CN114479895B - Reaction system and method for preparing high-quality mesophase pitch and co-producing spinnable isotropic pitch - Google Patents
Reaction system and method for preparing high-quality mesophase pitch and co-producing spinnable isotropic pitch Download PDFInfo
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- CN114479895B CN114479895B CN202210229310.5A CN202210229310A CN114479895B CN 114479895 B CN114479895 B CN 114479895B CN 202210229310 A CN202210229310 A CN 202210229310A CN 114479895 B CN114479895 B CN 114479895B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C1/00—Working-up tar
- C10C1/20—Refining by chemical means inorganic or organic compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C1/00—Working-up tar
- C10C1/04—Working-up tar by distillation
Abstract
The invention relates to a reaction system and a method for preparing high-quality mesophase pitch and co-producing spinnable isotropic pitch. Catalytic or thermal cracking tar, FCC slurry clarified oil, four-line reduced fraction, deasphalted oil of naphthenic vacuum residue, QI-removed refined coal tar and anthracene oil are used as raw materials, a centrifugal reaction separation device is utilized, the vertical and inclined rotation operations of a reaction sleeve are alternated for 2-3 times, so that the raw materials in the reaction sleeve are uniformly heated to carry out polycondensation reaction, an intermediate phase product is enriched at the lower part of the reaction sleeve, and by matching with the opening and closing of valves at the bottom of the sleeve and the bottom of a cavity of the device and the modulation of the molecular weight of the product by a flash tank, high-quality intermediate phase pitch with the yield of 30-50%, the softening point of 220-300 ℃, continuous spinning of more than ten thousand meters can be respectively obtained, and isotropic pitch with the yield of 40-50% and the softening point of 200-280 ℃ can be spun. The invention effectively solves the problems of nonuniform heating of materials and long reaction separation process, and can co-produce high-quality mesophase pitch and isotropic pitch for spinning.
Description
Technical Field
The invention relates to a reaction system and a method for preparing high-quality mesophase pitch and co-producing spinnable isotropic pitch, belonging to the technical field of preparation of high-quality carbon fibers of high-grade carbon materials.
Background
One of the main characteristics of the aromatic-rich component in the heavy oil in the process of medium-temperature (about 450 ℃) liquid phase pyrolysis (carbonization) is to generate polycyclic aromatic hydrocarbon macromolecules, thereby improving the softening point and the carbonization yield of the asphalt. If the reaction system mainly generates lamellar polycyclic aromatic hydrocarbon macromolecules and adjacent polycyclic aromatic hydrocarbon sheets are connected in a pi-pi conjugated bond mode to form a multilayer fused aromatic sheet stacking structure and are regularly arranged and oriented, the reaction system has the regular arrangement of molecules in crystals, shows the specific anisotropy of the crystals and keeps the liquidity of a liquid phase, and the special phase-carbonaceous intermediate phase between a solid phase and the liquid phase is the intermediate phase asphalt. In addition, if more alkyl side chains are retained in the polycyclic aromatic hydrocarbon molecules formed in the reaction system or the planeness of the aromatic ring system is poor, the obtained product is isotropic asphalt. By using mesophase pitch or isotropic pitch as a spinning precursor, two types of high-performance pitch-based carbon fiber (MPCF) and general-purpose pitch-based carbon fiber (GPCF) can be obtained respectively. The MPCF has the advantages of ultrahigh modulus, high strength, high heat conduction/electric conduction and the like, and has irreplaceability in high-end fields such as aerospace and the like. The general-purpose asphalt-based carbon fiber has low cost, has excellent basic physical and chemical properties such as low density, high strength, high temperature resistance, high chemical stability, fatigue resistance, abrasion resistance and the like, and is widely applied to civil and industrial fields such as transportation, machinery, sports and entertainment, leisure goods, medical sanitation, civil engineering and construction and the like. In general, both the mesophase pitch and isotropic pitch for spinning are produced by using heavy aromatic-rich oil as a raw material and by increasing the molecular size by thermal conversion or catalytic conversion. Therefore, the co-production of two spinning precursors can be realized by adopting the same set of production equipment or process, so that the production can be flexibly adjusted according to market demands.
