CN115404092B - Method and device for continuously preparing mesophase pitch - Google Patents
Method and device for continuously preparing mesophase pitch Download PDFInfo
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- CN115404092B CN115404092B CN202211176535.5A CN202211176535A CN115404092B CN 115404092 B CN115404092 B CN 115404092B CN 202211176535 A CN202211176535 A CN 202211176535A CN 115404092 B CN115404092 B CN 115404092B
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- melt pump
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- 239000011302 mesophase pitch Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 65
- 239000010426 asphalt Substances 0.000 claims abstract description 19
- 239000011301 petroleum pitch Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000011300 coal pitch Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000003245 coal Substances 0.000 claims abstract description 3
- 239000003208 petroleum Substances 0.000 claims abstract 2
- 238000001704 evaporation Methods 0.000 claims description 25
- 230000008020 evaporation Effects 0.000 claims description 25
- 238000004821 distillation Methods 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical group C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000000155 melt Substances 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000007701 flash-distillation Methods 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000011318 synthetic pitch Substances 0.000 abstract 1
- 239000011294 coal tar pitch Substances 0.000 description 7
- 239000011317 mixed pitch Substances 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 239000000852 hydrogen donor Substances 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- C10C3/06—Working-up pitch, asphalt, bitumen by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (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 and a device for continuously preparing mesophase pitch, and belongs to the technical field of synthetic pitch preparation methods. Aiming at the problem of large back mixing of a conventional kettle reactor, the device for continuously preparing the mesophase pitch is designed and comprises: mixing kettle, tubular reactor, flash distillation kettle, constant pressure system, make-up machine. The crushed refined coal asphalt and petroleum asphalt are mixed in proportion in a melting way, the mixture is reacted for a certain time by a melt pump through a tubular reactor, then the light component is flashed, then the hydrogen-supplying solvent is quantitatively added, the mixture is continuously reacted for a certain time by the melt pump through the tubular reactor, then the light component is flashed, and the intermediate phase asphalt is prepared after molding. The invention adopts the tubular reactor to carbonize the refined coal pitch and petroleum pitch, the whole reaction system has no back mixing, the temperature can be controlled in a segmented way, the heat efficiency is high, and the spinnable mesophase pitch with uniform molecular weight distribution, good flow property and moderate softening point can be continuously prepared.
Description
Technical Field
The invention belongs to the technical field of synthetic asphalt preparation methods, and particularly relates to a method and a device for continuously preparing mesophase asphalt.
Background
The high-performance asphalt carbon fiber has excellent performances of high strength, high modulus, high temperature resistance, corrosion resistance, fatigue resistance, electric conduction, heat conduction and the like, is an indispensable engineering material in the aerospace industry, and is widely applied to traffic, machinery, sports and entertainment.
The production of high-performance asphalt carbon fiber involves five process units, namely raw material refining, thermal polycondensation, melt spinning, pre-oxidation and carbonization/graphitization. The preparation of mesophase spinnable pitch by thermal polycondensation is a key step in the preparation of pitch carbon fibers. It is generally believed that superior mesophase structure is required to have better molecular planarity of the aromatic rings, contain some short alkyl and cycloalkyl structures and a concentrated molecular weight distribution. The viscosity of the system is low in the polycondensation process, so that the growth, flow and fusion of the mesophase liquid crystal are ensured, and the polycondensation reaction system is required to be carried out moderately in order to avoid the formation of excessive infusible asphalt molecules. Mesophase pitch is typically prepared by catalytic polymerization, hydromodified polymerization, and co-carbonization. Catalytic polymerization typically uses a Lewis acid metal catalyst and HF/BF3. The metal catalyst (AlCl 3 of Japanese patent laid-open No. 61-83317) remains in the spinnable pitch, is difficult to completely remove, and has a great influence on the performance of the final carbon fiber; the HF/BF3 catalyst (Japanese patent laid-open No. 1-139621, japanese patent laid-open No. 1-254796,CN200910064562,CN 106497591 B,CN 106350088B) reaction system is extremely corrosive to equipment and requires higher equipment. The hydrogenation modification polymerization needs to introduce the aliphatic hydrogen and the naphthene structure into the raw material asphalt molecules under the action of a Ni-Mo-Al2O3 catalyst at high temperature and high pressure (hydrogenated coal asphalt-based carbon fiber preparation and performance research, wang Yuanhua, doctor's treatises), but the operation pressure is up to 16MPa, and higher requirements are also put forward on equipment. Co-carbonization is an ideal method for preparing mesophase pitch, and by polymerizing, the fat structure in petroleum pitch is introduced into the high aromatic ring structure of coal pitch, thereby preparing mesophase pitch with excellent performance. (Guo J, et al, energy Fuels2020,34, 6474-6482). However, a kettle type reactor is generally used for preparing the mesophase pitch, so that back mixing is large, and polymerization reaction between small molecules and between large molecules is easy to occur, so that the molecular weight distribution of the produced mesophase pitch is wide, and the performance of the mesophase pitch is influenced.
