A mesophase pitch production method and system

Abstract

The present application relates to the technical field of asphalt preparation, and particularly relates to a mesophase pitch preparation method and system, which comprises the following steps: S1, distillation separation of raw oil slurry; S2, polymerization distillation of light aromatic oil, medium aromatic oil and heavy aromatic oil into low-softening-point mesophase pitch, medium-softening-point mesophase pitch and high-softening-point mesophase pitch, respectively; S3, mixing and blending of the low-softening-point mesophase pitch, the medium-softening-point mesophase pitch and the high-softening-point mesophase pitch in different proportions to obtain mesophase pitches with different characteristics. The present application realizes the conversion of materials to the greatest extent, and the yield is improved to 25-35%, realizes the controllability of key indexes of mesophase pitch, and realizes the stable preparation of mesophase pitch.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of asphalt preparation, in particular to a mesophase pitch preparation method and system. BACKGROUND

[0002] Pitch-based carbon fiber is a kind of special fiber with carbon content greater than 92% which is made of petroleum pitch, coal tar, naphthalene as raw material, through pitch refining, spinning, pre-oxidation, carbonization or graphitization. It is a new material with excellent mechanical properties, and the tensile strength of carbon fiber resin composite material is generally more than 3500Mpa, which is 7-9 times of steel. The tensile elastic modulus is 230-430Gpa, which is also higher than steel. It has excellent properties such as high strength, high modulus, high temperature resistance, corrosion resistance, fatigue resistance, creep resistance, electrical conductivity and thermal conductivity, and is an indispensable engineering material in aerospace industry. As a raw material for producing pitch-based carbon fiber, the yield and performance of mesophase pitch are the prerequisite for determining the yield and performance of pitch-based carbon fiber.

[0003] The traditional mesophase pitch preparation method is mostly intermittent polymerization or single preparation of mesophase pitch, and the conversion rate is only 10-20%, the conversion rate is low, and the utilization rate of oil slurry is low. The traditional process is mostly intermittent preparation of mesophase pitch. After completing the preparation of mesophase pitch in a single time, the used equipment needs to be disassembled, cleaned, installed and other links, which is time-consuming and laborious, the process fluctuation is large, the production efficiency is low, the performance of the produced mesophase pitch fluctuates greatly, and it cannot meet the requirements of engineering production.

[0004] The traditional process is mostly high temperature and high pressure polymerization of the material, and then high temperature and negative pressure polymerization to obtain mesophase pitch. With the extension of time in the high temperature and high pressure polymerization process, the concentration of reactive substances in the system gradually decreases, which leads to the gradual reduction of reaction conversion rate, and finally affects the yield of mesophase pitch and cannot effectively improve the yield. SUMMARY

[0005] In view of the low yield of mesophase pitch in the prior art, the present application provides a mesophase pitch preparation method and system.

[0006] The present application is realized by the following technical scheme:

[0007] A mesophase pitch preparation method, comprising the following steps:

[0008] S1, distillation and separation of raw oil slurry, the raw oil slurry is divided into light distillate, light aromatic oil, medium aromatic oil and heavy aromatic oil according to the distillation range;

[0009] S2, independently polymerizing and distilling the light aromatic oil, the medium aromatic oil and the heavy aromatic oil into low softening point mesophase pitch, medium softening point mesophase pitch and high softening point mesophase pitch respectively;

[0010] S3, mixing and modulating the low softening point mesophase pitch, the medium softening point mesophase pitch and the high softening point mesophase pitch in different proportions to obtain mesophase pitches with different properties;

[0011] Wherein, S1 and S2 are independent of each other and can be carried out simultaneously.

[0012] Preferably, in S1, the distillation temperature of the light fraction is room temperature to 250℃, the reaction pressure of the crude oil distillation kettle is -0.09MPa to -0.096MPa, and the stirring speed is 50 to 300 revolutions / min.

[0013] Preferably, in S1, the distillation temperature of the light aromatic oil is 250 to 300℃, the reaction pressure is -0.08MPa to -0.096MPa, and the stirring speed is 50 to 300 revolutions / min.

[0014] Preferably, in S1, the distillation temperature of the medium aromatic oil is 300 to 350℃, the reaction pressure of the crude oil distillation kettle is -0.08MPa to -0.096MPa, and the stirring speed is 50 to 300 revolutions / min.

[0015] Preferably, in S1, the distillation temperature of the heavy aromatic oil is 350 to 400℃, the reaction pressure of the crude oil distillation kettle is -0.08MPa to -0.096MPa, and the stirring speed is 50 to 300 revolutions / min.

[0016] Preferably, in S2, in the process of polymerization distillation of the light aromatic oil into low softening point mesophase pitch, the reaction temperature is 400 to 420℃, the pressure is 1 to 3MPa, the stirring speed is 50 to 300 revolutions / min, and the reaction time is 5 to 15h.

[0017] Preferably, in S2, in the process of polymerization distillation of the medium aromatic oil into medium softening point mesophase pitch, the reaction temperature is 410 to 430℃, the pressure is 1 to 3MPa, the stirring speed is 50 to 300 revolutions / min, and the reaction time is 5 to 10h.

[0018] Preferably, in S2, in the process of polymerization distillation of the high softening point mesophase pitch into high softening point mesophase pitch, the reaction temperature is 420 to 450℃, the pressure is 1 to 3MPa, the stirring speed is 50 to 300 revolutions / min, and the reaction time is 5 to 10h.

[0019] Preferably, in S3, in the process of mixing and modulation, the temperature is 400℃, the pressure is normal pressure, the stirring speed is 200 revolutions / min, and the time is 1 to 5h.