It is known that in the initial stage of the reaction for preparing mesophase pitch by liquid phase carbonization of heavy aromatic-rich oil, the density of the mesophase structure generated is significantly higher than that of the isotropic matrix. As the carbonization proceeds, the difference between the average molecular mass of the isotropic matrix and the mesophase molecules becomes smaller and smaller, so that the difference between the two densities becomes smaller and smaller, and complete separation is not easy to achieve. In this case, although the molecular weight (i.e., molecular size) of the isotropic matrix molecule meets the requirement for forming the mesophase structure, it is likely that the molecules cannot be stacked in parallel because the molecules still contain a large amount of alkyl side chains or the aromatic ring system has poor flatness, and thus do not participate in the formation of the mesophase structure. Excessive charring of the isotropic matrix is easily caused by further increasing the reaction severity and it is still difficult to convert it into planar aromatic macromolecules. Considering that the softening point of the isotropic matrix is relatively high, the softening point can be further regulated and controlled through simple operations such as reduced pressure distillation and the like, so that the isotropic pitch for spinning is obtained, and the utilization rate of the raw materials is improved to a certain extent. Chinese invention patent CN107488876B discloses an operation for continuously preparing high quality mesophase pitch from low mesophase content pitch raw material, mainly by means of melting and standing, thereby enriching mesophase pitch at the bottom of an autoclave and feeding the mesophase pitch into a spinning machine through a metering pump for spinning. And the control of the reaction process and the co-production of two kinds of asphalt are not involved. Chinese patent CN110272757B discloses a method for preparing high-purity mesophase pitch by performing secondary polycondensation on the upper layer low-ash isotropic pitch by performing standing sedimentation on a primary polycondensation product and removing mesophase pitch with higher ash content generated in the lower layer. This patent does not relate to a process for co-producing spinnable mesophase pitch and isotropic pitch, although there is an operation for separating mesophase pitch and isotropic pitch. Therefore, by utilizing the similarity of the mesophase pitch and the isotropic pitch in raw materials, production devices and reaction processes, a method and a reaction system integrating preparation and separation are further developed, and related patents and published reports are not seen at present.
Disclosure of Invention
The invention discloses a method and a reaction system for preparing high-quality mesophase pitch and co-producing spinnable isotropic pitch by using one or more of catalytic cracking tar, FCC slurry clarified oil, tetra-linear reduced fraction, deasphalted oil of naphthenic vacuum residue, QI-removed refined coal tar and anthracene oil as raw oil and by coupling distillation regulation and control of a centrifugal reaction separation device. The method and the reaction system of the invention effectively solve the problems of uneven heating of materials and long reaction separation process, and can co-produce high-quality mesophase pitch and isotropic pitch for spinning.
The invention provides a reaction system for preparing high-quality mesophase pitch and co-producing spinnable isotropic pitch, which comprises a reaction sleeve, a rotary telescopic device, a reaction chamber, a flash tank and a product storage tank, wherein the reaction sleeve is arranged in the reaction chamber; the reaction sleeve, the rotary telescopic device and the reaction chamber form a centrifugal reaction separation device; the reaction sleeve is vertically arranged in the reaction chamber, the conical bottom of the reaction chamber is communicated with the two flash tanks through a three-way valve, and the bottoms of the flash tanks are respectively communicated with the product storage tank; the reaction sleeve is arranged on the rotary telescopic device, and the bottom of the reaction sleeve is connected with an electromagnetic valve; the reaction chamber is in a sealed state, and the top of the reaction chamber is provided with a motor, a pressure gauge, a vacuumizing interface and an inert gas replacement interface.
According to the reaction system, the rotary telescopic device is driven by the motor to realize high-speed rotation of the reaction sleeve, and meanwhile, the adjustable reaction sleeve and the rotary central shaft show different inclinations. The optimized rotating speed is 1000-5000 r/min, and the material rotation effectively avoids the problems of nonuniform heating of the material and easy excessive polycondensation on the wall caused by overhigh temperature of the casing pipe wall in the polycondensation process. Preferably, the reaction sleeve is adjusted to be changed from a vertical state to an inclined state of 14-40 degrees with the central axis through a rotary telescopic device, so that the primary intermediate phase product is separated at the lower part of the sleeve.
The second aspect of the invention provides a method for preparing high-quality mesophase pitch and spinnable isotropic pitch, which is carried out in the reaction system for preparing high-quality mesophase pitch and spinnable isotropic pitch, and comprises the following specific steps:
(1) Adding equivalent raw oil into a reaction sleeve, adjusting the reaction sleeve to be in a vertical state, sealing a reaction chamber, and replacing air in the reaction chamber by vacuumizing and blowing inert gas;
(2) Starting rotation, keeping the temperature in the reaction sleeve at 380-500 ℃, the reaction pressure at 0.1 KPa-6 MPa, and reacting for 4-18 h, wherein the mass content of the intermediate phase of the product in the reaction sleeve reaches 10-30%;
(3) Adjusting the reaction sleeve and the rotating central shaft to present an inclination of 14-40 degrees, keeping rotating at a high speed for 5-30 min, enriching generated intermediate phase components to the lower part of the reaction sleeve through a centrifugal effect, opening an electromagnetic valve at the bottom of the reaction sleeve, and ejecting the intermediate phase components out of the reaction sleeve to enter a reaction chamber;
(4) Setting the temperature in the reaction chamber to be 300-350 ℃, spontaneously flowing and collecting the intermediate phase components to the conical bottom of the reaction chamber without further large-scale initiation of polycondensation, then distributing the intermediate phase components to a first flash tank with the temperature of 300-350 ℃ and the pressure of 1-100 mmHg by controlling a three-way valve at the bottom of the reaction chamber, and feeding the product at the bottom of the first flash tank into a first storage tank to obtain an intermediate phase asphalt product;
(5) Alternately carrying out the operations of the steps (2) and (3) for 2-3 times to obtain high-quality mesophase pitch with the yield of 30-50%, the softening point of 220-300 ℃, and the continuous spinning of more than ten thousand meters;
(6) And (5) after the step (5), the residual isotropic pitch in the reaction sleeve is isotropic pitch, the molten isotropic pitch product is guided to a second flash tank with the temperature of 300-350 ℃ and the pressure of 1-100 mmHg by opening an electromagnetic valve at the bottom of the reaction sleeve and adjusting a three-way valve at the bottom of the reaction chamber, and the spinnable isotropic pitch with the softening point of 200-280 ℃ is obtained at the lower part of the second flash tank and enters the second flash tank to obtain the isotropic pitch product.
