Petroleum-based coated asphalt with high coking value and low quinoline insolubles and preparation method of petroleum-based coated asphalt

Abstract

The preparation method comprises the following steps: adding a heavy oil raw material and a cross-linking agent into a reactor with non-meshing type reverse rotation double screws, raising the temperature in a nitrogen atmosphere, then replacing reaction gas with air, raising the temperature in the nitrogen atmosphere, and reacting for 2-4 hours at the temperature of 60-80 DEG C to obtain the high-coking-value low-quinoline-insoluble-substance petroleum-based coated asphalt with the high coking value and the low-quinoline-insoluble-substance petroleum-based coated asphalt with the low-quinoline-insoluble-substance petroleum-based coated asphalt. Carrying out constant-temperature stirring oxidation cross-linking reaction to obtain asphalt; and switching the obtained asphalt into a meshing type reverse spiral twin-screw reactor, carrying out screw extrusion degassing treatment, and discharging to obtain the petroleum-based coated asphalt with high coking value and low quinoline insoluble. The softening point (SP) of the prepared coated asphalt is 180-280 DEG C, and toluene insoluble (TI) is gt; 40%, quinoline insoluble (QI) lt; 1%, the coking value gt; the yield is gt; and 55%.

Description

Technical Field

[0001] The present invention relates to the field of coated asphalt preparation, and in particular to a petroleum-based coated asphalt with high coking value and low quinoline insoluble matter and a preparation method thereof. Background Art

[0002] Graphite, with its advantages of high specific capacity, low lithium intercalation and deintercalation platform voltage, reasonable cost, and long cycle life, has become the mainstream negative electrode material for lithium-ion batteries on the market. However, graphite has poor compatibility with organic electrolytes and weak intercalation between its carbon layers. The formation of a solid electrolyte interface (SEI) and intercalation of solvent molecules can lead to irreversible lithium ion consumption, changes in the graphite structure, and exfoliation of the graphite layers, resulting in a decrease in the first-cycle coulombic efficiency, energy density, and cycle performance of lithium-ion batteries. Currently, surface modification of graphite is the mainstream approach to addressing these issues. Coating the graphite particles with a layer of amorphous carbon, which is highly compatible with organic solvents, prevents the co-intercalation of solvent molecules from damaging the graphite structure, mitigates exfoliation, and allows for random insertion of lithium ions, effectively improving the electrochemical properties of graphite, such as high rate, first efficiency, and cycle life. Using coated asphalt to modify the graphite surface offers the advantages of high efficiency and low cost. The preparation of high-quality coated asphalt is currently a key focus of researchers.

[0003] At present, commonly used coated asphalts generally have problems such as low coking value and high quinoline insoluble matter. In the commercially commonly used graphite "dry method" coating asphalt carbon process, the uniformly mixed coating asphalt and graphite material need to be carbonized under an inert gas atmosphere. The higher the residual carbon value of the coating asphalt and the higher the carbonization yield, the better the coating effect on the graphite surface, the more uniform the amorphous carbon layer formed, the better the effect of repairing defects such as cracks and holes on the graphite surface, and the consumption of processes such as secondary coating can be reduced. The lower quinoline insoluble matter can ensure the fluidity of the coating asphalt, and can fully coat the graphite surface during the carbonization process, making the coated graphite surface more uniform and smooth. Therefore, the development of coating asphalt materials with high coking value and low quinoline insoluble matter is particularly important for improving the electrochemical performance of lithium battery negative electrodes.

[0004] To obtain coated asphalt with high coking values ​​and low quinoline insolubles, scholars at home and abroad have conducted extensive research. Patent CN102965136A discloses a method for producing coal tar pitch. Using medium-temperature coal tar pitch as raw material, the process is directly fed into a kettle and reacted at high temperature in an air atmosphere. The resulting asphalt has a softening point of 260-280°C, a coking value of 75.2-75.9%, and a quinoline insoluble content of 25.7-33%.

[0005] Patent CN103897714A discloses a method for preparing high-softening-point asphalt for coating natural graphite negative electrode materials for lithium-ion batteries. The method uses asphalt as raw material and prepares coated asphalt with a softening point of 260-290°C through negative pressure multi-stage oxidation. The quinoline-insoluble matter content is as high as 25-35%.

