Continuous preparation method of petroleum heat-resistant COPNA resin and prepared COPNA resin

Abstract

The invention provides a continuous preparation method of petroleum heat-resistant COPNA resin and the prepared COPNA resin, and relates to the technical field of petroleum deep processing. According to the method, one or more fractions of catalytic cracking oil slurry, ethylene tar, vacuum first-line oil slurry and vacuum second-line oil slurry, which are higher than 300 DEG C and lower than 560 DEG C, are used as raw materials, linear oxygen-containing macromolecules are used as a cross-linking agent, strong-acid protonic acid is used as a catalyst, and the COPNA resin is prepared through catalytic polycondensation reaction under certain conditions. Then polycyclic polynuclear aromatic hydrocarbon macromolecules with specific structures are enriched by utilizing a multistage supercritical extraction process, so that the purposes of further improving the heat resistance and wettability of the COPNA resin and shortening the curing time are achieved, and the large-scale utilization of the COPNA resin in industrial production is promoted.

Description

Technical Field

[0001] The present invention relates to the technical field of deep processing of petroleum, and in particular to a continuous preparation method of a petroleum-based heat-resistant COPNA resin and the prepared COPNA resin. Background Art

[0002] With the heavy-grade crude oil and the transformation of the refining industry, the annual output of heavy residue oil in my country has increased year by year, especially the production capacity of catalytic cracking oil slurry and ethylene tar. Usually these heavy residue oils are used as cheap fuel or asphalt blending components, resulting in extremely low residue oil utilization and product added value, and are prone to serious environmental pollution during use. How to improve the comprehensive utilization rate of heavy residue oil and the added value of its derivative products is one of the outstanding issues facing my country's petrochemical industry.

[0003] The high aromatic properties of heavy residual oil make it a potential high-quality raw material for the preparation of condensed polycyclic polynuclear aromatic resins (COPNA resins). In the production process of COPNA resins, the catalyst induces the activation of crosslinker molecules to generate carbon cations, which then undergo crosslinking reactions with aromatic molecules in the feed oil to generate polycyclic aromatic macromolecules of different molecular weights. Studies have found that COPNA resins prepared from aromatic-rich heavy oil are a mixture of thousands of polycyclic aromatic hydrocarbons condensed together. Due to the large differences in the molecular structure composition and spatial configuration of the resins, it is difficult to carry out the curing, pyrolysis and carbonization processes simultaneously, resulting in poor mechanical properties of carbon-carbon composites produced by combining COPNA resins with other materials, making it difficult to meet industrial production needs, which greatly limits its application areas.

[0004] CN 10375592A provides a method for preparing a condensed polycyclic polynuclear aromatic hydrocarbon resin, wherein the direct coal liquefaction residue is deashed to obtain high-temperature coal tar pitch, and then a catalyst and a crosslinking agent are added to carry out a crosslinking polymerization reaction under certain conditions to obtain a condensed polycyclic polynuclear aromatic hydrocarbon resin with high β resin content and carbonization yield. However, the COPNA resin prepared by this method has a high content of quinoline insoluble matter (QI), which affects its bonding performance.

[0005] CN 105419726A relates to a COPNA resin binder and a preparation method and a use method thereof, wherein coal tar powder is used as a raw material, p-phenylenediol is used as a cross-linking agent, and p-toluenesulfonic acid is used as a catalyst, and a heat treatment is performed at 250-300°C to prepare a COPNA resin, and then the COPNA resin is modified with boron carbide powder and short-cut carbon fibers to improve the bonding strength, heat resistance and shock resistance of the resin. Although this method can improve the performance of the COPNA resin to a certain extent, the complex modification process significantly increases its production cost.

[0006] CN 110283341A provides a petroleum-based COPNA resin and its preparation method and application. First, the FCC oil slurry is extracted and separated to obtain 2-4 ring polycyclic aromatic hydrocarbon components, and then the petroleum extraction separation is cross-linked with plant starch under the action of a catalyst to obtain a petroleum-based COPNA resin. This method uses plant starch instead of terephthalic acid as a cross-linking agent, which reduces the production cost of the COPNA resin to a certain extent, but there are still a lot of plant starch components remaining in the reaction product. Summary of the invention

[0007] One of the purposes of the present invention is to provide a continuous preparation method of a petroleum-based heat-resistant COPNA resin. The multi-stage supercritical extraction treatment technology can enrich macromolecules with similar structural compositions in the catalytic polycondensation product, thereby improving the heat resistance, lubricity and curing performance of the COPNA resin.