In the invention, the reaction sleeve, the rotary telescopic device and the reaction chamber form an integrated centrifugal reaction separation device, which has the functions of high-speed rotation and inclined telescopic, realizes the free alternate operation of rotary polycondensation and inclined separation, and simultaneously solves the problems of uneven heating and excessive polycondensation of materials in the preparation process of the intermediate phase and the difficult problem that the primary intermediate phase product is difficult to separate in time.
In step (2) of the present invention, by controlling the content of the mesophase in the reaction matrix to be between 10 and 30%, the density difference between the formed mesophase and the isotropic matrix is large, the complete separation of the mesophase and the isotropic matrix can be easily achieved, and the mesophase formed at this time also tends to have a lower softening point and more excellent spinnability. Therefore, in the step (3), the reaction sleeve and the rotating central shaft are inclined at 14-40 degrees by adjusting the telescopic rod, so that the centrifugal separation effect is generated; and the adjustment of centrifugal force is realized by regulating and controlling the rotating speed and the inclination angle of the reaction sleeve, so that the effective separation of the intermediate phase and the isotropic matrix in different raw materials and products obtained at different reaction stages is ensured.
In the step (4), the temperature of the reaction chamber is set to be 300-350 ℃, so that the intermediate phase component has good melt flow property and is not enough to initiate the intermediate phase to further perform polycondensation reaction, and the product quality is ensured. In addition, related researches show that the mesophase structural element is formed by parallel stacking of planar polycyclic aromatic hydrocarbon macromolecules, and compared with aromatic hydrocarbon molecules relatively dispersed in isotropic asphalt, the mesophase structure contains more delocalized pi bonds or delocalized electrons, so that the resistivity is lower. Based on this, in the step (4), the resistance sensor is arranged above the electromagnetic valve at the bottom of the reaction sleeve, so that whether the intermediate phase is thrown out of the reaction sleeve into the reaction chamber can be quickly and accurately judged.
After the rotary polycondensation and the inclined separation are alternately carried out for 2-3 times in the step (5), the residual isotropic substrate in the reaction sleeve is reacted for a long time, the molecular weight is larger, the softening point is higher, and the molecular structure of the isotropic substrate often contains more alkyl side chains or the planeness of an aromatic ring system of the isotropic substrate is poorer. If the reaction severity is further increased, the molecules are also difficult to be further converted into planar aromatic macromolecules; even if a part of mesophase structure can be obtained, the obtained mesophase is easy to be over-carbonized, and the quality of the mesophase asphalt product is seriously reduced. Therefore, the invention does not further convert the isotropic matrix, but adopts the step (6) to guide the residual isotropic matrix in the reaction sleeve to the flash tank to remove part of lighter components, thereby realizing the optimized improvement of the performance of the melting rheology and obtaining the spinnable isotropic asphalt.
Compared with the prior art, the invention has the beneficial effects that at least:
(1) The invention realizes the co-production of two pitch-based carbon fiber precursors by adopting the same set of production equipment and process, and effectively solves the problem of low conversion utilization rate of raw materials.
(2) The invention adopts a reaction system of coupling a centrifugal reaction separation device with distillation regulation and control, has simple flow and strong device controllability, is beneficial to the continuity of production, greatly reduces the device cost while flexibly producing, and improves the production efficiency.
(3) The mesophase pitch product obtained by the invention has excellent performance, the yield is 30-50%, the softening point is 220-300 ℃, and the continuous spinning can be carried out for more than ten thousand meters; the yield of the obtained spinnable isotropic pitch is 40-50%, and the softening point is 200-280 ℃; all have good comprehensive performance.
Drawings
FIG. 1 is a reaction system for the co-production of high quality mesophase pitch and spinnable isotropic pitch according to one embodiment of the present invention. Wherein 1-reaction sleeve; 2-rotating the telescoping device; 3-a reaction chamber; 4-three-way valves; 5-a first flash tank; 6-a second flash tank; 7-a first storage tank; 8-a second storage tank; 9-an electromagnetic valve; 21-a spindle shaft; 22-telescopic rod.
Detailed Description
The following examples further describe the reaction system and method for preparing high quality mesophase pitch and co-producing spinnable isotropic pitch.