[0006] Patent CN115093872A discloses a coated asphalt, its preparation method and application. Ethylene tar and catalytic oil slurry are mixed, settled and heated in sequence, followed by oxidation cross-linking catalytic reaction and condensation catalytic reaction. The crude asphalt is then extracted to obtain the coated asphalt. The prepared coated asphalt has a softening point of 240-265°C, a quinoline insoluble matter content of 0.4-1%, a coking value of 75-80%, and a yield of 25-31%. This process is relatively complex and the product yield is low.

[0007] Patent CN109251759A discloses a method for preparing high-softening-point asphalt suitable for use as a raw material for asphalt-based spherical activated carbon. The method uses special asphalt with a softening point of 130-220°C as raw material. Through the synergistic effect of negative pressure extraction-thermal polymerization reaction, the high-softening-point asphalt produced has a softening point of 240-280°C, a toluene-insoluble content of more than 70%, and a quinoline-insoluble content of more than 35%.

[0008] The high coking value coated asphalt prepared above has the problem of excessive quinoline insoluble matter content, or the process route to meet the indicators is too complicated and has poor economic efficiency. Summary of the Invention

[0009] In order to address the deficiencies in the prior art, the present invention aims to provide a petroleum-based coated asphalt with a high coking value and low quinoline insolubles and a preparation method thereof. The prepared coated asphalt has a softening point (SP) of 180-280°C, a toluene insoluble matter (TI) >40%, a quinoline insoluble matter (QI) <1%, a coking value >60%, and a yield >55%.

[0010] In order to achieve the above object, the present invention adopts the following technical solutions:

[0011] A method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insoluble matter comprises the following steps: adding a heavy oil raw material and a cross-linking agent into a reactor with a non-meshing counter-rotating twin-screw, heating the reactor under a nitrogen atmosphere, replacing the reaction gas with air, and subjecting the reactor to a constant temperature stirring oxidation and cross-linking reaction to obtain asphalt; switching the obtained asphalt into an intermeshing counter-rotating twin-screw reactor, subjecting the reactor to screw extrusion degassing treatment, and discharging the asphalt to obtain a petroleum-based coated asphalt with a high coking value and low quinoline insoluble matter.

[0012] Preferably, the heavy oil feedstock is ethylene tar or catalytic oil slurry.

[0013] Preferably, the heavy oil raw material is a mixture of ethylene tar and catalytic oil slurry, and the mass ratio of ethylene tar to catalytic oil slurry is 40:60 to 80:20.

[0014] Preferably, the cross-linking agent is selected from one or more of 2-3 ring aromatic hydrocarbons with 1-2 carbon branches.

[0015] Preferably, the added amount of the cross-linking agent accounts for 2 to 10 wt % of the heavy oil raw material.

[0016] Preferably, the added amount of the cross-linking agent accounts for 3 to 8 wt% of the heavy oil raw material.

[0017] Preferably, the temperature is raised to 300-380° C. at a rate of 2-5° C. / min under 0.4-2 MPa.

[0018] Preferably, the temperature is raised to 320-360° C. at a rate of 2-5° C. / min under 0.5-1 MPa.

[0019] Preferably, the oxidative crosslinking conditions are air flow (L / h) / ethylene tar (kg) = 60 to 300, the reaction time is 0.5 to 6 hours; the screw aspect ratio of the non-meshing counter-rotating twin screw is 20:1 to 50:1, and the screw speed is 20 to 250 r / min.

[0020] Preferably, the oxidative crosslinking conditions are air flow (L / h) / ethylene tar (kg) = 60 to 240, reaction time 1 to 4 hours; the screw aspect ratio of the non-meshing counter-rotating twin screw is 25:1 to 45:1, and the screw speed is 50 to 200 r / min.

[0021] Preferably, the screw segment aspect ratio of the intermeshing counter-rotating twin screw is 30:1 to 60:1, the screw speed is 20 to 100 r / min, the pressure inside the screw is -0.09 to 0.2 MPa, and the temperature is maintained at 250 to 400°C.