Disclosure of Invention
Aiming at the problem of large back mixing of a conventional kettle type reactor, the invention provides a method and a device for continuously preparing mesophase pitch.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
An apparatus for continuously preparing mesophase pitch comprising: mixing kettle, tubular reactor, flash evaporation kettle, constant pressure system and forming machine;
The mixing kettles comprise a first mixing kettle and a second mixing kettle; the tubular reactor comprises a first tubular reactor and a second tubular reactor; the flash evaporation kettle comprises a first flash evaporation kettle and a second flash evaporation kettle; the constant pressure system comprises a first constant pressure system and a second constant pressure system;
The first mixing kettle is provided with a first magnetic stirrer, a heater is arranged on the outer side of the first mixing kettle, a first feeding hole and a second feeding hole are formed in the top end of the first mixing kettle, and a first discharging hole is formed in the bottom end of the first mixing kettle; the second mixing kettle is provided with a second magnetic stirrer, a heater is arranged on the outer side of the second mixing kettle, a third feeding system is arranged at the top end of the second mixing kettle, and a third discharge hole is arranged at the bottom end of the second mixing kettle; the outer sides of the first tubular reactor and the second tubular reactor are respectively provided with a heater, a heat conduction filler is arranged in the middle of the tube array, and the filler is a graphite particle or aluminum particle heat conductor; the outer sides of the first flash evaporation kettle and the second flash evaporation kettle are respectively provided with a heater, the top end of the first flash evaporation kettle and the second flash evaporation kettle are respectively provided with a first distillation outlet and a second distillation outlet, and the bottom end of the first flash evaporation kettle and the second flash evaporation kettle are respectively provided with a second discharge outlet and a fourth discharge outlet;
The first discharge port is connected with the inlet of the first melt pump through a valve, and the outlet of the first melt pump is connected with the inlet of the first tubular reactor; the outlet of the first tubular reactor is connected with a first flash kettle through a first constant pressure system, and the first distillation outlet is connected with a first vacuum pump through a valve; the second discharge port is connected with a second melt pump inlet through a one-way valve and a stainless steel pipe, and a second melt pump outlet is connected with a second mixing kettle; the third discharge port is connected with a third melt pump inlet through a valve, and the third melt pump outlet is connected with the inlet of the second tubular reactor; the outlet of the second tubular reactor is connected with a second flash evaporation kettle through a second constant pressure system, and the second distillation outlet is connected with a second vacuum pump through a valve; the fourth discharge hole is connected with the inlet of a fourth melt pump through a one-way valve and a stainless steel pipe, and the outlet of the fourth melt pump is connected with the forming machine.