The invention provides a reaction system for preparing high-quality intermediate phase asphalt and co-producing spinnable isotropic asphalt, as shown in fig. 1, the reaction system comprises a reaction sleeve 1, a rotary expansion device 2, a reaction chamber 3, a first flash tank 5, a second flash tank 6, a first product storage tank 7 and a second product storage tank 8; the reaction sleeve 1, the rotary telescopic device 2 and the reaction chamber 3 form a centrifugal reaction separation device; the reaction sleeve 1 is vertically arranged in the reaction chamber 3, the conical bottom of the reaction chamber 3 is communicated with a first flash tank 5 and a second flash tank 6 through a three-way valve 4, the bottom of the first flash tank 5 is communicated with a first product storage tank 7, and the bottom of the second flash tank 6 is communicated with a second product storage tank 8; the reaction sleeve 1 is arranged on the rotary telescopic device 2, and the bottom of the reaction sleeve 1 is connected with an electromagnetic valve 9; the reaction chamber 3 is in a sealed state, and the top of the reaction chamber is provided with a motor, a pressure gauge, a vacuumizing interface and an inert gas replacement interface.
According to the reaction system of the invention, the rotary telescopic device 2 is driven by a motor to realize high-speed rotation of the reaction sleeve 1, and simultaneously the adjustable reaction sleeve 1 and the rotary central shaft present different inclinations. The optimized rotating speed is 1000-5000 r/min, and the material rotation effectively avoids the problems of nonuniform heating of the material and easy excessive polycondensation on the wall caused by overhigh temperature of the casing pipe wall in the polycondensation process. Preferably, the reaction sleeve 1 is adjusted by the rotary telescopic device 2 to be changed from a vertical state into an inclined state of 14-40 degrees with a rotary central axis, so that the primary intermediate phase product is separated at the lower part of the reaction sleeve 1.
As a typical implementation method, the rotary telescopic device 2 is located at the center of the upper middle part of the reaction chamber 3. The rotary telescopic device 2 comprises a rotating shaft rod 21 connected with a motor and a telescopic rod 22 horizontally fixed on the rotating shaft rod, the reaction sleeve 1 is fixedly connected to the end part of the telescopic rod 22, the telescopic rod 22 adjusts the reaction sleeve 1 and the rotary central shaft to present different gradients, and meanwhile, the high-speed rotation of the reaction sleeve 1 is realized under the driving of the motor. Usually, the rotation shaft 21 is the rotation central shaft.
More preferably, the middle part of the telescopic rod 22 is fixed on the rotating shaft rod 21, and the telescopic rod 22 extends and retracts in two directions along the horizontal direction; the reaction cannula 1 is fixedly connected with two ends of the telescopic rod 22 in pair and symmetry.
More preferably, the reaction sleeve 1 has 2n reaction sleeves, wherein n =1 to 4, and the equal heights are evenly distributed around the rotating shaft 21.
More preferably, 1-3 telescopic rods 22 are arranged in parallel and are simultaneously connected with one reaction sleeve 1, so that the stability is improved; preferably at least 2, connected at least at two positions of the upper, middle and lower parts of the reaction sleeve 1.
More preferably, a resistance sensor is installed above the electromagnetic valve 9 at the bottom of the reaction sleeve 1, and when the resistance sensor detects that the resistance is protruded, the electromagnetic valve 9 is automatically closed and the reaction sleeve 1 is restored to be in a vertical state.
According to the system disclosed by the invention, the reaction sleeve 1, the rotary telescopic device 2 and the reaction chamber 3 form an integrated centrifugal reaction separation device, the integrated centrifugal reaction separation device has high-speed rotation and inclined telescopic functions, the free alternate operation of rotary polycondensation and inclined separation is realized, and the problems of nonuniform heating and excessive polycondensation of materials and difficulty in timely separation of primary intermediate phase products in the intermediate phase preparation process are solved.
The second aspect of the invention provides a method for preparing high-quality mesophase pitch and co-producing spinnable isotropic pitch, which is carried out in the reaction system and comprises the following specific steps:
(1) Adding equivalent raw oil into a reaction sleeve 1, adjusting the reaction sleeve 1 to be in a vertical state, sealing a reaction chamber 3, and replacing air in the reaction chamber 3 by vacuumizing and blowing inert gas;
(2) Starting rotation, keeping the temperature in the reaction sleeve 1 at 380-500 ℃, the reaction pressure at 0.1 KPa-6 MPa, and reacting for 4-18 h to obtain a product with a mesophase content of 10-30% in the reaction sleeve 1;
(3) Adjusting the reaction sleeve 1 and the rotating central axis to present an inclination of 14-40 degrees, keeping rotating at a high speed for 5-30 min, enriching generated intermediate phase components to the lower part of the reaction sleeve 1 through centrifugal action, opening an electromagnetic valve 9 at the bottom of the reaction sleeve 1, and ejecting the intermediate phase components out of the reaction sleeve 1 and into a reaction chamber 3;
(4) Setting the temperature in the reaction chamber 3 to be 300-350 ℃, spontaneously flowing and collecting the intermediate phase components to the conical bottom of the reaction chamber 3 without further large-scale initiation of polycondensation, then distributing the intermediate phase components to a first flash tank 5 with the temperature of 300-350 ℃ and the pressure of 1-100 mmHg by controlling a three-way valve 4 at the bottom of the reaction chamber 3, and feeding the product at the bottom of the first flash tank 5 into a first storage tank 7 to obtain an intermediate phase asphalt product;
(5) Alternately carrying out the operations of the steps (2) and (3) for 2-3 times to obtain high-quality mesophase pitch with the yield of 30-50 percent, the softening point of 220-300 ℃ and the continuous spinning capacity of more than ten thousand meters;
(6) And (5) after the step (5), the residual isotropic pitch in the reaction sleeve 1 is isotropic pitch, the molten isotropic pitch product is guided to a second flash tank 6 with the temperature of 300-350 ℃ and the pressure of 1-100 mmHg by opening an electromagnetic valve 9 at the bottom of the reaction sleeve 1 and a three-way valve 4 at the bottom of an adjusting reaction chamber 3, and then the spinnable isotropic pitch with the softening point of 200-280 ℃ is obtained at the lower part of the second flash tank 6 and enters a second storage tank 8, so that the isotropic pitch product is obtained.