[0008] A second object of the present invention is to provide a COPNA resin prepared by the above method.

[0009] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0010] In a first aspect, the present invention provides a method for continuously preparing a petroleum-based heat-resistant COPNA resin, comprising the following steps:

[0011] (1) subjecting a raw material heavy residue oil, a cross-linking agent linear oxygen-containing polymer and a catalyst strong acid proton acid to a catalytic polycondensation reaction to obtain a COPNA resin;

[0012] (2) The COPNA resin was separated into narrow fractions with different molecular weights through a multi-stage supercritical extraction process to obtain an intermediate fraction with a molecular weight range of 470-1000.

[0013] The following is a detailed description:

[0014] Step (1):

[0015] The method uses heavy residual oil as a raw material, linear oxygen-containing polymers as a crosslinking agent, and strongly acidic proton acids as catalysts to prepare COPNA resins through catalytic polycondensation reactions under certain conditions.

[0016] The heavy residue oil in step (1) is the aromatics-rich feedstock oil, including but not limited to one or more fractions of catalytic cracking oil, ethylene tar, first-line oil and second-line oil with a temperature greater than 300° C. and less than 560° C. The fraction can be obtained by vacuum precise distillation of one or more of catalytic cracking oil, ethylene tar, first-line oil and second-line oil.

[0017] The linear oxygen-containing polymer in step (1) is a polyaldehyde and / or polyol polymer, preferably one or more selected from trioxymethylene, triphenylmethylene, polyglyoxal, polyethylene glycol, and polypropylene glycol.

[0018] Further preferably, the cross-linking agent is a mixture of triphenylmethylene and polyethylene glycol, and the mass ratio of triphenylmethylene to polyethylene glycol is 1:1-1:4.

[0019] The strongly acidic proton acid in step (1) is a sulfonic proton acid, preferably one or more selected from benzenesulfonic acid, 1-methyl-4-benzenesulfonic acid, 1,3-m-toluenesulfonic acid, and 1,3,5-trimethylbenzenesulfonic acid.

[0020] In step (1), the heavy residual oil, the catalyst and the cross-linking agent are uniformly mixed in a reactor by mechanical stirring, and the reaction parameters are adjusted to prepare polycondensation products with different polycondensation degrees and different molecular weights. In some embodiments, the amount of the cross-linking agent in the reaction system is 5-15wt% of the mass of the raw material heavy residual oil, and the amount of the catalyst is 3-10wt% of the mass of the raw material heavy residual oil; in some embodiments, the reaction temperature is 100-140°C, and the reaction time is 30-100min.

[0021] Step (2):

[0022] The present invention utilizes a multi-stage supercritical extraction process to enrich polycyclic polynuclear aromatic hydrocarbon macromolecules (COPNA resin) of specific structural composition. Specifically, organic solvents with different solubility parameters are selected, a two-stage multi-stage supercritical extraction process is adopted, and parameters such as the type of extractant, extraction temperature and agent-to-oil ratio are adjusted to separate the polycondensation product into narrow components with different molecular weights, wherein an intermediate component with a molecular weight of 470-1000 is obtained, which is mainly composed of dimers and trimers. The condensed polycyclic polynuclear aromatic hydrocarbon resin of the component has a suitable softening point (100-120°C), good temperature resistance (pyrolysis temperature is greater than 480°C), and exhibits good wettability and self-lubrication when combined with carbon materials, shortens the curing time, and can be widely used in the production of carbon-carbon composite materials with excellent performance.