The method for preparing the mesophase pitch by using the continuous mesophase pitch preparation device comprises the following steps:
Step 1, preparation of a sample: respectively crushing the refined coal pitch and the petroleum pitch on a crusher to be less than or equal to 60 meshes;
Step 2, adding crushed samples into a first mixing kettle through a first feed inlet and a second feed inlet in proportion, simultaneously starting an external heater of the first mixing kettle, starting a first magnetic stirrer, and simultaneously setting the flow rates of a first melt pump and a second melt pump, the temperatures of a first tubular reactor and a second tubular reactor, the temperatures of a first flash evaporation kettle and a second flash evaporation kettle, the pressures of a first constant pressure system and a second constant pressure system and the temperature of a forming machine; after mixing for a certain time, opening a first melt pump, and when the mixed asphalt reaches the outlet of the first tubular reactor through the flow rate of the first melt pump, the length and the pipe diameter of the first tubular reactor, opening a first vacuum pump and a second melt pump; and simultaneously setting the flow of a third feeding system, adding hydrogen-supplying solvent by the third feeding system, and simultaneously opening a third melt pump, a second vacuum pump, a fourth melt pump and a forming machine.
And 3, obtaining the product at the outlet of the forming machine, namely the mesophase pitch.
Further, the working temperatures of the first mixing kettle and the second mixing kettle are 160-180 ℃ and 420-450 ℃ respectively.
Further, the rotating speeds of the first magnetic stirrer and the second magnetic stirrer are 150-200 revolutions per minute.
Further, the working temperatures of the first tubular reactor and the second tubular reactor are 420-450 ℃ and 400-420 ℃ respectively, and the temperature of the forming machine is 320-350 ℃.
Further, the set pressures of the first low pressure system and the second low pressure system are 3-5 MPa and 2-3 MPa respectively.
Further, the mixing ratio of the crushed coal tar pitch to the crushed petroleum pitch is 1:1-3:1.
Further, the hydrogen-supplying solvent is tetrahydronaphthalene, and the addition amount is 5-10% of the flux of the melt pump outlet asphalt.
Further, the residence time of the mixed asphalt in the first tubular reactor is 6-8 h, and the residence time in the second tubular reactor is 4-6 h.
Further, the lengths of the first tubular reactor and the second tubular reactor are 80m, and the pipe diameters are 50mm.
Compared with the prior art, the invention has the following advantages:
The method and the device for continuously preparing the mesophase pitch solve the problem of large back mixing of a conventional kettle type reactor by adopting a tubular reactor plug flow mode, can continuously feed and discharge materials, greatly improve the production efficiency, have uniform temperature of the whole reaction system, and realize the preparation of the spinnable mesophase pitch with uniform molecular weight distribution, moderate softening point and good flow property on one set of instrument.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing mesophase pitch according to the present invention;
FIG. 2 is a molecular weight distribution diagram of mesophase pitch prepared in accordance with the present invention;
FIG. 3 is a graph of flow properties of mesophase pitch made in accordance with the present invention.
Reference numerals: 1. a first magnetic stirrer; 2. a first feed port; 3. a first mixing kettle; 4. a first discharge port; 5. a first melt pump; 6. a second melt pump; 7. a second mixing kettle; 8. a third melt pump; 9. a second feed inlet; 10. a first tubular reactor; 11. a first compression system; 12. a first vacuum pump; 13. a first distillation outlet; 14. a first flash tank; 15. a second discharge port; 16. a first one-way valve; 17. a second magnetic stirrer; 18. a feed system; 19. a third discharge port; 20. a second tubular reactor; 21. a second constant pressure system; 22. a second vacuum pump; 23. a second distillation outlet; 24. a second flash tank; 25. a fourth discharge port; 26. a fourth melt pump; 27. a molding machine; 28. and a second one-way valve.