[0022] Preferably, the screw segment aspect ratio of the intermeshing counter-rotating twin screw is 36:1 to 48:1, the screw speed is 30 to 80 r / min, the pressure inside the screw is -0.05 to 0.05 MPa, and the temperature is maintained at 280 to 380°C.

[0023] The present invention also claims protection for a petroleum-based coated asphalt with high coking value and low quinoline insoluble matter prepared by the preparation method.

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

[0025] 1) The present invention provides a method for preparing a petroleum-based coated asphalt with high coking value and low quinoline insoluble matter. The preparation of the coated asphalt with high coking value, low quinoline insoluble matter and high product yield is achieved by an oxidative crosslinking method. The prepared coated asphalt has a softening point (SP) of 180-280°C, a toluene insoluble matter (TI) >40%, a quinoline insoluble matter (QI) <1%, a coking value >60%, and a coated asphalt yield >55%. Compared with the existing petroleum-based coated asphalt production process, the coking value of products with the same softening point is increased by 3-10%, and the yield is increased by 10-20%.

[0026] 2) The present invention directly adds heavy oil feedstocks such as ethylene tar and catalytic oil slurry and a crosslinker to a high-temperature, high-pressure reactor equipped with a non-intermeshing, counter-rotating twin-screw extruder. This eliminates the need for pretreatment, ensures uniform stirring and heating, effectively shortens reaction time, and enables continuous production. The crosslinker readily generates methyl radicals, which trigger further free radical formation at low temperatures within the branched polycyclic aromatic hydrocarbons (PAHs) of the heavy oil feedstock. These PAHs undergo oligomerization to form long-chain condensed polycyclic and polynuclear aromatic hydrocarbons, effectively reducing the fluidity of the matrix and disrupting the pre-regularization of the condensed aromatic lamellar molecules, thereby limiting the production of quinoline-insoluble materials. However, an excessive amount of crosslinker generates a large number of free radicals within a short period of time, further forming a large number of macromolecular clusters. This increases the aromaticity of the product, but the degree of condensation is low, creating significant steric resistance to the macromolecules in the reaction system. This hinders further reaction of the 2- to 4-ring aromatics in the reaction system, resulting in a low coke value. Therefore, this patent screens the crosslinker and matches appropriate oxidative crosslinking conditions to promote an increase in coke value while controlling the degree of oxidative crosslinking, reducing the production of quinoline-insoluble materials, and improving product yield.

[0027] 3) The present invention controls the degassing conditions of the screw extrusion after the oxidative cross-linking reaction, utilizes the combination of screw extrusion and a reduced pressure atmosphere to efficiently separate the light components in a short time, further improves the coking value of the product while controlling the amount of quinoline insoluble matter, and realizes the production of coated asphalt with different industrial indicators; compared with the continuous cutting method, the process flow is short and the energy consumption is low; compared with the flash steam stripping method, a large amount of purge gas is not required; compared with the extraction purification method, a large amount of extractant is not required, and the economic benefit is higher. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with the embodiments. Of course, the specific embodiments described here are only used to explain the present invention and are not used to limit the present invention.

[0029] Unless otherwise specified, the chemical reagents and materials in the present invention are purchased from commercial sources or synthesized from commercially purchased raw materials.

[0030] The present invention provides a method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insoluble matter, comprising the following steps: adding heavy oil into a reactor, then adding a cross-linking agent, heating under a nitrogen atmosphere, then replacing the reaction gas with air, and reacting at a constant temperature with stirring to obtain asphalt; decompressing the obtained asphalt at the final temperature stage of the reaction, performing a degassing treatment by screw extrusion, and discharging the asphalt to obtain a petroleum-based coated asphalt with a high coking value and low quinoline insoluble matter.

[0031] Specifically, the heavy oil is ethylene tar or catalytic oil slurry.

[0032] Specifically, the heavy oil is a mixture of ethylene tar and catalytic oil slurry, and the mass ratio of ethylene tar to catalytic oil slurry is 40:60 to 80:20, and can be 40:60, 50:50, 60:40, 70:30, or 80:20.