[0020] The application relates to a mesophase pitch preparation system, which comprises a crude oil distillation kettle, a crude oil metering pump, a first collecting tank, a second collecting tank, a third collecting tank, a fourth collecting tank, a first metering pump, a second metering pump, a third metering pump, a first reaction kettle, a second reaction kettle, a third reaction kettle and a fourth reaction kettle; the inlet of the crude oil distillation kettle is connected with the outlet of the crude oil metering pump; the inlets of the first, second, third and fourth collecting tanks are connected with the outlet of the crude oil distillation kettle;

[0021] A first valve is arranged between the first collecting tank and the crude oil distillation kettle, a second valve is arranged between the second collecting tank and the crude oil distillation kettle, a third valve is arranged between the third collecting tank and the crude oil distillation kettle, and a fourth valve is arranged between the fourth collecting tank and the crude oil distillation kettle;

[0022] The outlet of the first collecting tank and the outlet of the second collecting tank are connected with the inlet of the first reaction kettle, the outlet of the first reaction kettle is connected with the inlet of the first metering pump; the outlet of the third collecting tank is connected with the inlet of the second reaction kettle, the outlet of the second reaction kettle is connected with the inlet of the second metering pump; the outlet of the fourth collecting tank is connected with the inlet of the third reaction kettle, the outlet of the third reaction kettle is connected with the inlet of the third metering pump; and the outlets of the first, second and third metering pumps are connected with the inlet of the fourth reaction kettle;

[0023] The outlet of the fourth reaction kettle is connected with an extruding granulator; and the bottom of the crude oil distillation kettle is further connected with a heavy oil slurry receiving tank.

[0024] Compared with the prior art, the application has the following beneficial effects:

[0025] The application is a mesophase pitch preparation method which uses petroleum slurry as raw material and realizes material conversion to the maximum extent through distillation, re-polymerization, re-distillation, modulation and extrusion processes, and the yield is improved to 25-35%, the key indicators of the mesophase pitch are controllable, and the stable preparation of the mesophase pitch is realized.

[0026] The production process of the application is simple, the process is easy to control, the product performance is stable, and the engineering preparation can be realized. Secondly, the distillation separation process and the polymerization distillation process are independent of each other and can be carried out separately, compared with the traditional intermittent polymerization preparation method, the production efficiency of the mesophase pitch is improved by reducing the links such as disassembly, cleaning and installation of the equipment. In addition, in the polymerization distillation process, the low-softening-point mesophase pitch, the medium-softening-point mesophase pitch and the high-softening-point mesophase pitch can be independently prepared, the cross of different mesophase pitches is avoided, the mesophase pitch can be extracted according to the use of materials during preparation, and the production efficiency of the mesophase pitch is further improved.

[0027] The intermediate phase pitch preparation method can realize effective separation of effective components, ensure that the molecular weight distribution of the raw oil slurry is narrower and more reasonable, correspondingly, the reaction control difficulty is smaller, the conversion efficiency is higher, and the product performance is more stable.

[0028] The intermediate phase pitch preparation method can realize effective separation of effective components, ensure that the molecular weight distribution of the raw oil slurry is narrower and more reasonable, correspondingly, the reaction control difficulty is smaller, the conversion efficiency is higher, and the product performance is more stable. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 The intermediate phase pitch preparation method can realize effective separation of effective components, ensure that the molecular weight distribution of the raw oil slurry is narrower and more reasonable, correspondingly, the reaction control difficulty is smaller, the conversion efficiency is higher, and the product performance is more stable.

[0030] Figure 2 The intermediate phase pitch preparation method can realize effective separation of effective components, ensure that the molecular weight distribution of the raw oil slurry is narrower and more reasonable, correspondingly, the reaction control difficulty is smaller, the conversion efficiency is higher, and the product performance is more stable.

[0031] In the figure, 1 is an oil slurry storage tank, 2 is a crude oil distillation still, 3 is a heavy oil slurry receiving tank, 4 is a second reaction kettle, 5 is a third reaction kettle, 6 is a third metering pump, 7 is a fourth reaction kettle, 8 is an extrusion granulator, 9 is a first reaction kettle, 10 is a first metering pump, 11 is a second metering pump, 12 is a first collection tank, 13 is a second collection tank, 14 is a third collection tank, 15 is a fourth collection tank, 16 is a first valve, 17 is a second valve, 18 is a third valve, and 19 is a fourth valve. DETAILED DESCRIPTION

[0032] The application will be further described in detail below in combination with specific examples, which are an explanation of the application but not a limitation.

[0033] The application discloses a kind of intermediate phase pitch preparation system, refer to Figure 1 、 2The distillation system comprises a crude oil distillation kettle, a crude oil metering pump, a first collection tank, a second collection tank, a third collection tank, a fourth collection tank, a first metering pump, a second metering pump, a third metering pump, a first reaction kettle, a second reaction kettle, a third reaction kettle and a fourth reaction kettle. The inlet of the crude oil distillation kettle is connected with the outlet of the crude oil metering pump, and the inlets of the first collection tank, the second collection tank, the third collection tank and the fourth collection tank are connected with the outlet of the crude oil distillation kettle. The first valve is arranged between the first collection tank and the crude oil distillation kettle, the second valve is arranged between the second collection tank and the crude oil distillation kettle, the third valve is arranged between the third collection tank and the crude oil distillation kettle, and the fourth valve is arranged between the fourth collection tank and the crude oil distillation kettle. The outlet of the first collection tank and the outlet of the second collection tank are connected with the inlet of the first reaction kettle, and the outlet of the first reaction kettle is connected with the inlet of the first metering pump. The outlet of the third collection tank is connected with the inlet of the second reaction kettle, and the outlet of the second reaction kettle is connected with the inlet of the second metering pump. The outlet of the fourth collection tank is connected with the inlet of the third reaction kettle, and the outlet of the third reaction kettle is connected with the inlet of the third metering pump. The outlets of the first metering pump, the second metering pump and the third metering pump are connected with the inlet of the fourth reaction kettle. The outlet of the fourth reaction kettle is connected with an extruding granulator. The bottom of the crude oil distillation kettle is further connected with a heavy oil slurry receiving tank.