Detailed Description
Example 1
An apparatus for continuously preparing mesophase pitch comprising: mixing kettle, tubular reactor, flash kettle, constant pressure system, forming machine 27;
The mixing kettles comprise a first mixing kettle 3 and a second mixing kettle 7; the tubular reactors include a first tubular reactor 10 and a second tubular reactor 20; the flash tank includes a first flash tank 14 and a second flash tank 24; the constant pressure system comprises a first constant pressure system 11 and a second constant pressure system 21;
The first mixing kettle 3 is provided with a first magnetic stirrer 1, a heater is arranged on the outer side of the first mixing kettle, a first feed inlet 2 and a second feed inlet 9 are arranged at the top end of the first mixing kettle, and a first discharge outlet 4 is arranged at the bottom end of the first mixing kettle; the second mixing kettle 7 is provided with a second magnetic stirrer 17, a heater is arranged on the outer side of the second mixing kettle, a third feeding system 18 is arranged at the top end of the second mixing kettle, and a third discharge port 19 is arranged at the bottom end of the second mixing kettle; the outside of the first tubular reactor 10 and the outside of the second tubular reactor 20 are respectively provided with a heater, a heat conduction filler is arranged in the middle of the tube array, and the filler is a graphite particle or aluminum particle heat conductor; the outer sides of the first flash evaporation kettle 14 and the second flash evaporation kettle 24 are respectively provided with a heater, the top end is respectively provided with a first distillation outlet 13 and a second distillation outlet 23, and the bottom end is respectively provided with a second discharge outlet 15 and a fourth discharge outlet 25;
The first discharge port 4 is connected with the inlet of a first melt pump 5 through a valve, and the outlet of the first melt pump 5 is connected with the inlet of a first tubular reactor 10; the outlet of the first tubular reactor 10 is connected with a first flash kettle 14 through a first pressure system 11, and the first distillation outlet 13 is connected with a first vacuum pump 12 through a valve; the second discharge port 15 is connected with the inlet of the second melt pump 6 through a one-way valve 16 and a stainless steel pipe, and the outlet of the second melt pump 6 is connected with the second mixing kettle 7; the third discharge port 19 is connected with the inlet of the third melt pump 8 through a valve, and the outlet of the third melt pump 8 is connected with the inlet of the second tubular reactor 20; the outlet of the second tubular reactor 20 is connected with a second flash evaporation kettle 24 through a second constant pressure system 21, and the second distillation outlet 23 is connected with a second vacuum pump 22 through a valve; the fourth discharge port 25 is connected with the inlet of a fourth melt pump 26 through a one-way valve 28 and a stainless steel pipe, and the outlet of the fourth melt pump 26 is connected with a forming machine 27.
Example 2
The reaction device of the example 1 is connected in the mode shown in figure 1, and refined coal pitch and petroleum pitch are crushed on a crusher to be less than or equal to 60 meshes;
Continuously adding crushed samples into a first mixing kettle 3 according to the ratio of coal tar pitch to petroleum pitch (weight ratio) of 1:1 through a first feed inlet 2 and a second feed inlet 9 respectively, simultaneously starting an external heater of the first mixing kettle 3, setting the temperature to 160 ℃, starting a first magnetic stirrer 1, setting the rotating speed to 150 revolutions per minute, simultaneously starting a first melt pump 5, setting the flow rate to ensure that the residence time of the crushed samples in a tubular reactor with the diameter of 50mm and the length of 80m is 6h, simultaneously starting heaters of a first tubular reactor 10 and a second tubular reactor 20, setting the temperature to 450 ℃ and 420 ℃, starting heaters of a first flash kettle 14 and a second flash kettle 24, setting the temperature to 420 ℃ and 400 ℃ respectively, setting the vacuum degree to-0.09 MPa (gauge pressure), setting the pressure of a first constant pressure system 11 and a second constant pressure system 21 to 3MPa and 2MPa respectively, and setting the temperature of a forming machine 27 to 320 ℃; after coal tar pitch and petroleum pitch are mixed at 180 ℃ for 10min, the first melt pump 5 is turned on, when the mixed pitch reaches the outlet of the first tubular reactor 10, the second melt pump 6 and the third melt pump 8 are turned on, the flow rate is set so that the residence time of the mixed pitch in the second tubular reactor 20 with the diameter of 60mm and the length of 80m is 4h, meanwhile, the third feeding system 18 is turned on, the hydrogen donor tetrahydronaphthalene is added according to 5% of the flow rate of the second melt pump 6, when the mixture reaches the outlet of the second tubular reactor 20, the fourth melt pump 26 and the forming machine 27 are turned on, and the product at the outlet of the forming machine 27 is mesophase pitch with the softening point of 270 ℃.