[0033] Specifically, the cross-linking agent is selected from one or more aromatic rings with short side chains.

[0034] Specifically, the cross-linking agent is methylnaphthalene and / or ethylnaphthalene.

[0035] Specifically, the addition amount of the cross-linking agent is 2-10wt%, which can be 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, and preferably 3-8wt%.

[0036] Specifically, the heating conditions are as follows: heating to 300-380°C at a rate of 2-5°C / min under 0.4-2 MPa; the reaction pressure may be 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, 1.0 MPa, 1.1 MPa, 1.2 MPa, 1.3 MPa, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 1.9 MPa, 2.0 MPa, preferably 0.5-1 MPa; the heating rate may be 2°C / min, 3°C / min, 4°C / min, 5°C / min; the reaction temperature may be 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, preferably 320-360°C.

[0037] Specifically, the oxidative crosslinking conditions are air flow (L / h) / ethylene tar (kg) = 60 to 300, which can be 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, and preferably 60 to 240; the reaction time is 0.5 to 6 h, which can be 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, and preferably 1 to 4 h.

[0038] Specifically, the screw length-to-diameter ratio of the non-meshing counter-rotating twin screw is 20:1-50:1, which can be 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, preferably 25:1-45:1, and the screw speed is 20-250 r / min, preferably 50-200 r / min.

[0039] Specifically, the internal pressure of the intermeshing counter-rotating twin-screw is -0.09~0.2Mpa, which can be -0.09MPa, -0.05MPa, 0MPa, 0.1MPa, 0.2MPa, and preferably -0.05~0.05Mpa; the temperature is maintained at 250~400℃, which can be 250℃, 300℃, 350℃, 400℃, and preferably 280~380℃.

[0040] Specifically, the screw segment aspect ratio of the intermeshing counter-rotating twin screw is 30:1 to 60:1, which can be 30:1, 40:1, 50:1, 60:1, and preferably 36:1 to 48:1; the screw speed is 20 to 100 r / min, which can be 20 r / min, 30 r / min, 40 r / min, 50 r / min, 60 r / min, 70 r / min, 80 r / min, 90 r / min, 100 r / min, and preferably 30 to 80 r / min;

[0041] The present invention also claims protection for a petroleum-based coated asphalt with high coking value and low quinoline insoluble matter prepared by the preparation method.

[0042] The present invention will be further described below with reference to specific examples.

[0043] Example 1

[0044] A method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insolubles comprises the following steps:

[0045] Ethylene tar and 7% methylnaphthalene are added to a reactor with a non-meshing counter-rotating twin-screw (the screw aspect ratio is 30:1 and the rotation speed is 100r / min). Under a nitrogen atmosphere, the reaction pressure is controlled to 0.5MPa, the temperature is raised to 320°C at 5°C / min, the reaction gas is replaced with air, and the air flow rate (L / h) / ethylene tar (kg) = 60. The oxidative cross-linking reaction is carried out for 1h to obtain asphalt; the obtained asphalt is switched to a reactor with a meshing counter-rotating twin-screw for decompression, and degassing treatment is carried out by using the screw. The pressure inside the screw is controlled to 0.1MPa, the screw speed is 30r / min, and the temperature is maintained at 320°C. The discharge material is a petroleum-based coated asphalt with a high coking value and low quinoline insolubles.

[0046] Example 2

[0047] A method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insolubles comprises the following steps:

[0048] Ethylene tar and 7% methylnaphthalene are added to a reactor with a non-meshing counter-rotating twin-screw (the screw aspect ratio is 30:1 and the rotation speed is 100r / min). Under a nitrogen atmosphere, the reaction pressure is controlled to 0.5MPa, the temperature is raised to 320°C at 5°C / min, the reaction gas is replaced with air, and the air flow rate (L / h) / ethylene tar (kg) = 60. The oxidative cross-linking reaction is carried out for 2h to obtain asphalt; the obtained asphalt is switched to a reactor with a meshing counter-rotating twin-screw for decompression, and degassing treatment is carried out by using the screw. The pressure inside the screw is controlled to 0.1MPa, the screw speed is 30r / min, and the temperature is maintained at 320°C. The discharge material is a petroleum-based coated asphalt with a high coking value and low quinoline insolubles.