[0034] The application discloses a preparation method of intermediate pitch, which comprises the following steps:

[0035] S1, distillation separation of raw oil slurry, according to the distillation range, the raw oil slurry is divided into light aromatic oil, medium aromatic oil and heavy aromatic oil; in S1, the distillation range of the light aromatic oil is 250-300 DEG C, the distillation range of the medium aromatic oil is 300-350 DEG C, and the distillation range of the heavy aromatic oil is 350-400 DEG C.

[0036] When the distillation temperature is room temperature-250 DEG C, the reaction pressure of the crude oil distillation kettle is-0.09 MPa--0.096 MPa, and the stirring speed is 50-300 r / min, the first valve is opened, and the second valve, the third valve and the fourth valve are closed, and the light distillate below 250 DEG C is collected into the first collection tank.

[0037] When the distillation temperature is 250-300 DEG C, the reaction pressure of the crude oil distillation kettle is-0.08 MPa--0.096 MPa, and the stirring speed is 50-300 r / min, the second valve is opened, and the first valve, the third valve and the fourth valve are closed, and the light aromatic oil in 250 DEG C-300 DEG C is collected into the second collection tank.

[0038] When the distillation temperature is 300-350℃, the reaction pressure of the crude oil distillation kettle is -0.08MPa to -0.096MPa, and the stirring speed is 50-300r / min; at this time, the third valve is opened, and the first valve, the second valve and the fourth valve are closed, and the medium aromatic oil in 300-350℃ is collected into the third collection tank.

[0039] When the distillation temperature is 350-400℃, the reaction pressure of the crude oil distillation kettle is -0.08MPa to -0.096MPa, and the stirring speed is 50-300r / min; at this time, the fourth valve is opened, and the first valve, the second valve and the third valve are closed, and the heavy aromatic oil in 350-400℃ is collected into the fourth collection tank.

[0040] The remaining components in the crude oil distillation kettle are discharged into the heavy oil slurry receiving tank.

[0041] S2, the light aromatic oil, the medium aromatic oil and the heavy aromatic oil are independently polymerized and distilled into low softening point mesophase pitch, medium softening point mesophase pitch and high softening point mesophase pitch, respectively;

[0042] Among them, the process of polymerizing and distilling the light aromatic oil into low softening point mesophase pitch is carried out in the first reaction kettle, the reaction temperature is 400-420℃, the pressure is 1-3MPa, the stirring speed is 50-300r / min, and the reaction time is 5-15h.

[0043] The process of polymerizing and distilling the medium aromatic oil into medium softening point mesophase pitch is carried out in the second reaction kettle, the reaction temperature is 410-430℃, the pressure is 1-3MPa, the stirring speed is 50-300r / min, and the reaction time is 5-10h.

[0044] The process of polymerizing and distilling the high softening point mesophase pitch into high softening point mesophase pitch is carried out in the third reaction kettle, the reaction temperature is 420-450℃, the pressure is 1-3MPa, the stirring speed is 50-300r / min, and the reaction time is 5-10h.

[0045] S3, the low softening point mesophase pitch, the medium softening point mesophase pitch and the high softening point mesophase pitch are mixed and prepared in different proportions to obtain mesophase pitches with different properties.

[0046] Among them, the process of mixing and preparation is carried out in the fourth reaction kettle, at this time, the temperature is 400℃, the pressure is normal pressure, the stirring speed is 200r / min, and the time is 1-5h.

[0047] According to the characteristics of the target mesophase pitch, the amounts of materials in the first, second and third reaction kettles are adjusted by the first, second and third metering pumps (as shown in Table 1), and the materials in each reaction kettle are input into the corresponding thin film evaporator in proportion for devolatilization treatment. The temperature during the devolatilization treatment is 350-420°C, the pressure is -0.080 to -0.095 MPa, and the nitrogen flow rate is 0.1-10 m3 / h.

[0048] The materials after the devolatilization treatment are input into the fourth reaction kettle for mixing and conditioning by a metering pump, and the standard mesophase pitch is prepared by an extruder granulator after uniform mixing. The extrusion process is as follows: 1# temperature zone 300-320°C, 2# temperature zone 360-380°C, 3# temperature zone 360-380°C, 4# temperature zone 300-320°C, nitrogen flow rate 1-10 m3 / h, extrusion pressure 0-3 MPa, and discharge rate 50-100 kg.

[0049] Table 1: Proportioning table of the amounts of materials in the first, second and third reaction kettles

[0050] Name First reactor material usage Second reactor material usage Third reactor material usage Material example 0～100％ 0～100％ 0～100％

[0051] In addition, S1 and S2 are independent of each other and can be performed simultaneously. The distillation separation process and the polymerization distillation process are independent of each other and can be performed separately. Compared with the traditional batch polymerization preparation method, the device is reduced in disassembly, cleaning and installation, etc., which helps to improve the production efficiency of mesophase pitch.

[0052] Example 1

[0053] The raw oil slurry (FCC oil slurry) in the storage tank is delivered to the crude oil distillation kettle by a metering pump. Distillation treatment is performed at a distillation temperature of room temperature to 400°C, a reaction pressure of -0.096 MPa, and a stirring speed of 300 revolutions / min. When the distillation temperature is below 250°C, the first valve is opened, and the second, third and fourth valves are closed, so that all the light fraction below 250°C is collected into the first collection tank. After the collection of the current fraction is completed, the second valve is opened, and the first, third and fourth valves are closed, so that all the fraction of 250-300°C is collected into the second collection tank. When the collection of the fraction of 250-300°C is completed, the third valve is opened, and the first, second and fourth valves are closed, so that all the fraction of 300-350°C is collected into the third collection tank. When the collection of the fraction of 300-350°C is completed, the fourth valve is opened, and the first, second and third valves are closed, so that all the fraction of 350-400°C is collected into the fourth collection tank. When the collection of the fraction of 350-400°C is completed, the remaining components in the distillation kettle after distillation are discharged into the heavy oil receiving tank. The materials in the second, third and fourth collection tanks are ready for use.