The present invention will be described in detail by the following embodiments, taking an example of a reaction system having 2 reaction sleeves, wherein the 2 reaction sleeves are symmetrically fixed at two ends of a telescopic rod, the middle part of the telescopic rod is fixed on a rotating shaft rod, and the telescopic rod is arranged in parallel with 2 reaction sleeves connected to the upper part and the middle part of the reaction sleeves.
Example 1:
in the reaction system shown in fig. 1, catalytic cracking tar is used as a raw material and is added into a reaction sleeve 1 of a centrifugal reaction separation device, and the reaction sleeve 1 is kept in a vertical state; the adding amount of the raw materials is about 70% of the volume of the reaction sleeve 1, and the consistent adding amount of the raw materials in the reaction sleeve 1 at the symmetrical position is ensured; then sealing the reaction chamber 3, vacuumizing and blowing 99.99% of nitrogen to normal pressure, operating for three times to completely replace air in the reaction chamber 3, setting the initial reaction pressure in the reaction sleeve 1 to normal pressure, keeping the pressures of the reaction sleeve 1 and the reaction chamber 3 the same in the reaction separation process, and keeping the pressure constant to normal pressure by using a back pressure valve;
then, the motor is started to drive the rotating shaft rod 21 to further drive the reaction sleeve 1 to rotate rapidly and stably, and the rotating speed is set to be 1000r/min all the time; simultaneously heating the reaction sleeve 1 to 400 ℃, setting the temperature of the reaction chamber to 300 ℃, and generating an intermediate phase with the content of 15% in the reaction sleeve 1 after reacting at constant temperature for 10 hours;
then, adjusting the telescopic rod 22 to change the reaction sleeve 1 from a vertical state to an inclined state which forms an angle of 15 degrees with the rotation central axis, keeping rotating at a high speed for 30min, then opening the electromagnetic valve 9 at the lower part of the reaction sleeve 1, throwing the mesophase pitch out of the reaction sleeve 1, and entering the reaction chamber 3;
when a resistance sensor above the electromagnetic valve 9 at the bottom of the reaction sleeve 1 monitors that the resistance value is suddenly increased, the electromagnetic valve 9 is automatically closed, the telescopic rod 22 is automatically shortened to restore the reaction sleeve 1 to a vertical state, and the rotation reaction is continued for 10 hours;
the mesophase pitch automatically flows into the first flash tank 5 with the temperature of 350 ℃ and the pressure of 90mmHg from top to bottom in the reaction chamber 3, the mixed light components are separated and removed from the upper part of the first flash tank 5, and the heavy components at the bottom of the first flash tank 5 enter the first storage tank 7; by alternately operating the rotary polycondensation and the inclined separation of the reaction sleeve 1 for 2 times, the mesophase pitch product with the mass yield of 35 percent and the softening point of 230 ℃ can be obtained in the first storage tank 7;
when all the mesophase pitch in the reaction chamber 3 is guided to the first flash tank 5, the reaction sleeve 1 is in a vertical state, the lower electromagnetic valve 9 is opened to enable the residual isotropic matrix to flow into the reaction chamber 3 and flow to the second flash tank 6 with the temperature of 350 ℃ and the pressure of 50mmHg through the three-way valve 4, the lighter components are separated and recovered at the upper part, the heavy components at the bottom of the tank enter the second storage tank 8, and the isotropic pitch with the mass yield of 50% and the softening point of 210 ℃ is obtained.
The obtained mesophase pitch and isotropic pitch are subjected to melt spinning at a temperature higher than the softening points of the mesophase pitch and the isotropic pitch respectively and the continuous filament-receiving length can reach more than ten thousand meters.
