crop straws and the like, and the mesophase asphalt has the advantages of reproducibility, low cost, low nitrogen, low sulfur, sufficient global supply and the like, and the invention realizes the effective utilization of the biomass asphalt.
2. According to the invention, the biomass pitch is mixed with the coal tar pitch, the composition of the mixed pitch and the proportion of C, H, O, N, S element content are adjusted after refining, and the mesophase pitch with excellent performance is prepared. The biomass asphalt has the characteristics of small molecular weight, high hydrogen content, low heteroatom content and the like, so that the defects of low hydrogen content and high N, S heteroatom content in the coal asphalt are overcome, and a naphthenic structure can be introduced in the polymerization process of the mixed asphalt. The low impurity content can also effectively adjust the composition and the structure of the asphalt and reduce the influence of the dipole moment of the heteroatom-containing compound on the viscosity of the system. Under the condition of high-temperature co-carbonization, the system viscosity of the mesophase pitch is reduced, the system fluidity is enhanced, and the generated mesophase structure develops more orderly. The prepared mesophase pitch can be used as an excellent raw material for preparing high-quality carbon materials such as needle coke, carbon foam and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
a) The aromatic hydrocarbon solvent is washing oil, the aliphatic hydrocarbon solvent is kerosene, and the aromatic hydrocarbon solvent and the aliphatic hydrocarbon solvent are mixed according to the weight ratio of 0.25:1 to prepare the mixed solvent.
b) And (3) filtering the biomass asphalt in a centrifugal filter, and separating out the filtered biomass asphalt. And mixing the filtered biomass pitch and the coal tar pitch according to the weight ratio of 0.1:1 to prepare the mixed pitch.
c) Mixing the mixed asphalt and the mixed solvent according to the weight ratio of 1:3, placing the mixture in a pressure separation kettle, introducing nitrogen, controlling the pressure in the kettle to be 0.5Mpa, heating to 130 ℃, controlling the temperature to be in a condition of stirring and reacting for 1h, and standing and settling for 2h at constant temperature and constant pressure.
d) And (3) carrying out reduced pressure distillation on the upper layer solution after standing and settling, and recovering the solvent to obtain the refined mixed asphalt, wherein the recovery rate of the solvent can reach more than 90%.
e) And (2) putting 30g of refined mixed asphalt into a pressurized polymerization kettle, blowing nitrogen, introducing nitrogen again, adjusting the pressure in the kettle to 0.5MPa, heating the kettle to 300 ℃ from room temperature at the heating rate of 5 ℃/min, heating the kettle to 410 ℃ at the heating rate of 1 ℃/min, performing carbonization thermal polycondensation for 4 hours, and naturally cooling to obtain the mesophase asphalt.
The content of quinoline insoluble in the refined mixed pitch obtained after removal of the quinoline insoluble was controlled to 0.04 wt%, the H/C atomic ratio of the refined mixed pitch was 0.055%, the proportion of n-Hexane Soluble (HS) was 16.68 wt%, the proportion of n-hexane insoluble toluene soluble (HI-TS) was 69.85 wt%, and the proportion of toluene insoluble quinoline soluble (TI-QS) was 13.43 wt%.
The optical structure of the mesophase pitch was a streamline wide area structure measured by a polarization microscope, the mesophase content was 100%, the content of C, H, N, S, O of the mesophase pitch was 91.61 wt.%, 5.06 wt.%, 1.09 wt.%, 1.21 wt.% and 1.03 wt.%, respectively, as measured by an element analyzer, the atomic ratio of H/C was 0.523, the aromaticity index of the mesophase pitch was 0.494 as measured by a fourier transform infrared spectrometer, and the softening point of the mesophase pitch was 327.6 ℃ as measured by a thermomechanical analyzer, and the viscosity at 410 ℃ was 12.81 mpa.s. The high-temperature viscosity after melting is low, the rheological property is excellent, and the high-temperature melt-processed high-viscosity carbon can be used as an excellent raw material for preparing carbon materials such as high-quality needle coke, foam carbon and the like.