[0023] In some embodiments, step (2) comprises the following steps:

[0024] The COPNA resin obtained in step (1) first enters the first supercritical extraction tower for supercritical extraction, and obtains light components (components with a molecular weight less than 1000, including unreacted aromatics, alkanes, and dimers and trimers generated by the reaction) at the top of the tower, and obtains heavy components (including tetramers generated by the reaction and components with a molecular weight above tetramers) at the bottom of the tower; the light components then enter the second supercritical extraction tower for supercritical extraction, and obtains light components (unreacted aromatics, alkanes) and catalyst components at the top of the tower, and obtains intermediate components with a molecular weight of 470-1000 (i.e., dimers, trimers, etc.) at the bottom of the tower;

[0025] The extractant used in the first supercritical extraction tower is one or more selected from n-hexane, carbon disulfide, acetonitrile, xylene, nitrogen methyl pyrrolidone, and pyridine, and the agent-oil ratio (mass ratio of the extractant to the raw oil) is 3:1-10:1; the first supercritical extraction tower adopts infrared heating, wherein the top temperature is 380-420°C, the middle temperature is 360-390°C, the bottom temperature is 330-360°C, and the extraction pressure is 4-8MPa;

[0026] The extractant used in the second supercritical extraction tower is one or more selected from n-pentane, acetone, n-hexane, carbon disulfide, and acetonitrile, and the agent-to-oil ratio is 4:1-9:1; the second supercritical extraction tower adopts infrared heating, wherein the top temperature is 270-310°C, the middle temperature is 240-270°C, the bottom temperature is 210-240°C, and the extraction pressure is 0.5-2MPa.

[0027] Preferably, the extractant used in the first supercritical extraction tower is a mixed solvent of acetonitrile and pyridine, and the mass ratio of acetonitrile to pyridine is 3:1-5:1;

[0028] Preferably, the top temperature of the first supercritical extraction tower is 385°C, the middle temperature is 375°C, the bottom temperature is 350°C, and the extraction pressure is 5MPa;

[0029] Preferably, the extractant used in the second supercritical extraction tower is a mixture of n-hexane and carbon disulfide, and the mass ratio of n-hexane to carbon disulfide is 4:1-7:1;

[0030] Preferably, the top temperature of the second supercritical extraction tower is 285°C, the middle temperature is 255°C, the bottom temperature is 220°C, and the extraction pressure is 1.5 MPa.

[0031] Preferably, the heavy component obtained at the bottom of the first supercritical extraction tower can be used as a precursor for preparing asphalt-based carbon fibers after recovering the solvent through vacuum distillation;

[0032] Preferably, the light components and catalyst components obtained from the top of the second supercritical extraction tower are transported back to the reactor.

[0033] In a second aspect, the present invention provides a COPNA resin prepared by the above method.

[0034] The COPNA resin obtained by the invention has a narrow molecular weight distribution, a weight average molecular weight distribution in the range of 470-1000, and a similar molecular structure composition.

[0035] Technical effects:

[0036] The present invention uses petroleum-based aromatic-rich heavy oil as raw material and prepares COPNA resin by catalytic polycondensation reaction. In order to improve the heat resistance, wettability and adhesion of COPNA resin, the present invention innovatively uses polyaldehyde and polyol crosslinking agents to simultaneously introduce triarylmethane structure and diarylmethane structure into the polycyclic polynuclear aromatic molecules to improve the spatial configuration of resin molecules. The triarylmethane structure in the resin molecule can significantly improve the carbonization yield of the resin and enhance the wettability with carbon materials. The diarylmethane structure helps to improve the spatial configuration of the resin molecules, improve the linearity of the polycyclic polynuclear aromatic molecules, increase the β resin content, and enhance the adhesion performance.

[0037] In order to solve the problem that the curing and pyrolysis are difficult to synchronize due to the large difference in the molecular composition of COPNA resin, the present invention innovatively adopts a multi-stage supercritical extraction process and combines it with organic solvents with different solubilities to achieve efficient enrichment of condensed polycyclic polynuclear aromatic resin molecules with a molecular weight of 470-1000. The COPNA resin after supercritical extraction treatment has a narrow molecular weight distribution and similar molecular structure composition. It exhibits high heat resistance and adhesion in the subsequent preparation of carbon-carbon composite materials, greatly improving the mechanical strength of the composite materials.

[0038] The present invention has been described in detail above, but the above embodiments are only illustrative in nature and are not intended to limit the present invention. In addition, this article is not limited by any theory described in the above prior art or invention content or the following examples. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 The figure is a process flow diagram of the continuous preparation method of the petroleum-based heat-resistant COPNA resin of the present invention;

[0040] Diagram: 1-preheating furnace; 2-reactor; 3-1#supercritical extraction tower; 4-2#supercritical extraction tower; 5, 6, 7, 8, 9-pipeline pumps. DETAILED DESCRIPTION

[0041] The present invention is further described below in conjunction with the examples. It should be noted that the following examples are provided for illustrative purposes only and do not constitute a limitation on the scope of the present invention. Unless otherwise specified, the raw materials, reagents, methods, etc. used in the examples are all conventional raw materials, reagents, methods in the art.