Example 2:
in the above reaction system shown in fig. 1, FCC slurry clarified oil is used as a raw material and is fed into a reaction sleeve 1 of a centrifugal reaction separation device, and the reaction sleeve 1 is kept in a vertical state; the adding amount of the raw materials is about 60 percent of the volume of the reaction sleeve, and the consistent adding amount of the raw materials in the reaction sleeve 1 at the symmetrical position is ensured; then sealing the reaction chamber 3, vacuumizing and blowing 99.99% nitrogen to normal pressure, operating for three times to completely replace air in the reaction chamber 3, setting the initial reaction pressure in the reaction sleeve 1 to be 0.05MPa, keeping the pressures of the reaction sleeve 1 and the reaction chamber 3 the same in the reaction separation process, and keeping the pressure constant to be 0.05MPa by using a back pressure valve;
then, the motor is started to drive the rotating shaft rod 21 to further drive the reaction sleeve 1 to rotate rapidly and stably, and the rotating speed is set to be 2500r/min all the time; simultaneously heating the reaction sleeve 1 to 435 ℃, setting the temperature of the reaction chamber to 320 ℃, and generating an intermediate phase with the content of 20% in the reaction sleeve 1 after reacting for 6 hours at constant temperature;
then, adjusting the telescopic rod 22 to change the reaction sleeve 1 from a vertical state to an inclined state of 25 degrees with the rotating central axis, keeping rotating at a high speed for 30min, then opening the electromagnetic valve 9 at the lower part of the reaction sleeve 1, throwing the mesophase pitch out of the reaction sleeve 1, and entering the reaction chamber 3;
when a resistance sensor above the electromagnetic valve 9 at the bottom of the reaction sleeve 1 monitors that the resistance value is suddenly increased, the electromagnetic valve 9 is automatically closed, the telescopic rod 22 is automatically shortened to restore the reaction sleeve 1 to a vertical state, and the rotation reaction is continued for 6 hours;
the mesophase pitch automatically flows into the first flash tank 5 with the temperature of 330 ℃ and the pressure of 50mmHg from top to bottom in the reaction chamber 3, the mixed light components are separated and removed from the upper part of the first flash tank 5, and the heavy components at the bottom of the first flash tank 5 enter the first storage tank 7; by alternately operating the rotary polycondensation and the inclined separation of the reaction sleeve 1 for 2 times, a mesophase pitch product with the mass yield of 30 percent and the softening point of 270 ℃ can be obtained in the first storage tank 7;
when all the mesophase pitch in the reaction chamber 3 is guided to the first flash tank 5, the reaction sleeve 1 is in a vertical state, the lower electromagnetic valve 9 is opened to enable the residual isotropic matrix to flow into the reaction chamber 3 and flow to the second flash tank 6 with the temperature of 330 ℃ and the pressure of 50mmHg through the three-way valve 4, the lighter components are separated and recovered at the upper part, the heavy components at the bottom of the tank enter the second storage tank 8, and the isotropic pitch with the mass yield of 48% and the softening point of 250 ℃ is obtained.
The obtained mesophase pitch and isotropic pitch are subjected to melt spinning at a temperature higher than the softening points of the mesophase pitch and the isotropic pitch by 50 ℃, and the continuous filament collecting length can reach more than ten thousand meters.
Example 3:
in the above reaction system shown in fig. 1, a mixed oil of minus four-line distillate and anthracene oil in a mass ratio of 1; the adding amount of the raw materials is about 50% of the volume of the reaction sleeve 1, and the consistent adding amount of the materials in the reaction sleeve 1 at the symmetrical position is ensured; then sealing the reaction chamber 3, vacuumizing and blowing 99.99% of nitrogen to normal pressure, operating for three times to completely replace air in the reaction chamber 3, setting the initial pressure in the reaction sleeve 1 to be 4MPa, keeping the pressures of the reaction sleeve 1 and the reaction chamber 3 to be the same in the reaction separation process, and keeping the pressure to be 4MPa by utilizing a back pressure valve;
then, the motor is started to drive the rotating shaft rod 21 to further drive the reaction sleeve 1 to rotate rapidly and stably, and the rotating speed is set to be 2500r/min all the time; simultaneously heating the reaction sleeve 1 to 480 ℃, setting the temperature of the reaction chamber to 320 ℃, and generating 16% of intermediate phase in the reaction sleeve after reacting for 4 hours at constant temperature;
then, adjusting the length of the telescopic rod 22 to change the reaction sleeve 1 from a vertical state to an inclined state which forms 40 degrees with the rotating central axis, keeping high-speed rotation for 30min, opening the electromagnetic valve 9 at the lower part of the reaction sleeve 1, throwing the mesophase pitch out of the reaction sleeve 1, and entering the reaction chamber 3;
when a resistance sensor above the electromagnetic valve 9 at the bottom of the reaction sleeve 1 monitors that the resistance value is suddenly increased, the electromagnetic valve 9 is automatically closed, the telescopic rod 22 is automatically shortened to restore the reaction sleeve 1 to a vertical state, and the reaction sleeve continues to rotate for 4 hours;
the mesophase pitch automatically flows into the first flash tank 5 with the temperature of 320 ℃ and the pressure of 10mmHg from top to bottom in the reaction chamber 3, the mixed light components are separated and removed from the upper part of the first flash tank 5, and the heavy components at the bottom of the first flash tank 5 enter the first storage tank 7; by alternately operating the rotary polycondensation and the inclined separation of the reaction sleeve 1 for 3 times, the mesophase pitch product with the mass yield of 50 percent and the softening point of 290 ℃ can be obtained in the first storage tank 7.