[0054] The distillation material in the second collection tank is input into the first reactor through a metering pump (input amount 20 kg / min), and when the material in the reactor reaches 700 kg, the input is stopped. The reaction starts at a temperature of 410°C, a pressure of 2 MPa, a stirring speed of 200 rpm, and a reaction time of 10 h, and the material is used after the reaction is completed. The distillation material in the third collection tank is input into the second reactor through a metering pump (input amount 20 kg / min), and when the material in the reactor reaches 700 kg, the input is stopped. The reaction starts at a temperature of 420°C, a pressure of 2 MPa, a stirring speed of 200 rpm, and a reaction time of 7.5 h, and the material is used after the reaction is completed. The distillation material in the fourth collection tank is input into the third reactor through a metering pump (input amount 20 kg / min), and when the material in the reactor reaches 700 kg, the input is stopped. The reaction starts at a temperature of 430°C, a pressure of 2 MPa, a stirring speed of 200 rpm, and a reaction time of 10 h, and the material is used after the reaction is completed.

[0055] The material in the first reactor is input into a distillation tower through a metering pump for devolatilization treatment, the treatment temperature is 400°C, the pressure is -0.090 MPa, the nitrogen flow is 10 m 3 ; and after the treatment is completed, the material is transported into the fourth reactor through a first metering pump, and the total amount of the material added is 300 kg (input amount 60 kg / min).

[0056] The material in the second reactor is input into a distillation tower through a metering pump for devolatilization treatment, the treatment temperature is 400°C, the pressure is -0.090 MPa, the nitrogen flow is 10 m 3 ; and after the treatment is completed, the material is transported into the fourth reactor through a second metering pump, and the total amount of the material added is 100 kg (input amount 20 kg / min).

[0057] The material in the third reactor is input into a distillation tower through a metering pump for devolatilization treatment, the treatment temperature is 400°C, the pressure is -0.090 MPa, the nitrogen flow is 10 m 3 ; and after the treatment is completed, the material is transported into the fourth reactor through a third metering pump, and the amount of the material added is 100 kg (input amount 20 kg / min), and the total amount of the material added is 500 kg.

[0058] After the addition is completed, the material mixing and conditioning starts, and the process parameters are set as follows: the treatment temperature is 400°C, the pressure is normal, the nitrogen protection is used, the speed is 200 rpm, and the material mixing and stirring is performed for 2 h. After the material is uniformly mixed, the product mesophase pitch is extruded and granulated through an extruder, the temperature of the extruder is set as follows (a total of four temperature zones are set as 320°C, 380°C, 380°C, and 320°C), the speed is 100 rpm, the nitrogen flow is 5 m 3 / h, the extrusion pressure is 1 MPa, and the output is 100±10 kg / h.

[0059] The test results of the intermediate pitch prepared in the implementation case 1 are shown in Table 2.

[0060] Table 2: Test results of the intermediate pitch

[0061] Name Softening point °C Mesophase content % Carbon residue content % Quinoline insolubles % Yield % Mesophase pitch product 225 100％ 55 3.2 24

[0062] Implementation case 2

[0063] The raw oil slurry (FCC oil slurry) in the storage tank is transported to the crude oil distillation kettle through a metering pump. Distillation treatment is carried out, distillation temperature: room temperature to 400℃, reaction pressure-0.096 MPa, stirring speed 300 revolutions / min. When the distillation temperature is below 250℃, open the first valve, close the second valve, the third valve and the fourth valve, and all the light fraction below 250℃ is collected into the first collection tank; after the current fraction collection is completed, open the second valve, close the first valve, the third valve and the fourth valve, and all the fraction of 250-300℃ is collected into the second collection tank; when the fraction of 250-300℃ is collected, open the third valve, close the first valve, the second valve and the fourth valve, and all the fraction of 300-350℃ is collected into the third collection tank; when the fraction of 300-350℃ is collected, open the fourth valve, close the first valve, the second valve and the third valve, and all the fraction of 350-400℃ is collected into the fourth collection tank; when the fraction of 350-400℃ is collected, the remaining components in the distillation kettle are discharged into the heavy oil receiving tank. The materials in the second collection tank, the third collection tank and the fourth collection tank are ready for use.

[0064] The distillation material in the second collection tank is input into the first reaction kettle through a metering pump (feed amount 20 kg / min), and the feeding is stopped when the material in the kettle reaches 700 kg. Start the reaction: reaction temperature 420℃, pressure 3 MPa, stirring speed 300 revolutions / min, reaction 5h, and the material is ready for use after the reaction is completed; the distillation material in the third collection tank is input into the second reaction kettle through a metering pump (feed amount 20 kg / min), and the feeding is stopped when the material in the kettle reaches 700 kg. Start the reaction: reaction temperature 430℃, pressure 3 MPa, stirring speed 300 revolutions / min, reaction 5h, and the material is ready for use after the reaction is completed; the distillation material in the fourth collection tank is input into the third reaction kettle through a metering pump (feed amount 20 kg / min), and the feeding is stopped when the material in the kettle reaches 700 kg. Start the reaction: reaction temperature 440℃, pressure 3 MPa, stirring speed 300 revolutions / min, reaction 5h, and the material is ready for use after the reaction is completed.

[0065] The material in the first reaction kettle is input into the distillation column through a metering pump for devolatilization treatment, the treatment temperature is 420℃, the pressure is-0.096 MPa, the nitrogen flow is 10 m 3; After the treatment, the material is delivered to the fourth reactor through the first metering pump, and the total amount of the material is 400 kg (the delivery amount is 50 kg / min).