Example 2
a) The aromatic hydrocarbon solvent is washing oil, the aliphatic hydrocarbon solvent is kerosene, and the aromatic hydrocarbon solvent and the aliphatic hydrocarbon solvent are mixed according to the weight ratio of 0.25:1 to prepare the mixed solvent.
b) And (3) filtering the biomass asphalt in a centrifugal filter, and separating out the filtered biomass asphalt. And mixing the filtered biomass pitch and the coal tar pitch according to the weight ratio of 0.15:1 to prepare the mixed pitch.
c) Mixing the mixed asphalt and the mixed solvent according to the weight ratio of 1:3, placing the mixture in a pressure separation kettle, introducing nitrogen, controlling the pressure in the kettle to be 0.5Mpa, heating to 130 ℃, controlling the temperature to be in a condition of stirring and reacting for 1h, and standing and settling for 2h at constant temperature and constant pressure.
d) And (3) carrying out reduced pressure distillation on the upper layer solution after standing and settling, and recovering the solvent to obtain the refined mixed asphalt, wherein the recovery rate of the solvent can reach more than 90%.
e) And (2) putting 30g of refined mixed asphalt into a pressurized polymerization kettle, blowing nitrogen, introducing nitrogen again, adjusting the pressure in the kettle to 0.5MPa, heating the kettle to 300 ℃ from room temperature at the heating rate of 5 ℃/min, heating the kettle to 410 ℃ at the heating rate of 1 ℃/min, performing carbonization thermal polycondensation for 4 hours, and naturally cooling to obtain the mesophase asphalt.
The content of quinoline insoluble in the refined mixed pitch obtained after removal of the quinoline insoluble was controlled to 0.06 wt%, the H/C atomic ratio of the refined mixed pitch was 0.056 wt%, the proportion of n-Hexane Soluble (HS) was 15.39 wt%, the proportion of n-hexane insoluble toluene soluble (HI-TS) was 73.63 wt%, and the proportion of toluene insoluble quinoline soluble (TI-QS) was 10.92 wt%.
The optical structure of the mesophase pitch was measured to be a streamline wide area structure by a polarizing microscope, the mesophase content was 100%, the content of C, H, N, S, O of the mesophase pitch was measured to be 92.98 wt.%, 4.15 wt.%, 0.98 wt.%, 0.76 wt.% and 1.13 wt.% by an element analyzer, the atomic ratio of H/C was 0.536, the aromaticity index of the mesophase pitch was measured to be 0.492 by a fourier transform infrared spectrometer, and the softening point of the mesophase pitch was measured to be 321.2 ℃ by a thermomechanical analyzer, and the viscosity at 410 ℃ was 17.12 mpa.s. The high-temperature viscosity after melting is low, the rheological property is excellent, and the high-temperature melt-processed high-viscosity carbon can be used as an excellent raw material for preparing carbon materials such as high-quality needle coke, foam carbon and the like.
Example 3
a) The aromatic hydrocarbon solvent is washing oil, the aliphatic hydrocarbon solvent is kerosene, and the aromatic hydrocarbon solvent and the aliphatic hydrocarbon solvent are mixed according to the weight ratio of 0.25:1 to prepare the mixed solvent.
b) And (3) filtering the biomass asphalt in a centrifugal filter, and separating out the filtered biomass asphalt. And mixing the filtered biomass pitch and the coal tar pitch according to the weight ratio of 0.2:1 to prepare the mixed pitch.
c) Mixing the mixed asphalt and the mixed solvent according to the weight ratio of 1:3, placing the mixture in a pressure separation kettle, introducing nitrogen, controlling the pressure in the kettle to be 0.5Mpa, heating to 130 ℃, controlling the temperature to be in a condition of stirring and reacting for 1h, and standing and settling for 2h at constant temperature and constant pressure.
d) And (3) carrying out reduced pressure distillation on the upper layer solution after standing and settling, and recovering the solvent to obtain the refined mixed asphalt, wherein the recovery rate of the solvent can reach more than 90%.
e) And (2) putting 30g of refined mixed asphalt into a pressurized polymerization kettle, blowing nitrogen, introducing nitrogen again, adjusting the pressure in the kettle to 0.5MPa, heating the kettle to 300 ℃ from room temperature at the heating rate of 5 ℃/min, heating the kettle to 410 ℃ at the heating rate of 1 ℃/min, performing carbonization thermal polycondensation for 4 hours, and naturally cooling to obtain the mesophase asphalt.