[0049] Example 3

[0050] A method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insolubles comprises the following steps:

[0051] Ethylene tar and 7% methylnaphthalene are added to a reactor with a non-meshing counter-rotating twin-screw (the screw aspect ratio is 30:1 and the rotation speed is 100r / min). Under a nitrogen atmosphere, the reaction pressure is controlled to 0.5MPa, the temperature is raised to 340°C at 5°C / min, the reaction gas is replaced with air, and the air flow rate (L / h) / ethylene tar (kg) = 60. The oxidative cross-linking reaction is carried out for 3h to obtain asphalt; the obtained asphalt is switched to a reactor with a meshing counter-rotating twin-screw for decompression, and degassing treatment is carried out by using the screw. The pressure inside the screw is controlled to 0.1MPa, the screw speed is 30r / min, and the temperature is maintained at 340°C. The discharge material is a petroleum-based coated asphalt with a high coking value and low quinoline insolubles.

[0052] Example 4

[0053] A method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insolubles comprises the following steps:

[0054] Ethylene tar and 7% methylnaphthalene are added to a reactor with a non-meshing counter-rotating twin-screw (the screw aspect ratio is 30:1 and the rotation speed is 100r / min). Under a nitrogen atmosphere, the reaction pressure is controlled to 0.5MPa, the temperature is raised to 360°C at 5°C / min, the reaction gas is replaced with air, and the air flow rate (L / h) / ethylene tar (kg) = 60. The oxidative cross-linking reaction is carried out for 3h to obtain asphalt; the obtained asphalt is switched to a reactor with a meshing counter-rotating twin-screw for decompression, and degassing treatment is carried out by using the screw. The pressure inside the screw is controlled to 0.1MPa, the screw speed is 30r / min, and the temperature is maintained at 360°C. The discharge material is a petroleum-based coated asphalt with a high coking value and low quinoline insolubles.

[0055] Example 5

[0056] A method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insolubles comprises the following steps:

[0057] Ethylene tar and 7% methylnaphthalene are added to a reactor with a non-meshing counter-rotating twin-screw (the screw aspect ratio is 30:1 and the rotation speed is 100r / min). Under a nitrogen atmosphere, the reaction pressure is controlled to 0.5MPa, the temperature is raised to 360°C at 5°C / min, the reaction gas is replaced with air, and the air flow rate (L / h) / ethylene tar (kg) = 120. The oxidative cross-linking reaction is carried out for 3h to obtain asphalt; the obtained asphalt is switched to a reactor with a meshing counter-rotating twin-screw for decompression, and degassing treatment is carried out by using the screw. The pressure inside the screw is controlled to 0.1MPa, the screw speed is 30r / min, and the temperature is maintained at 360°C. The discharge material is a petroleum-based coated asphalt with a high coking value and low quinoline insolubles.

[0058] Example 6

[0059] A method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insolubles comprises the following steps:

[0060] Ethylene tar and 7% methylnaphthalene are added to a reactor with a non-meshing counter-rotating twin-screw (the screw aspect ratio is 30:1 and the rotation speed is 100r / min). Under a nitrogen atmosphere, the reaction pressure is controlled to 0.5MPa, the temperature is raised to 360°C at 5°C / min, the reaction gas is replaced with air, and the air flow rate (L / h) / ethylene tar (kg) = 60. The oxidative cross-linking reaction is carried out for 2h to obtain asphalt; the obtained asphalt is switched to a reactor with a meshing counter-rotating twin-screw for decompression, and degassing treatment is carried out by using the screw. The pressure inside the screw is controlled to -0.03MPa, the screw speed is 60r / min, and the temperature is maintained at 360°C. The discharge material is a petroleum-based coated asphalt with a high coking value and low quinoline insolubles.