[0066] The material in the second reactor is input into the distillation column through the metering pump for devolatilization treatment, the treatment temperature is 420℃, the pressure is -0.096 MPa, the nitrogen flow is 10 m 3 ; After the treatment, the material is delivered to the fourth reactor through the second metering pump, and the total amount of the material is 50 kg (the delivery amount is 20 kg / min).

[0067] The material in the third reactor is input into the distillation column through the metering pump for devolatilization treatment, the treatment temperature is 420℃, the pressure is -0.096 MPa, the nitrogen flow is 10 m 3 ; After the treatment, the material is delivered to the fourth reactor through the third metering pump, and the total amount of the material is 50 kg (the delivery amount is 20 kg / min).

[0068] After the material is added, the mixing and conditioning are started, and the process parameters are set as follows: the treatment temperature is 400℃, the normal pressure, the nitrogen protection, the rotating speed is 200 revolutions / min, the material mixing and stirring is 5 h, when the material is uniformly mixed, the product mesophase pitch is extruded and granulated through the extruder, the extruder temperature is set as (the total of four temperature zones are set as 320℃, 380℃, 380℃, 320℃), the rotating speed is 100 revolutions / min, the nitrogen flow is 10 m 3 / h, the extrusion pressure is 1 MPa, and the yield is 100±10 kg / h.

[0069] The test results of the mesophase pitch prepared in the implementation case 2 are shown in Table 3.

[0070] Table 3 Test results of mesophase pitch

[0071]

[0072]

[0073] Implementation case 3

[0074] The raw oil slurry (FCC oil slurry) in the storage tank is delivered to the crude oil distillation kettle by a metering pump. Distillation treatment is carried out, distillation temperature: room temperature to 400℃, reaction pressure -0.092 MPa, stirring speed 300 revolutions / min. When the distillation temperature is below 250℃, open the first valve, close the second valve, the third valve and the fourth valve, and all the light fraction below 250℃ is collected into the first collection tank; after the current fraction collection is completed, open the second valve, close the first valve, the third valve and the fourth valve, and all the fraction of 250-300℃ is collected into the second collection tank; when the fraction of 250-300℃ is collected, open the third valve, close the first valve, the second valve and the fourth valve, and all the fraction of 300-350℃ is collected into the third collection tank; when the fraction of 300-350℃ is collected, open the fourth valve, close the first valve, the second valve and the third valve, and all the fraction of 350-400℃ is collected into the fourth collection tank; when the fraction of 350-400℃ is collected, the remaining components in the distillation kettle are discharged into the heavy oil receiving tank. The materials in the second collection tank, the third collection tank and the fourth collection tank are used later.

[0075] The distillation material in the second collection tank is input into the first reaction kettle by a metering pump (the input amount is 20 kg / min), and the input is stopped when the material in the kettle reaches 700 kg. Start the reaction: reaction temperature 400℃, pressure 1 MPa, stirring speed 50 revolutions / min, reaction time 15 h, and the material is used later after the reaction is completed; the distillation material in the third collection tank is input into the second reaction kettle by a metering pump (the input amount is 20 kg / min), and the input is stopped when the material in the kettle reaches 700 kg. Start the reaction: reaction temperature 410℃, pressure 1 MPa, stirring speed 50 revolutions / min, reaction time 15 h, and the material is used later after the reaction is completed; the distillation material in the fourth collection tank is input into the third reaction kettle by a metering pump (the input amount is 20 kg / min), and the input is stopped when the material in the kettle reaches 700 kg. Start the reaction: reaction temperature 420℃, pressure 1 MPa, stirring speed 50 revolutions / min, reaction time 15 h, and the material is used later after the reaction is completed.

[0076] The material in the first reaction kettle is input into a distillation column by a metering pump for devolatilization treatment, the treatment temperature is 350℃, the pressure is -0.08 MPa, and the nitrogen flow is 1 m 3 After the treatment is completed, the material is delivered into the fourth reaction kettle by a first metering pump, and the total amount of the material is 200 kg (the input amount is 50 kg / min).

[0077] The material in the second reaction kettle is input into a distillation column by a metering pump for devolatilization treatment, the treatment temperature is 350℃, the pressure is -0.08 MPa, and the nitrogen flow is 1 m 3; after the treatment, the material is delivered into the fourth reactor through the second metering pump, and the total feeding amount is 150 kg (feeding amount: 20 kg / min).

[0078] The material in the third reactor is input into the distillation column through the metering pump for devolatilization treatment, the treatment temperature is 350 ℃, the pressure is -0.08 MPa, the nitrogen flow is 1 m 3 ; after the treatment, the material is delivered into the fourth reactor through the third metering pump, and the feeding amount is 150 kg (feeding amount: 20 kg / min), and the total feeding amount is 500 kg.

[0079] After the feeding is completed, the material mixing and conditioning is started, and the process parameters are set as follows: the treatment temperature is 400 ℃, the pressure is normal pressure, the nitrogen protection is used, the rotating speed is 200 r / min, and the material mixing and stirring is performed for 5 h. After the material is uniformly mixed, the product mesophase pitch is extruded and granulated through the extruder, the extruder temperature is set as (the four temperature zones are set as 320 ℃, 380 ℃, 380 ℃ and 320 ℃ respectively), the rotating speed is 100 r / min, the nitrogen flow is 5 m 3 / h, the extrusion pressure is 1 MPa, and the yield is 100±10 kg / h.

[0080] The test results of the mesophase pitch prepared in the implementation case 3 are shown in Table 4.