The content of quinoline insoluble in the refined mixed pitch obtained after removal of the quinoline insoluble was controlled to 0.07 wt%, the H/C atomic ratio of the refined mixed pitch was 0.061%, the proportion of n-Hexane Soluble (HS) was 20.26 wt%, the proportion of n-hexane insoluble toluene soluble (HI-TS) was 71.16 wt%, and the proportion of toluene insoluble quinoline soluble (TI-QS) was 8.51 wt%.
The optical structure of the mesophase pitch was a streamline wide area structure measured with a polarizing microscope, the mesophase content was 100%, the content of C, H, N, S, O of the mesophase pitch was 91.69 wt.%, 4.44 wt.%, 1.02 wt.%, 0.63 wt.% and 2.22 wt.%, respectively, as measured with an element analyzer, and the H/C atomic ratio was 0.581, the aromaticity index of the mesophase pitch was 0.488 as measured with a fourier transform infrared spectrometer, and the softening point of the mesophase pitch was 301.6 ℃ as measured with a thermomechanical analyzer, and the viscosity was 12.48mpa.s at 410 ℃. The high-temperature viscosity after melting is low, the rheological property is excellent, and the high-temperature melt-processed high-viscosity carbon can be used as an excellent raw material for preparing carbon materials such as high-quality needle coke, foam carbon and the like.
Comparative example 1
Same as in embodiment 1, except that: in the step b), biomass pitch is not added to prepare mixed pitch, and in the step c), only coal tar pitch is adopted to be mixed with the mixed solvent.
After quinoline insoluble substances are removed, the content of quinoline insoluble substances in the coal tar pitch is controlled to be 0.08 wt%, the H/C atomic ratio of the refined mixed pitch is 0.048%, the proportion of n-hexane soluble substances (HS) is 43.21 wt%, the proportion of n-hexane insoluble toluene soluble substances (HI-TS) is 48.28 wt%, and the proportion of toluene insoluble quinoline soluble substances (TI-QS) is 8.51 wt%.
The optical structure of the mesophase pitch was a streamline wide area structure measured by a polarizing microscope, the mesophase content was 100%, the content of C, H, N, S, O in the mesophase pitch was 94.48 wt.%, 3.70 wt.%, 1.15 wt.%, 0.89 wt.% and 0.31 wt.%, respectively, as measured by an elemental analyzer, the atomic ratio of H/C was 0.470, the aromaticity index of the mesophase pitch was 0.502 as measured by a fourier transform infrared spectrometer, the softening point of the mesophase pitch was 334.3 ℃ as measured by a thermomechanical analyzer, and the viscosity at 410 ℃ was 136.51 mpa.s.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A method of producing mesophase pitch comprising:
(1) placing the biomass asphalt in a centrifugal filter for centrifugal filtration to obtain filtered biomass asphalt;
(2) preparing a mixed solvent: mixing an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent according to a certain weight ratio to prepare a mixed solvent;
(3) preparing mixed asphalt: mixing the filtered biomass pitch obtained in the step (1) with coal tar pitch according to a certain weight ratio to prepare mixed pitch;
(4) mixing the mixed asphalt obtained in the step (3) and the mixed solvent obtained in the step (2) according to a certain weight ratio, and placing the mixture in a pressure separation kettle;
(5) introducing inert gas into the pressure separation kettle for purging, keeping the pressure of the inert gas atmosphere increased to 0.5-1Mpa, heating to 120-;
(6) taking out the upper layer solution after standing and settling in the pressure separation kettle, placing the upper layer solution in a reduced pressure distillation device for reduced pressure distillation, and recovering the solvent to obtain refined mixed asphalt;
(7) and (4) placing the refined mixed asphalt obtained in the step (6) into a pressurized polymerization kettle, raising the pressure and the temperature under the inert gas atmosphere, and keeping the temperature and the pressure constant for a period of time to perform a co-carbonization thermal polycondensation reaction to obtain the mesophase asphalt.