Example 3
The reaction device of the example 1 is connected in the mode shown in figure 1, and refined coal pitch and petroleum pitch are crushed on a crusher to be less than or equal to 60 meshes;
Continuously adding crushed samples into a first mixing kettle 3 according to the ratio of coal tar pitch to petroleum pitch (weight ratio) of 2:1 through a first feed inlet 2 and a second feed inlet 9 respectively, simultaneously starting an external heater of the first mixing kettle 3, setting the temperature to 180 ℃, starting a first magnetic stirrer 1, setting the rotating speed to 170 revolutions per minute, simultaneously starting a first melt pump 5, setting the flow rate to ensure that the residence time of the crushed samples in a tubular reactor with the diameter of 60mm and the length of 80m is 7h, simultaneously starting heaters of a first tubular reactor 10 and a second tubular reactor 20, setting the temperature to 430 ℃ and 400 ℃, starting heaters of a first flash kettle 14 and a second flash kettle 24, setting the temperature to 400 ℃ and 380 ℃ respectively, setting the vacuum degree to-0.09 MPa (gauge pressure), setting the pressure of a first constant pressure system 11 and a second constant pressure system 21 to 5MPa and 3MPa respectively, and setting the temperature of a forming machine 27 to 350 ℃; after coal tar pitch and petroleum pitch are mixed at 180 ℃ for 10min, the first melt pump 5 is turned on, when the mixed pitch reaches the outlet of the first tubular reactor 10, the second melt pump 6 and the third melt pump 8 are turned on, the flow rate is set so that the residence time of the mixed pitch in the second tubular reactor 20 with the diameter of 60mm and the length of 80m is 5h, meanwhile, the third feeding system 18 is turned on, the hydrogen donor tetrahydronaphthalene is added according to 7% of the flow rate of the second melt pump 6, when the mixture reaches the outlet of the second tubular reactor 20, the fourth melt pump 26 and the forming machine 27 are turned on, and the product at the outlet of the forming machine 27 is mesophase pitch with the softening point of 295 ℃.
Example 4
Continuously adding crushed samples into a first mixing kettle 3 according to the ratio of coal tar pitch to petroleum pitch (weight ratio) of 3:1 through a first feed inlet 2 and a second feed inlet 9 respectively, simultaneously starting an external heater of the first mixing kettle 3, setting the temperature to 170 ℃, starting a first magnetic stirrer 1, setting the rotating speed to 200 revolutions per minute, simultaneously starting a first melt pump 5, setting the flow rate to ensure that the residence time of the crushed samples in a tubular reactor with the diameter of 60mm and the length of 80m is 8h, simultaneously starting heaters of a first tubular reactor 10 and a second tubular reactor 20, setting the temperature to 420 ℃ and 410 ℃, starting heaters of a first flash kettle 14 and a second flash kettle 24, setting the temperature to 410 ℃ and 390 ℃ respectively, setting the vacuum degree to-0.09 MPa (gauge pressure), setting the pressure of a first constant pressure system 11 and a second constant pressure system 21 to 4MPa and 2MPa respectively, and setting the temperature of a forming machine 27 to 330 ℃; after coal tar pitch and petroleum pitch are mixed at 170 ℃ for 10min, the first melt pump 5 is turned on, when the mixed pitch reaches the outlet of the first tubular reactor 10, the second melt pump 6 and the third melt pump 8 are turned on, the flow rate is set so that the residence time of the mixed pitch in the second tubular reactor 20 with the diameter of 60mm and the length of 80m is 6h, meanwhile, the third feeding system 18 is turned on, the hydrogen donor tetrahydronaphthalene is added according to 10% of the flow rate of the second melt pump 6, when the mixture reaches the outlet of the second tubular reactor 20, the fourth melt pump 26 and the forming machine 27 are turned on, and the product at the outlet of the forming machine 27 is mesophase pitch with the softening point of 280 ℃.