When all the mesophase pitch in the reaction chamber 3 is guided to the first flash tank 5, the reaction sleeve 1 is in a vertical state, the lower electromagnetic valve 9 is opened to enable the residual isotropic matrix to flow into the reaction chamber 3 and flow to the second flash tank 6 with the temperature of 330 ℃ and the pressure of 5mmHg through the three-way valve 4, the lighter components are separated and recovered at the upper part, the heavy components at the bottom of the tank enter the second storage tank 8, and the isotropic pitch with the mass yield of 40% and the softening point of 260 ℃ is obtained.
The obtained mesophase pitch and isotropic pitch are subjected to melt spinning at a temperature higher than the softening points of the mesophase pitch and the isotropic pitch respectively and the continuous filament-receiving length can reach more than ten thousand meters.
Claims (10)
1. A reaction system for preparing high-quality mesophase pitch and co-producing spinnable isotropic pitch is characterized by comprising a reaction sleeve, a rotary expansion device, a reaction chamber, a flash tank and a product storage tank; the reaction sleeve, the rotary telescopic device and the reaction chamber form a centrifugal reaction separation device; the reaction sleeve is vertically arranged in the reaction chamber, the conical bottom of the reaction chamber is communicated with the two flash tanks through a three-way valve, and the bottoms of the flash tanks are respectively communicated with the product storage tank; the reaction sleeve is arranged on the rotary telescopic device, and the bottom of the reaction sleeve is connected with an electromagnetic valve; the reaction chamber is in a sealed state, and the top of the reaction chamber is provided with a motor, a pressure gauge, a vacuumizing interface and an inert gas replacement interface; the rotary telescopic device is driven by a motor to realize high-speed rotation of the reaction sleeve, and simultaneously the reaction sleeve and the rotary central shaft can be adjusted to present different inclinations; 2-3 telescopic rods of the rotary telescopic device are arranged in parallel and are connected with the reaction sleeve, so that the stability is improved; is connected to at least two of the upper, middle and lower parts of the reaction sleeve.
2. The reaction system of claim 1, wherein the rotary telescopic device is located at the center of the middle upper part of the reaction chamber; among the rotatory telescoping device, including the pivot pole that links to each other with the motor and the telescopic link of level fixing on the pivot pole, reaction sleeve pipe fixed connection is in the tip of telescopic link, and the telescopic link is adjusted reaction sleeve pipe and is rotated the axis and demonstrate different gradients, and motor drive pivot pole drives reaction sleeve pipe and realizes high-speed rotation simultaneously.
3. The reaction system of claim 2, wherein the middle part of the telescopic rod is fixed on the rotating shaft rod, and the telescopic rod is bi-directionally telescopic along the horizontal direction; the reaction sleeves are symmetrically and fixedly connected to two ends of the telescopic rod in pairs.
4. The reaction system of claim 3, wherein the reaction sleeves have 2n, n =1 to 4, equal heights evenly distributed around the rotating shaft.
5. The reaction system of claim 1, wherein a resistance sensor is installed above the electromagnetic valve at the bottom of the reaction casing, and when the resistance sensor detects the resistance protrusion, the electromagnetic valve is automatically closed and the vertical state of the reaction casing is restored.
6. A method for preparing high-quality mesophase pitch and spinnable isotropic pitch, which is carried out in the reaction system for preparing high-quality mesophase pitch and spinnable isotropic pitch according to any one of claims 1 to 5, and is characterized by comprising the following specific steps:
(1) Adding raw oil into a reaction sleeve, adjusting the reaction sleeve to be in a vertical state, sealing a reaction chamber, and replacing air in the reaction chamber by vacuumizing and blowing inert gas;
(2) Starting a motor, rotating at the speed of 1000-5000 r/min, keeping the temperature in the reaction sleeve at 380-500 ℃, the reaction pressure at 0.1KPa-6 MPa, and reacting for 4-18h, wherein the mass content of the intermediate phase of the product in the reaction sleeve reaches 10-30%;
(3) Adjusting the reaction sleeve and a rotating central axis to present an inclination of 14 to 40 degrees, keeping rotating at a high speed for 5 to 30min, enriching generated intermediate phase components to the lower part of the reaction sleeve through a centrifugal effect, opening an electromagnetic valve at the bottom of the reaction sleeve, and ejecting the intermediate phase components out of the reaction sleeve to enter a reaction chamber;
(4) Setting the temperature in the reaction chamber to be 300-350 ℃, setting the pressure to be the same as that of the reaction sleeve, enabling the intermediate phase components to spontaneously flow and converge at the conical bottom of the reaction chamber without further large-scale initiation of polycondensation reaction, then distributing the intermediate phase components into a first flash tank with the temperature of 300-350 ℃ and the pressure of 1-100mmHg by controlling a three-way valve at the bottom of the reaction chamber, and enabling a product at the bottom of the first flash tank to enter a first storage tank to obtain an intermediate phase asphalt product;
(5) Alternately carrying out the operations in the steps (2) and (3) for 2 to 3 times to obtain high-quality mesophase pitch with the softening point of 220 to 300 ℃;
(6) And (5) after the step (5), isotropic asphalt is remained in the reaction sleeve, an electromagnetic valve at the bottom of the reaction sleeve is opened, a three-way valve at the bottom of the reaction chamber is adjusted, the molten isotropic asphalt product is guided to a second flash tank with the temperature of 300-350 ℃ and the pressure of 1-100mmHg, and then spinnable isotropic asphalt with the softening point of 200-280 ℃ is obtained at the lower part of the second flash tank and enters a second storage tank, so that an isotropic asphalt product is obtained.