2. The process for producing mesophase pitch according to claim 1, wherein in the step (2), the aromatic hydrocarbon solvent is wash oil, and the aliphatic hydrocarbon solvent is kerosene.
3. The process for producing mesophase pitch according to claim 1, wherein in the step (2), the weight ratio of the aromatic hydrocarbon solvent to the aliphatic hydrocarbon solvent is 0.2 to 0.4: 1.
4. The method for preparing mesophase pitch according to claim 1, wherein the weight ratio of biomass pitch to coal tar pitch in step (3) is 0.1-0.2: 1.
5. The process for producing mesophase pitch according to claim 1, wherein in the step (4), the weight ratio of the mixed pitch to the mixed solvent is 1:2 to 4.
6. The process for preparing mesophase pitch as claimed in claim 1, wherein, in the step (6), the removal of quinoline insolubles is carried out by removing quinoline insolubles using a pressurized separation vessel to obtain refined mixed pitch, wherein the extraction pressure is 0.5-1MPa and the extraction temperature is 120-140 ℃.
7. The process for producing mesophase pitch according to claim 1, wherein the quinoline insoluble content in the refined mixed pitch obtained in the step (6) is 0.1% by weight or less.
8. The method for preparing mesophase pitch as defined in claim 1, wherein in the step (7), the refined mixed pitch is placed in a pressurized polymerization vessel, an inert gas is introduced for purging, then the inert gas atmosphere is maintained, the pressure is increased to 0.5-1Mpa, the temperature is raised to 400-440 ℃, and then the constant temperature and pressure are maintained for 4-6h to perform the co-carbonization thermal polycondensation reaction, thereby obtaining the mesophase pitch.
9. The method for producing mesophase pitch according to claim 1, wherein the temperature increase in the step (7) is a gradient temperature increase comprising: the temperature is raised from room temperature to 300 ℃ at a heating rate of 4-6 ℃/min, and then from 300 ℃ to 400-440 ℃ at a heating rate of 1-2 ℃/min.
10. Mesophase pitch produced by the process for producing mesophase pitch according to claims 1 to 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115029801A (en) * | 2022-06-13 | 2022-09-09 | 中国科学院山西煤炭化学研究所 | Method and device for high-temperature centrifugal filtration continuous spinning of spinnable asphalt |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2970039A1 (en) * | 2013-03-15 | 2016-01-20 | Pinova, Inc. | Asphalt emulsifiers derived from pyrolyzed wood |
| JP2017179072A (en) * | 2016-03-29 | 2017-10-05 | 日工株式会社 | Apparatus for carbonization of woody biomass |
| CN107312561A (en) * | 2017-07-17 | 2017-11-03 | 青岛科技大学 | A kind of method that FCC clarified oils hydro-upgrading Co carbonization prepares mesophase pitch |
| CN110256858A (en) * | 2019-06-12 | 2019-09-20 | 台州立拓能源有限公司 | Application of the bio-oil as pitch |
-
2021
- 2021-12-02 CN CN202111458090.5A patent/CN114164014A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2970039A1 (en) * | 2013-03-15 | 2016-01-20 | Pinova, Inc. | Asphalt emulsifiers derived from pyrolyzed wood |
| JP2017179072A (en) * | 2016-03-29 | 2017-10-05 | 日工株式会社 | Apparatus for carbonization of woody biomass |
| CN107312561A (en) * | 2017-07-17 | 2017-11-03 | 青岛科技大学 | A kind of method that FCC clarified oils hydro-upgrading Co carbonization prepares mesophase pitch |
| CN110256858A (en) * | 2019-06-12 | 2019-09-20 | 台州立拓能源有限公司 | Application of the bio-oil as pitch |
Non-Patent Citations (2)
| Title |
|---|
| LI, L ET AL.: "Characteristics of the mesophase and needle coke derived from the blended coal tar and biomass tar pitch", 《JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS》 * |
| 郝建生: "煤焦油沥青改质生产碳材料", 《科技情报开发与经济》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115029801A (en) * | 2022-06-13 | 2022-09-09 | 中国科学院山西煤炭化学研究所 | Method and device for high-temperature centrifugal filtration continuous spinning of spinnable asphalt |
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Application publication date: 20220311 |