What is not described in detail in the present specification belongs to the prior art known to those skilled in the art. While the foregoing describes illustrative embodiments of the present invention to facilitate an understanding of the present invention by those skilled in the art, it should be understood that the present invention is not limited to the scope of the embodiments, but is to be construed as protected by the accompanying claims insofar as various changes are within the spirit and scope of the present invention as defined and defined by the appended claims.
Claims (10)
1. An apparatus for continuously preparing mesophase pitch, characterized in that: comprising the following steps: a mixing kettle, a tubular reactor, a flash evaporation kettle, a constant pressure system and a forming machine (27);
The mixing kettle comprises a first mixing kettle (3) and a second mixing kettle (7); the tubular reactor comprises a first tubular reactor (10) and a second tubular reactor (20); the flash evaporation kettle comprises a first flash evaporation kettle (14) and a second flash evaporation kettle (24); the constant pressure system comprises a first constant pressure system (11) and a second constant pressure system (21);
The first mixing kettle (3) is provided with a first magnetic stirrer (1), a heater is arranged on the outer side of the first mixing kettle, a first feed inlet (2) and a second feed inlet (9) are arranged at the top end of the first mixing kettle, and a first discharge outlet (4) is arranged at the bottom end of the first mixing kettle; the second mixing kettle (7) is provided with a second magnetic stirrer (17), a heater is arranged on the outer side of the second mixing kettle, a third feeding system (18) is arranged at the top end of the second mixing kettle, and a third discharge hole (19) is arranged at the bottom end of the second mixing kettle; the outer sides of the first tubular reactor (10) and the second tubular reactor (20) are respectively provided with a heater, a heat-conducting filler is arranged in the middle of the tube array, and the filler is a graphite particle or aluminum particle heat conductor; heaters are arranged on the outer sides of the first flash evaporation kettle (14) and the second flash evaporation kettle (24), a first distillation outlet (13) and a second distillation outlet (23) are respectively arranged at the top end of the first flash evaporation kettle, and a second discharge outlet (15) and a fourth discharge outlet (25) are respectively arranged at the bottom end of the first flash evaporation kettle;
The first discharge port (4) is connected with the inlet of the first melt pump (5) through a valve, and the outlet of the first melt pump (5) is connected with the inlet of the first tubular reactor (10); the outlet of the first tubular reactor (10) is connected with a first flash kettle (14) through a first constant pressure system (11), and the first distillation outlet (13) is connected with a first vacuum pump (12) through a valve; the second discharge port (15) is connected with the inlet of a second melt pump (6) through a one-way valve (16) and a stainless steel pipe, and the outlet of the second melt pump (6) is connected with a second mixing kettle (7); the third discharge hole (19) is connected with the inlet of a third melt pump (8) through a valve, and the outlet of the third melt pump (8) is connected with the inlet of a second tubular reactor (20); the outlet of the second tubular reactor (20) is connected with a second flash evaporation kettle (24) through a second constant pressure system (21), and the second distillation outlet (23) is connected with a second vacuum pump (22) through a valve; the fourth discharge hole (25) is connected with the inlet of a fourth melt pump (26) through a one-way valve (28) and a stainless steel pipe, and the outlet of the fourth melt pump (26) is connected with a forming machine (27).
2. A method for continuously preparing mesophase pitch using an apparatus for continuously preparing mesophase pitch as set forth in claim 1, which is characterized in that: the method comprises the following steps:
Step 1, preparation of a sample: respectively crushing the refined coal pitch and the petroleum pitch on a crusher to be less than or equal to 60 meshes;
Step 2, adding crushed samples into a first mixing kettle (3) through a first feed inlet (2) and a second feed inlet (9) in proportion, simultaneously starting an external heater of the first mixing kettle (3), starting a first magnetic stirrer (1), and simultaneously setting the flow of a first melt pump (5) and a second melt pump (6), the temperatures of a first tubular reactor (10) and a second tubular reactor (20), the temperatures of a first flash kettle (14) and a second flash kettle (24), the pressures of a first constant pressure system (11) and a second constant pressure system (21) and the temperature of a forming machine (27); after mixing for a certain time, opening a first melt pump (5), and when the mixed asphalt reaches the outlet of the first tubular reactor (10) through the flow of the first melt pump (5), the length and the pipe diameter of the first tubular reactor (10), opening a first vacuum pump (12) and a second melt pump (6); simultaneously setting the flow rate of a third feeding system (18), adding hydrogen-supplying solvent by the third feeding system (18), and simultaneously opening a third melt pump (8), a second vacuum pump (22), a fourth melt pump (26) and a forming machine (27);
And 3, obtaining the product at the outlet of the forming machine (27) which is the mesophase pitch.