[0042] equipment:

[0043] The supercritical extraction tower and fluidized bed device were purchased from Nantong Hua'an Machinery Factory. The 1# supercritical extraction tower is 1-1.5m high, 50-80mm in diameter, and filled with metal spherical fillers with a diameter of 2-20mm. The 2# supercritical extraction tower is 1.2-2.0m high, 20-50mm in diameter, and filled with porous ceramic honeycomb fillers.

[0044] Figure 1 The preheating furnace 1, the reactor 2, the 1# supercritical extraction tower 3, and the 2# supercritical extraction tower 4 are connected in sequence, and the materials are transported through the pipeline pumps therebetween. After the crude oil enters the preheating furnace 1 for heating treatment, it is transported to the reactor 2 by the pipeline pump 5. The reaction product after the reaction under specific conditions is transported to the top feed port of the 1# supercritical extraction tower 3 by the pipeline pump 6, and the extractant is transported to the bottom of the tower by the pipeline pump 7. After the extraction is completed, the light component with a smaller molecular weight flowing out from the top of the 1# extraction tower directly enters the top of the 2# supercritical extraction tower 4 through the pipeline pump 8, and the extractant is transported to the bottom of the tower by the pipeline pump 9. After the extraction is completed, the light component obtained at the top of the 2# supercritical extraction tower 4 is transported to the storage tank, and the COPNA resin obtained at the bottom is transported to the storage tank.

[0045] Example 1

[0046] Under the condition of absolute pressure of 3KPa, 50kg of catalytic cracking oil slurry is subjected to vacuum precision distillation to obtain refined aromatic fraction oil with a temperature greater than 300℃ and less than 560℃. The specific process flow is as follows: Figure 1As shown, the refined aromatic-rich fraction oil is preheated by a preheating furnace 1, 1000 g of the preheated refined aromatic-rich fraction oil is taken and transported to the reactor 2 by a pipeline pump 5, and 30 g of benzenesulfonic acid and 50 g of polyethylene glycol are added to the reactor, and the reaction temperature is adjusted to 100° C. for 60 min, and then the reaction product is transported to the top feed port of the 1# supercritical extraction tower 3 by a pipeline pump 6, and at the same time, the extractant feed switch at the bottom of the extraction tower is opened, and the extractant is transported to the bottom of the extraction tower by a pipeline pump 7, and the top temperature of the extraction tower is set to 410° C., the middle temperature of the tower is set to 380° C., the bottom temperature of the tower is set to 350° C., and the pressure in the extraction tower is set to 100° C. The pressure is 4.5MPa, acetonitrile is selected as the extractant, and the agent-oil ratio in the 1# supercritical extraction tower is 5:1. The effluent from the top of the 1# extraction tower is a light component with a smaller molecular weight, which directly enters the top of the 2# supercritical extraction tower 4 through the pipeline pump 8. At the same time, the extractant feed switch at the bottom of the extraction tower is turned on, and the extractant is transported to the bottom of the extraction tower by the pipeline pump 9. The top temperature of the 2# extraction tower is set to 310°C, the temperature in the middle part of the tower is 270°C, the bottom temperature is 240°C, the pressure in the extraction tower is 1.0MPa, and a mixed solution of n-hexane and carbon disulfide is selected as the extractant. The mass ratio of the two is 5:1, and the agent-oil ratio in the 2# extraction tower is 7:1.

[0047] Among them, the bottom effluent of the 1# extraction tower is a heavy component with a molecular weight greater than 1000. After the solvent is recovered by vacuum distillation, the softening point of this component is about 220°C, which can be used as a precursor for preparing asphalt-based carbon fiber. The top effluent of the 2# extraction tower is a light component and a catalyst component with a molecular weight less than 470. It is directly transported to the reactor by a pipeline pump and can be used as a raw material for secondary utilization. The bottom effluent of the 2# extraction tower is an intermediate component with a molecular weight of 470-1000. The softening point of the B-stage COPNA resin composed of this component is 100°C. After curing treatment, the thermal decomposition starting temperature of the C-stage COPNA resin is 350°C.