[0061] Example 7

[0062] A method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insolubles comprises the following steps:

[0063] Ethylene tar and 7% methylnaphthalene are added to a reactor with a non-meshing counter-rotating twin-screw (the screw aspect ratio is 30:1 and the rotation speed is 100r / min). Under a nitrogen atmosphere, the reaction pressure is controlled to 0.5MPa, the temperature is raised to 360°C at 5°C / min, the reaction gas is replaced with air, and the air flow rate (L / h) / ethylene tar (kg) = 60. The oxidative cross-linking reaction is carried out for 2h to obtain asphalt; the obtained asphalt is switched to a reactor with a meshing counter-rotating twin-screw for decompression, and degassing treatment is carried out by using the screw. The pressure inside the screw is controlled to -0.05MPa, the screw speed is 60r / min, and the temperature is maintained at 360°C. The discharge material is a petroleum-based coated asphalt with a high coking value and low quinoline insolubles.

[0064] Example 8

[0065] A method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insolubles comprises the following steps:

[0066] Ethylene tar and 7% methylnaphthalene are added to a reactor with a non-meshing counter-rotating twin-screw (the screw aspect ratio is 30:1 and the rotation speed is 100r / min). Under a nitrogen atmosphere, the reaction pressure is controlled to 0.5MPa, the temperature is raised to 360°C at 5°C / min, the reaction gas is replaced with air, and the air flow rate (L / h) / ethylene tar (kg) = 60. The oxidative cross-linking reaction is carried out for 2h to obtain asphalt; the obtained asphalt is switched to a reactor with a meshing counter-rotating twin-screw for decompression, and degassing treatment is carried out by using the screw. The pressure inside the screw is controlled to 0MPa, the screw speed is 60r / min, and the temperature is maintained at 360°C. The discharge material is a petroleum-based coated asphalt with a high coking value and low quinoline insolubles.

[0067] Example 9

[0068] A method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insolubles comprises the following steps:

[0069] Catalytic oil slurry and 7% methylnaphthalene are added to a reactor with a non-meshing counter-rotating twin-screw (the screw aspect ratio is 30:1 and the rotation speed is 100r / min). Under a nitrogen atmosphere, the reaction pressure is controlled to 0.5MPa, the temperature is raised to 360°C at 5°C / min, the reaction gas is replaced with air, and the air flow rate (L / h) / ethylene tar (kg) = 60. The oxidative cross-linking reaction is carried out for 2h to obtain asphalt; the obtained asphalt is switched to a reactor with a meshing counter-rotating twin-screw for decompression, and the screw is used for degassing. The pressure inside the screw is controlled to -0.05MPa, the screw speed is 30r / min, and the temperature is maintained at 360°C. The discharge material is a petroleum-based coated asphalt with a high coking value and low quinoline insolubles.

[0070] Example 10

[0071] A method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insolubles comprises the following steps:

[0072] Ethylene tar and 7% methylnaphthalene are added to a reactor with a non-meshing counter-rotating twin-screw (the screw aspect ratio is 30:1 and the rotation speed is 100r / min). Under a nitrogen atmosphere, the reaction pressure is controlled to 0.5MPa, the temperature is raised to 360°C at 5°C / min, the reaction gas is replaced with air, and the air flow rate (L / h) / ethylene tar (kg) = 60. The oxidative cross-linking reaction is carried out for 2h to obtain asphalt; the obtained asphalt is switched to a reactor with a meshing counter-rotating twin-screw for decompression, and degassing treatment is carried out by using the screw. The pressure inside the screw is controlled to -0.03MPa, the screw speed is 30r / min, and the temperature is maintained at 280°C. The discharge material is a petroleum-based coated asphalt with a high coking value and low quinoline insolubles.

[0073] Comparative Example 1

[0074] A method for preparing a petroleum-based coated asphalt with a high coking value and low quinoline insolubles comprises the following steps:

[0075] Ethylene tar and 7% methylnaphthalene are added to a reactor with ordinary stirring (rotation speed is 100r / min), under nitrogen atmosphere, the reaction pressure is controlled to 0.5MPa, the temperature is raised to 360°C at 5°C / min, the reaction gas is replaced with air, the air flow rate (L / h) / ethylene tar (kg) = 60, and the oxidative cross-linking reaction is carried out for 2h to obtain asphalt; the obtained asphalt is decompressed at the final temperature stage of the reaction, the pressure in the reactor is controlled to -0.03MPa, the screw speed is 60r / min, the temperature is maintained at 360°C, and the discharge is a petroleum-based coated asphalt with high coking value and low quinoline insoluble matter.