3. The method for continuously preparing mesophase pitch as claimed in claim 2, wherein: the working temperatures of the first mixing kettle (3) and the second mixing kettle (7) are 160-180 ℃ and 420-450 ℃ respectively.
4. The method for continuously preparing mesophase pitch as claimed in claim 2, wherein: the rotating speeds of the first magnetic stirrer (1) and the second magnetic stirrer (17) are 150-200 revolutions per minute.
5. The method for continuously preparing mesophase pitch as claimed in claim 2, wherein: the working temperatures of the first tubular reactor (10) and the second tubular reactor (20) are 420-450 ℃ and 400-420 ℃ respectively, and the temperature of the forming machine (27) is 320-350 ℃.
6. The method for continuously preparing mesophase pitch as claimed in claim 2, wherein: the pressure of the first constant pressure system (11) is 3-5 MPa, and the pressure of the second constant pressure system (21) is 2-3 MPa.
7. The method for continuously preparing mesophase pitch as claimed in claim 2, wherein: the mixing ratio of the crushed coal asphalt to the crushed petroleum asphalt is 1:1-3:1.
8. The method for continuously preparing mesophase pitch as claimed in claim 2, wherein: the hydrogen-supplying solvent is tetrahydronaphthalene, and the addition amount is 5-10% of the asphalt flow at the outlet of the second melt pump (6).
9. The method for continuously preparing mesophase pitch as claimed in claim 2, wherein: the residence time of the mixed asphalt in the first tubular reactor (10) is 6-8 h, and the residence time of the mixed asphalt in the second tubular reactor (20) is 4-6 h.
10. The method for continuously preparing mesophase pitch as claimed in claim 2, wherein: the lengths of the first tubular reactor (10) and the second tubular reactor (20) are 80m, and the pipe diameters are 50 mm.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103787A (en) * | 1986-05-26 | 1987-12-23 | 饭塚幸三 | The method for preparing mesophase pitch |
| CN1031556A (en) * | 1987-06-18 | 1989-03-08 | 丸善石油化学株式会社 | Preparation bituminous method |
| CN103965932A (en) * | 2014-04-30 | 2014-08-06 | 上海宝聚新化能源科技有限公司 | Treatment method for mixed asphalt as raw material for preparing needle coke |
| US9376626B1 (en) * | 2011-04-28 | 2016-06-28 | Advanced Carbon Products, LLC | Turbulent mesophase pitch process and products |
| CN113667505A (en) * | 2020-05-15 | 2021-11-19 | 中国石油化工股份有限公司 | Production method and production system of mesophase pitch |
-
2022
- 2022-09-26 CN CN202211176535.5A patent/CN115404092B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103787A (en) * | 1986-05-26 | 1987-12-23 | 饭塚幸三 | The method for preparing mesophase pitch |
| CN1031556A (en) * | 1987-06-18 | 1989-03-08 | 丸善石油化学株式会社 | Preparation bituminous method |
| US9376626B1 (en) * | 2011-04-28 | 2016-06-28 | Advanced Carbon Products, LLC | Turbulent mesophase pitch process and products |
| CN103965932A (en) * | 2014-04-30 | 2014-08-06 | 上海宝聚新化能源科技有限公司 | Treatment method for mixed asphalt as raw material for preparing needle coke |
| CN113667505A (en) * | 2020-05-15 | 2021-11-19 | 中国石油化工股份有限公司 | Production method and production system of mesophase pitch |
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