[0048] Example 2

[0049] Under the condition of an absolute pressure of 3KPa, 50kg of catalytic cracking oil slurry was subjected to vacuum precision fractionation to obtain a refined aromatic-rich fraction oil with a temperature greater than 300°C and less than 560°C. 1000g of the preheated refined aromatic-rich fraction oil was transported to the reactor by a pipeline pump. At the same time, 50g of benzenesulfonic acid and 100g of triphenylmethane were added to the reactor. The reaction temperature was adjusted to 120°C for 80min. Then, the reaction product was transported to the top feed port of the No. 1 supercritical extraction tower by a pipeline pump. At the same time, the extractant feed switch at the bottom of the extraction tower was turned on. The top temperature of the extraction tower was set to 420°C, the middle temperature of the tower was set to 390°C, and the bottom temperature of the tower was set to 400°C. The temperature is 360°C, the pressure in the extraction tower is 5.0MPa, a mixture of acetonitrile and pyridine (4:1) is selected as the extractant, and the agent-to-oil ratio in the 1# extraction tower is 8:1. The top effluent of the 1# extraction tower is a light component with a smaller molecular weight, which directly enters the top of the 2# supercritical extraction tower through a pipeline pump. At the same time, the extractant feed switch at the bottom of the extraction tower is turned on, and the top temperature of the 2# extraction tower is set to 300°C, the temperature in the middle part of the tower is 250°C, the bottom temperature is 220°C, the pressure in the extraction tower is 1.0MPa, and a mixed solution of n-hexane and carbon disulfide is selected as the extractant. The mass ratio of the two is 5:1, and the agent-to-oil ratio in the 2# extraction tower is 7:1.

[0050] Among them, the bottom effluent of the 1# extraction tower is a heavy component with a molecular weight greater than 880. After the solvent is recovered by vacuum distillation, the softening point of this component is about 190°C, which can be used as a precursor for preparing asphalt-based carbon fiber. The top effluent of the 2# extraction tower is a light component and a catalyst component with a molecular weight less than 500, which is directly transported to the reactor for raw materials by a pipeline pump. The bottom effluent of the 2# extraction tower is an intermediate component with a molecular weight of 500-880. The softening point of the B-stage COPNA resin composed of this component is 110°C. After curing treatment, the thermal decomposition starting temperature of the C-stage COPNA resin is 380°C.

[0051] Example 3

[0052] Under the condition of an absolute pressure of 3KPa, 50kg of catalytic cracking oil slurry was subjected to vacuum precision fractionation to obtain a refined aromatic-rich fraction oil with a temperature greater than 300°C and less than 560°C. 1000g of the preheated refined aromatic-rich fraction oil was taken and transported to the reactor by a pipeline pump. At the same time, 60g of 1-methyl-4-benzenesulfonic acid, 80g of a mixture of triphenylmethane and polyethylene glycol (mass ratio 1:3) were added to the reactor. The reaction temperature was adjusted to 100°C for 60min. Then, the reaction product was transported to the top feed port of the 1# supercritical extraction tower by a pipeline pump. At the same time, the extractant feed switch at the bottom of the extraction tower was turned on. The top temperature of the extraction tower was set to 385°C, the middle temperature of the tower was set to 375°C, the bottom temperature of the tower was set to 350°C, the pressure in the extraction tower was 5.0MPa, and a mixture of acetonitrile and pyridine (4:1) was selected. The extractant is the extractant, and the agent-to-oil ratio in the 1# extraction tower is 5:1. The top effluent of the 1# extraction tower is the light component with a smaller molecular weight, which directly enters the top of the 2# supercritical extraction tower through a pipeline pump. At the same time, the extractant feed switch at the bottom of the extraction tower is turned on, and the top temperature of the 2# extraction tower is set to 310°C, the temperature in the middle part of the tower is 270°C, the bottom temperature is 240°C, the pressure in the extraction tower is 1.0MPa, and a mixed solution of n-hexane and carbon disulfide is selected as the extractant. The mass ratio of the two is 5:1, and the agent-to-oil ratio in the 2# extraction tower is 7:1.