[0081] Table 4: Test results of mesophase pitch

[0082] Name Softening point °C Mesophase content % Carbon residue content % Quinoline insolubles % Yield % Mesophase pitch product 207 90％ 45 1.7 31

[0083] Implementation case 4

[0084] The raw oil slurry (FCC oil slurry) in the storage tank is delivered into the crude oil distillation kettle through the metering pump. The distillation treatment is performed, the distillation temperature is room temperature to 400 ℃, the reaction pressure is -0.094 MPa, and the stirring rotating speed is 300 r / min. When the distillation temperature is below 250 ℃, the first valve is opened, and the second valve, the third valve and the fourth valve are closed, and all the light fraction below 250 ℃ is collected into the first collection tank. After the collection of the current fraction is completed, the second valve is opened, and the first valve, the third valve and the fourth valve are closed, and all the fraction of 250-300 ℃ is collected into the second collection tank. When the collection of the fraction of 250-300 ℃ is completed, the third valve is opened, and the first valve, the second valve and the fourth valve are closed, and all the fraction of 300-350 ℃ is collected into the third collection tank. When the collection of the fraction of 300-350 ℃ is completed, the fourth valve is opened, and the first valve, the second valve and the third valve are closed, and all the fraction of 350-400 ℃ is collected into the fourth collection tank. When the collection of the fraction of 350-400 ℃ is completed, the remaining components in the distillation kettle after the distillation are discharged into the heavy oil receiving tank. The materials in the second collection tank, the third collection tank and the fourth collection tank are used.

[0085] The distillation material in the second collection tank is input into the first reactor through the metering pump (the input amount is 20 kg / min), and the input is stopped when the material in the reactor reaches 700 kg. The reaction starts at a temperature of 420 ℃, a pressure of 2 MPa, a stirring speed of 200 r / min, and a reaction time of 10 h. After the reaction, the material is used. The distillation material in the third collection tank is input into the second reactor through the metering pump (the input amount is 20 kg / min), and the input is stopped when the material in the reactor reaches 700 kg. The reaction starts at a temperature of 420 ℃, a pressure of 2 MPa, a stirring speed of 200 r / min, and a reaction time of 10 h. After the reaction, the material is used. The distillation material in the fourth collection tank is input into the third reactor through the metering pump (the input amount is 20 kg / min), and the input is stopped when the material in the reactor reaches 700 kg. The reaction starts at a temperature of 430 ℃, a pressure of 2 MPa, a stirring speed of 200 r / min, and a reaction time of 8 h. After the reaction, the material is used.

[0086] The material in the first reactor is input into the distillation tower through the metering pump for devolatilization treatment, the treatment temperature is 400 ℃, the pressure is -0.094 MPa, the nitrogen flow is 5 m 3 ; After the treatment, the material is transported into the fourth reactor through the first metering pump, and the total amount of the material is 100 kg (the input amount is 50 kg / min).

[0087] The material in the second reactor is input into the distillation tower through the metering pump for devolatilization treatment, the treatment temperature is 400 ℃, the pressure is -0.094 MPa, the nitrogen flow is 5 m 3 ; After the treatment, the material is transported into the fourth reactor through the second metering pump, and the total amount of the material is 200 kg (the input amount is 20 kg / min).

[0088] The material in the third reactor is input into the distillation tower through the metering pump for devolatilization treatment, the treatment temperature is 400 ℃, the pressure is -0.094 MPa, the nitrogen flow is 5 m 3 ; After the treatment, the material is transported into the fourth reactor through the third metering pump, and the total amount of the material is 200 kg (the input amount is 20 kg / min).

[0089] After the feeding is completed, the mixing and conditioning start, and the process parameters are set as follows: the treatment temperature is 400 ℃, the pressure is normal, the nitrogen protection is used, the speed is 200 r / min, and the material mixing and stirring are performed for 1 h. After the material is uniformly mixed, the product mesophase pitch is extruded and granulated through the extruder, the temperature of the extruder is set as follows (the four temperature zones are set as 320 ℃, 380 ℃, 380 ℃, and 320 ℃, respectively), the speed is 100 r / min, the nitrogen flow is 5 m 3 / h, the extrusion pressure is 1 MPa, and the yield is 100±10 kg / h.

[0090] The test results of the intermediate pitch prepared in the case 4 are shown in Table 5.

[0091] Table 5 Test results of the intermediate pitch

[0092]

[0093]

[0094] Case 5

[0095] The raw oil slurry (FCC oil slurry) in the storage tank is delivered to the crude oil distillation kettle through a metering pump. Distillation treatment is carried out, distillation temperature: room temperature to 400°C, reaction pressure -0.094 MPa, stirring speed 300 revolutions / min. When the distillation temperature is below 250°C, open the first valve, close the second valve, the third valve and the fourth valve, and all the light fraction below 250°C is collected into the first collection tank; after the current fraction collection is completed, open the second valve, close the first valve, the third valve and the fourth valve, and all the fraction of 250-300°C is collected into the second collection tank; when the fraction of 250-300°C is collected, open the third valve, close the first valve, the second valve and the fourth valve, and all the fraction of 300-350°C is collected into the third collection tank; when the fraction of 300-350°C is collected, open the fourth valve, close the first valve, the second valve and the third valve, and all the fraction of 350-400°C is collected into the fourth collection tank; when the fraction of 350-400°C is collected, the remaining components in the distillation kettle are discharged into the heavy oil receiving tank. The materials in the second collection tank, the third collection tank and the fourth collection tank are ready for use.