[0076] Using ethylene tar and purified catalytic oil slurry from a Sinopec refinery as raw materials, the basic physical properties are shown in Table 1, and the data of the coated asphalt prepared in each embodiment are shown in Table 2.

[0077] Table 1 Raw material properties data

[0078] project Ethylene tar Catalytic slurry <![CDATA[Density, 20 °C, kg / m 3 > 1046.3 1093.1 Residual carbon, w% 10.32 20.38 <![CDATA[Viscosity, mm 2 / s (40 °C)]]> 1979 24 Saturated hydrocarbons, w% 0 5.4 Aromatics, w% 92.1 90.4 Resin + asphalt, w% 7.9 4.2 IBP 170 263 10％ 203 324 50％ 271 387 70％ 417 529 90％ 583 650

[0079] Table 2 Data of coated asphalt prepared in each embodiment

[0080]

[0081] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A method for preparing a petroleum-based coated asphalt with high coking value and low quinoline insoluble matter, characterized in that: The method comprises the following steps: adding heavy oil raw material and cross-linking agent into a reactor with a non-meshing counter-rotating twin-screw, heating under a nitrogen atmosphere, then replacing the reaction gas with air, and performing an oxidation cross-linking reaction with constant temperature stirring; switching the obtained asphalt into a meshing counter-rotating twin-screw reactor, performing screw extrusion degassing treatment, and discharging the asphalt to obtain a petroleum-based coated asphalt with a high coking value and low quinoline insoluble matter.

2. The preparation method according to claim 1, characterized in that The heavy oil raw material is ethylene tar or catalytic oil slurry.

3. The preparation method according to claim 1, characterized in that The heavy oil raw material is a mixture of ethylene tar and catalytic oil slurry, and the mass ratio of ethylene tar to catalytic oil slurry is 40:60 to 80:

20.

4. The preparation method according to claim 1, characterized in that The cross-linking agent is selected from one or more 2-3 ring aromatic hydrocarbons with 1-2 carbon branches.

5. The preparation method according to claim 1, characterized in that The added amount of the cross-linking agent accounts for 2 to 10 wt % of the heavy oil raw material.

6. The preparation method according to claim 1, characterized in that The added amount of the cross-linking agent accounts for 3-8 wt% of the heavy oil raw material.

7. The preparation method according to claim 1, characterized in that The heating condition is to increase the temperature to 300-380°C at 2-5°C / min under 0.4-2 MPa.

8. The preparation method according to claim 1, characterized in that The heating condition is to increase the temperature to 320-360°C at 2-5°C / min under 0.5-1 MPa.

9. The preparation method according to claim 1, characterized in that The oxidative crosslinking conditions are: air flow (L / h) / ethylene tar (kg) = 60-300, reaction time is 0.5-6h; the screw segment aspect ratio of the non-meshing counter-rotating twin screw is 20:1-50:1, and the screw speed is 20-250r / min.

10. The preparation method according to claim 1, characterized in that The oxidative crosslinking conditions are: air flow (L / h) / ethylene tar (kg) = 60-240, reaction time 1-4h; the screw segment aspect ratio of the non-meshing counter-rotating twin screw is 25:1-45:1, and the screw speed is 50-200r / min.

11. The preparation method according to claim 1, characterized in that The screw segment length-diameter ratio of the intermeshing counter-rotating twin-screw is 30:1-60:1, the screw speed is 20-100 r / min, the pressure inside the screw is -0.09-0.2 MPa, and the temperature is maintained at 250-400°C.

12. The preparation method according to claim 1, characterized in that The screw segment length-diameter ratio of the intermeshing counter-rotating twin-screw is 36:1-48:1, the screw speed is 30-80 r / min, the pressure inside the screw is -0.05-0.05 MPa, and the temperature is maintained at 280-380°C.

13. A petroleum-based coated asphalt with high coking value and low quinoline insoluble content prepared by the preparation method according to any one of claims 1 to 12.

Images