[0053] Among them, the bottom effluent of the 1# extraction tower is a heavy component with a molecular weight greater than 940. After the solvent is recovered by vacuum distillation, the softening point of this component is about 240°C, which can be used as a precursor for preparing asphalt-based carbon fiber. The top effluent of the 2# extraction tower is a light component and a catalyst component with a molecular weight less than 470, which is directly transported to the reactor for raw materials by a pipeline pump. The bottom effluent of the 2# extraction tower is an intermediate component with a molecular weight of 470-940. The softening point of the B-stage COPNA resin composed of this component is 100°C. After curing treatment, the thermal decomposition starting temperature of the C-stage COPNA resin is 410°C.

[0054] Example 4

[0055] Under the condition of an absolute pressure of 3KPa, 50kg of catalytic cracking oil slurry was subjected to vacuum precision fractionation to obtain a refined aromatic-rich distillate oil with a temperature greater than 300°C and less than 560°C. 1000g of the preheated refined aromatic-rich distillate oil was taken and transported to the reactor by a pipeline pump. At the same time, 60g of 1-methyl-4-benzenesulfonic acid, 80g of triphenylmethane and polyethylene glycol mixture (mass ratio 1:3) were added to the reactor. The reaction temperature was adjusted to 100°C for 60min, and then the reaction product was transported to the top feed port of the 1# supercritical extraction tower by a pipeline pump. At the same time, the extractant feed switch at the bottom of the extraction tower was opened, and the top temperature of the extraction tower was set to 385°C, the middle temperature of the tower was 375°C, the bottom temperature of the tower was 350°C, the pressure in the extraction tower was 5.0MPa, and a mixture of acetonitrile and pyridine (4:1 ) is the extractant, and the agent-to-oil ratio in the 1# extraction tower is 5:1. The top effluent of the 1# extraction tower is the light component with a smaller molecular weight, which directly enters the top of the 2# supercritical extraction tower through a pipeline pump. At the same time, the extractant feed switch at the bottom of the extraction tower is turned on, and the top temperature of the 2# extraction tower is set to 285°C, the temperature in the middle part of the tower is 255°C, the bottom temperature is 220°C, the pressure in the extraction tower is 1.5MPa, and a mixture of n-hexane and carbon disulfide is selected as the extractant. The mass ratio of the two is 6:1, and the agent-to-oil ratio in the 2# extraction tower is 7:1.

[0056] Among them, the bottom effluent of the 1# extraction tower is a heavy component with a molecular weight greater than 950. After the solvent is recovered by vacuum distillation, the softening point of this component is about 200°C, which can be used as a precursor for preparing asphalt-based carbon fiber. The top effluent of the 2# extraction tower is a light component and a catalyst component with a molecular weight less than 470, which is directly transported to the reactor for raw materials by a pipeline pump. The bottom effluent of the 2# extraction tower is an intermediate component with a molecular weight of 470-950. The softening point of the B-stage COPNA resin composed of this component is 120°C. After curing treatment, the thermal decomposition starting temperature of the C-stage COPNA resin is 470°C.

[0057] Comparative Example 1

[0058] Under an absolute pressure of 3 KPa, 50 kg of catalytic cracking oil slurry was subjected to vacuum precision distillation to obtain a refined aromatic-rich distillate oil with a temperature greater than 300°C and less than 560°C. 1000 g of the preheated refined aromatic-rich distillate oil was transported to a reactor by a pipeline pump. At the same time, 60 g of 1-methyl-4-benzenesulfonic acid, 80 g of a mixture of triphenylmethane and polyethylene glycol (mass ratio 1:3) were added to the reactor, and the reaction temperature was adjusted to 100°C for 60 min to obtain a B-stage COPNA resin.

[0059] The softening point of the obtained B-stage COPNA resin is 80°C, and after curing, the thermal decomposition starting temperature of the C-stage COPNA resin is 170°C.