[0096] The distillation material in the second collection tank is input into the first reaction kettle through a metering pump (feed amount 20 kg / min), and when the material in the kettle reaches 700 kg, the feeding is stopped. Start the reaction: reaction temperature 415°C, pressure 2 MPa, stirring speed 100 revolutions / min, reaction 11 h, and the material is ready for use after the reaction is completed; the distillation material in the third collection tank is input into the second reaction kettle through a metering pump (feed amount 20 kg / min), and when the material in the kettle reaches 700 kg, the feeding is stopped. Start the reaction: reaction temperature 425°C, pressure 2 MPa, stirring speed 200 revolutions / min, reaction 9 h, and the material is ready for use after the reaction is completed; the distillation material in the fourth collection tank is input into the third reaction kettle through a metering pump (feed amount 20 kg / min), and when the material in the kettle reaches 700 kg, the feeding is stopped. Start the reaction: reaction temperature 425°C, pressure 2 MPa, stirring speed 300 revolutions / min, reaction 11 h, and the material is ready for use after the reaction is completed.

[0097] The material in the first reactor was inputted into the distillation column for devolatilization treatment by the metering pump, the treatment temperature was 395℃, the pressure was -0.094MPa, the nitrogen flow was 8m 3 After the treatment, the material was transported into the fourth reactor by the first metering pump, the total amount of the material was 50kg (the transportation amount was 50kg / min).

[0098] The material in the second reactor was inputted into the distillation column for devolatilization treatment by the metering pump, the treatment temperature was 395℃, the pressure was -0.094MPa, the nitrogen flow was 8m 3 After the treatment, the material was transported into the fourth reactor by the second metering pump, the total amount of the material was 150kg (the transportation amount was 20kg / min).

[0099] The material in the third reactor was inputted into the distillation column for devolatilization treatment by the metering pump, the treatment temperature was 395℃, the pressure was -0.094MPa, the nitrogen flow was 8m 3 After the treatment, the material was transported into the fourth reactor by the third metering pump, the amount of the material was 300kg (the transportation amount was 20kg / min), the total amount of the material was 500kg.

[0100] After the feeding was completed, the mixing and conditioning were started, the process parameters were set as follows: the treatment temperature was 400℃, the normal pressure, the nitrogen protection, the rotation speed was 200r / min, the material mixing and stirring were 3h, when the material was mixed uniformly, the product mesophase pitch was extruded and granulated by the extruder, the temperature of the extruder was set as follows (the four temperature zones were set as 320℃, 380℃, 380℃, 320℃ respectively), the rotation speed was 100r / min, the nitrogen flow was 8m 3 / h, the extrusion pressure was 1.6MPa, the yield was 100±10kg / h.

[0101] The test results of the mesophase pitch prepared in the implementation case 5 were shown in Table 6.

[0102] Table 6 Test results of mesophase pitch

[0103] Name Softening point °C Mesophase content % Carbon residue content % Quinoline insolubles % Yield % Mesophase pitch product 281 100％ 73 6.8 32

[0104] Implementation case 6

[0105] The raw oil slurry (FCC oil slurry) in the storage tank is delivered to the crude oil distillation kettle by a metering pump. Distillation treatment is carried out, distillation temperature: room temperature to 400℃, reaction pressure -0.094 MPa, stirring speed 300 revolutions / min. When the distillation temperature is below 250℃, open the first valve, close the second valve, the third valve and the fourth valve, and all the light fraction below 250℃ is collected into the first collection tank; after the current fraction collection is completed, open the second valve, close the first valve, the third valve and the fourth valve, and all the fraction of 250-300℃ is collected into the second collection tank; when the fraction of 250-300℃ is collected, open the third valve, close the first valve, the second valve and the fourth valve, and all the fraction of 300-350℃ is collected into the third collection tank; when the fraction of 300-350℃ is collected, open the fourth valve, close the first valve, the second valve and the third valve, and all the fraction of 350-400℃ is collected into the fourth collection tank; when the fraction of 350-400℃ is collected, the remaining components in the distillation kettle are discharged into the heavy oil receiving tank. The materials in the second collection tank, the third collection tank and the fourth collection tank are used later.

[0106] The distillation material in the second collection tank is input into the first reaction kettle by a metering pump (the input amount is 20 kg / min), and the input is stopped when the material in the kettle reaches 700 kg. Start the reaction: reaction temperature 415℃, pressure 2 MPa, stirring speed 100 revolutions / min, reaction 11 h, and the material is used later after the reaction is completed; the distillation material in the third collection tank is input into the second reaction kettle by a metering pump (the input amount is 20 kg / min), and the input is stopped when the material in the kettle reaches 700 kg. Start the reaction: reaction temperature 425℃, pressure 2 MPa, stirring speed 200 revolutions / min, reaction 9 h, and the material is used later after the reaction is completed; the distillation material in the fourth collection tank is input into the third reaction kettle by a metering pump (the input amount is 20 kg / min), and the input is stopped when the material in the kettle reaches 700 kg. Start the reaction: reaction temperature 425℃, pressure 2 MPa, stirring speed 300 revolutions / min, reaction 11 h, and the material is used later after the reaction is completed.

[0107] The material in the first reaction kettle is input into a distillation column by a metering pump for devolatilization treatment, the treatment temperature is 395℃, the pressure is -0.094 MPa, and the nitrogen flow is 8 m 3 After the treatment is completed, the material is delivered to the fourth reaction kettle by a first metering pump, and the total amount of the material is 50 kg (the input amount is 50 kg / min).

[0108] The material in the second reaction kettle is input into a distillation column by a metering pump for devolatilization treatment, the treatment temperature is 395℃, the pressure is -0.094 MPa, and the nitrogen flow is 8 m 3After the treatment, the material is delivered into the fourth reactor through the second metering pump, and the total feeding amount is 150 kg (feeding amount 20 kg / min).

[0109] The material in the third reactor is input into the distillation column through the metering pump for devolatilization treatment, the treatment temperature is 395 ℃, the pressure is -0.094 MPa, the nitrogen flow is 8 m 3 After the treatment, the material is delivered into the fourth reactor through the third metering pump, the feeding amount is 300 kg (feeding amount 20 kg / min), and the total feeding amount is 500 kg.