7. The method of claim 6, wherein the feedstock oil is selected from one or more of catalytic cracking tar, FCC slurry clarified oil, reduced crude, naphthenic vacuum residue deasphalted oil, QI-removed refined coal tar, and anthracene oil.
8. The method as claimed in claim 6, wherein the amount of the raw materials added is about 50-80% of the volume of the reaction sleeve, and the amount of the raw materials added in a plurality of reaction sleeves is the same.
9. The method as claimed in claim 6, wherein the reaction sleeve is set at 400 to 480 ℃, the reaction chamber is set at 300 to 330 ℃, and the mass content of the mesophase in the reaction sleeve is 10 to 30%.
10. The method of claim 6, wherein: the mass yield of the high-quality mesophase pitch is 30-50%, the mass yield of the spinnable isotropic pitch is 40-50%, and the continuous filament collecting length reaches more than ten thousand meters when melt spinning is carried out at the temperature of 50 ℃ higher than the respective softening point.
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| CN202210229310.5A CN114479895B (en) | 2022-03-09 | 2022-03-09 | Reaction system and method for preparing high-quality mesophase pitch and co-producing spinnable isotropic pitch |
| PCT/CN2023/080367 WO2023169486A1 (en) | 2022-03-09 | 2023-03-09 | Reaction system and method for preparing high-quality mesophase pitch and co-producing spinnable isotropic pitch |
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| DE3724102C1 (en) * | 1987-07-21 | 1989-02-02 | Didier Eng | Method and device for producing anisotropic carbon fibers |
| US4891126A (en) * | 1987-11-27 | 1990-01-02 | Mitsubishi Gas Chemical Company, Inc. | Mesophase pitch for use in the making of carbon materials and process for producing the same |
| CN1769553A (en) * | 2005-05-10 | 2006-05-10 | 甄铭三 | Multifunctional two-for-one twister design principle, and spinning and twisting application technology |
| US9376626B1 (en) * | 2011-04-28 | 2016-06-28 | Advanced Carbon Products, LLC | Turbulent mesophase pitch process and products |
| WO2017072771A1 (en) * | 2015-10-28 | 2017-05-04 | Bar-Ilan University | Robotic cooperative system |
| CN108291151A (en) * | 2015-11-20 | 2018-07-17 | 理查德·斯通 | Single-stage pitch technique and product |
| CN106092694A (en) * | 2016-08-05 | 2016-11-09 | 成都理工大学 | A kind of shale mechanics parameter test sample |
| US10913901B2 (en) * | 2017-09-12 | 2021-02-09 | Saudi Arabian Oil Company | Integrated process for mesophase pitch and petrochemical production |
| CN109504417A (en) * | 2017-09-14 | 2019-03-22 | 大连正邦新能源材料有限公司 | A kind of interphase can spin the production method and system of pitch |
| CN208219029U (en) * | 2018-05-25 | 2018-12-11 | 韶关学院 | A kind of centrifugal spinning is at wadding molding equipment |
| CN111496214A (en) * | 2020-04-03 | 2020-08-07 | 浙江大学 | Cantilever type centrifugal supergravity casting device |
| CN112645304B (en) * | 2021-01-13 | 2022-07-29 | 中国石油大学(华东) | Method for preparing high-performance mesocarbon microbeads from heavy oil |
| CN112852464B (en) * | 2021-01-13 | 2022-05-10 | 中国石油大学(华东) | Pretreatment method of raw oil for preparing spinnable mesophase pitch and high-performance pitch-based carbon fiber |
| CN113680301B (en) * | 2021-07-23 | 2022-05-31 | 东华大学 | Method and device for preparing spinnable mesophase pitch |
| CN215312409U (en) * | 2021-08-05 | 2021-12-28 | 广州市浩立生物科技有限公司 | Rotary thermal polycondensation reaction device and mesophase pitch preparation system |
| CN113549466B (en) * | 2021-08-05 | 2022-09-20 | 广州市浩立生物科技有限公司 | Preparation method of high-quality mesophase pitch |
| CN114479895B (en) * | 2022-03-09 | 2022-11-25 | 中国石油大学(华东) | Reaction system and method for preparing high-quality mesophase pitch and co-producing spinnable isotropic pitch |
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