[0110] After the feeding is completed, the mixing and conditioning are started, and the process parameters are set as follows: the treatment temperature is 400 ℃, the normal pressure, the nitrogen protection, the rotating speed is 200 r / min, the material mixing and stirring are 3 h, when the material is uniformly mixed, the product mesophase pitch is extruded and granulated through the extruder, the extruder temperature is set as (the total four temperature zones are set as 300 ℃, 360 ℃, 360 ℃, 300 ℃ respectively), the rotating speed is 100 r / min, the nitrogen flow is 8 m 3 / h, the extrusion pressure is 3 MPa, and the yield is 50±5 kg / h.

[0111] The test results of the mesophase pitch prepared in the embodiment 6 are shown in table 7.

[0112] Table 7 Test results of mesophase pitch

[0113]

[0114]

[0115] The method realizes the stable preparation of mesophase pitch by the process flow of distillation classification, staged polymerization, distillation, conditioning and extrusion, etc. First, the raw oil slurry is distilled and separated, and the raw oil slurry is divided into light aromatic oil with a distillation range of 250-300 ℃, medium aromatic oil with a distillation range of 300-350 ℃, and heavy aromatic oil with a distillation range of 350-400 ℃ according to different distillation ranges. Different polymerization processes are formulated according to the physical and chemical properties of different materials, and mesophase pitches with different properties are prepared. The pitches are mixed according to the proportion to obtain mesophase pitches with different physical and chemical properties, and the stable and controllable preparation of mesophase pitches with different properties from one oil slurry is realized.

[0116] The above only describes the preferred embodiments of the present application, and does not use to limit the technical solutions of the present application in any way, and those skilled in the art should understand that the technical solutions can be simply modified and replaced without departing from the spirit and principles of the present application, and these modifications and replacements also belong to the protection scope covered by the claims.

Claims

1. A mesophase pitch production method characterized by, It comprises the following steps: S1, distillation separation of raw oil slurry, according to the distillation range, the raw oil slurry is divided into light distillate, light aromatic oil, medium aromatic oil and heavy aromatic oil; The distillation temperature of light distillate is room temperature~250℃, the reaction pressure of crude oil distillation still is-0.09MPa~-0.096Mpa, and the stirring speed is 50~300r / min; The distillation temperature of light aromatic oil is 250~300℃, the reaction pressure is-0.08MPa~-0.096MPa, and the stirring speed is 50~300r / min; The distillation temperature of medium aromatic oil is 300~350℃, the reaction pressure of crude oil distillation still is-0.08MPa~-0.096MPa, and the stirring speed is 50~300r / min; The distillation temperature of heavy aromatic oil is 350~400℃, the reaction pressure of crude oil distillation still is-0.08MPa~-0.096MPa, and the stirring speed is 50~300r / min; S2, light aromatic oil, medium aromatic oil and heavy aromatic oil are respectively polymerized and distilled into low softening point mesophase pitch, medium softening point mesophase pitch and high softening point mesophase pitch; In the process of polymerization and distillation of light aromatic oil into low softening point mesophase pitch, the reaction temperature is 400~420℃, the pressure is 1~3MPa, the stirring speed is 50~300r / min, and the reaction time is 5~15h; In the process of polymerization and distillation of medium aromatic oil into medium softening point mesophase pitch, the reaction temperature is 410~430℃, the pressure is 1~3MPa, the stirring speed is 50~300r / min, and the reaction time is 5~10h; In the process of polymerization and distillation of high softening point mesophase pitch into high softening point mesophase pitch, the reaction temperature is 420~450℃, the pressure is 1~3MPa, the stirring speed is 50~300r / min, and the reaction time is 5~10h; S3, low softening point mesophase pitch, medium softening point mesophase pitch and high softening point mesophase pitch are mixed and prepared in different proportions to obtain mesophase pitch with different properties; In the process of mixing and preparation, the temperature is 400℃, the pressure is normal pressure, the stirring speed is 200r / min, and the time is 1~5h; Wherein, S1 and S2 are independent and simultaneous.

2. The mesophase pitch production method according to claim 1, characterized by, The system of mesophase pitch preparation method comprises a crude oil distillation still, a crude oil metering pump, a first collection tank, a second collection tank, a third collection tank, a fourth collection tank, a first metering pump, a second metering pump, a third metering pump, a first reaction kettle, a second reaction kettle, a third reaction kettle and a fourth reaction kettle, the inlet of the crude oil distillation still is connected with the outlet of the crude oil metering pump, and the inlets of the first collection tank, the second collection tank, the third collection tank and the fourth collection tank are connected with the outlet of the crude oil distillation still; The first valve is arranged between the first collection tank and the crude oil distillation still, the second valve is arranged between the second collection tank and the crude oil distillation still, the third valve is arranged between the third collection tank and the crude oil distillation still, and the fourth valve is arranged between the fourth collection tank and the crude oil distillation still; The first valve is arranged between the first collection tank and the crude oil distillation still, the second valve is arranged between the second collection tank and the crude oil distillation still, the third valve is arranged between the third collection tank and the crude oil distillation still, and the fourth valve is arranged between the fourth collection tank and the crude oil distillation still; The outlet of the second collecting tank is connected with the inlet of the first reaction kettle, the outlet of the first reaction kettle is connected with the inlet of the first metering pump; the outlet of the third collecting tank is connected with the inlet of the second reaction kettle, the outlet of the second reaction kettle is connected with the inlet of the second metering pump; the outlet of the fourth collecting tank is connected with the inlet of the third reaction kettle, the outlet of the third reaction kettle is connected with the inlet of the third metering pump; the outlets of the first metering pump, the second metering pump and the third metering pump are all connected with the inlet of the fourth reaction kettle; The outlet of the fourth reaction kettle is connected with an extruding granulator; the bottom of the crude oil distillation kettle is further connected with a heavy oil slurry receiving tank.

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