[0060] Comparative Example 2

[0061] Under the condition of an absolute pressure of 3KPa, 50kg of catalytic cracking oil slurry was subjected to vacuum precision fractionation to obtain a refined aromatic-rich distillate oil with a temperature greater than 300°C and less than 560°C. 1000g of the preheated refined aromatic-rich distillate oil was taken and transported to the reactor by a pipeline pump. At the same time, 60g of 1-methyl-4-benzenesulfonic acid and 20g of triphenylmethane were added to the reactor. The reaction temperature was adjusted to 100°C for reaction for 60min. Then, the reaction product was transported to the top feed port of the No. 1 supercritical extraction tower by a pipeline pump. At the same time, the extractant feed switch at the bottom of the extraction tower was opened. The top temperature of the extraction tower was set to 385°C, the middle temperature of the tower was set to 375°C, the bottom temperature of the tower was set to 350°C, the pressure in the extraction tower was set to 5.0MPa, and a mixture of acetonitrile and pyridine (4:1) was selected as the extractant. No. 1 The agent-oil ratio in the extraction tower is 5:1. The effluent from the top of the 1# extraction tower is a light component with a smaller molecular weight, which directly enters the top of the 2# supercritical extraction tower through a pipeline pump. At the same time, the extractant feed switch at the bottom of the extraction tower is turned on, and the top temperature of the 2# extraction tower is set to 285°C, the temperature in the middle part of the tower is 255°C, the bottom temperature is 220°C, the pressure in the extraction tower is 1.5MPa, and a mixture of n-hexane and carbon disulfide is selected as the extractant. The mass ratio of the two is 6:1, and the agent-oil ratio in the 2# extraction tower is 7:1.

[0062] Among them, the bottom effluent of the 2# extraction tower is an intermediate component with a molecular weight of 440-910. The softening point of the B-stage COPNA resin composed of this component is 80°C. After curing treatment, the thermal decomposition starting temperature of the C-stage COPNA resin is 270°C.

[0063] Comparative Example 3

[0064] Under the condition of an absolute pressure of 3KPa, 50kg of catalytic cracking oil slurry was subjected to vacuum precision fractionation to obtain a refined aromatic-rich distillate oil with a temperature greater than 300°C and less than 560°C. 1000g of the preheated refined aromatic-rich distillate oil was taken and transported to the reactor by a pipeline pump. At the same time, 60g of 1-methyl-4-benzenesulfonic acid and 60g of polyethylene glycol were added to the reactor. The reaction temperature was adjusted to 100°C for reaction for 60min. Then, the reaction product was transported to the top feed port of the 1# supercritical extraction tower by a pipeline pump. At the same time, the extractant feed switch at the bottom of the extraction tower was turned on. The top temperature of the extraction tower was set to 385°C, the middle temperature of the tower was set to 375°C, the bottom temperature of the tower was set to 350°C, the pressure in the extraction tower was set to 5.0MPa, and a mixture of acetonitrile and pyridine (4:1) was selected as the extractant. #The agent-oil ratio in the extraction tower is 5:1. The effluent from the top of the 1# extraction tower is a light component with a smaller molecular weight, which directly enters the top of the 2# extraction tower through a pipeline pump. At the same time, the extractant feed switch at the bottom of the extraction tower is turned on, and the top temperature of the 2# extraction tower is set to 285°C, the temperature in the middle part of the tower is 255°C, the bottom temperature is 220°C, the pressure in the extraction tower is 1.5MPa, and a mixture of n-hexane and carbon disulfide is selected as the extractant. The mass ratio of the two is 6:1, and the agent-oil ratio in the 2# extraction tower is 7:1.

[0065] Among them, the bottom effluent of the 2# extraction tower is an intermediate component with a molecular weight of 540-990. The softening point of the B-stage COPNA resin composed of this component is 131°C. After curing treatment, the thermal decomposition starting temperature of the C-stage COPNA resin is 255°C.

[0066] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that the technical solutions described in the above embodiments may be modified, or some or all of the technical features thereof may be replaced by equivalents, without departing from the spirit and essence of the claims of the present invention; and these modifications or replacements are still within the scope defined by the claims of the present invention.

Claims

1. A continuous preparation method of a petroleum-based heat-resistant COPNA resin, characterized in that: The following steps are involved: (1) subjecting a raw material heavy residue oil, a cross-linking agent linear oxygen-containing polymer and a catalyst strong acid proton acid to a catalytic polycondensation reaction to obtain a COPNA resin; (2) The COPNA resin was separated into narrow fractions with different molecular weights through a multi-stage supercritical extraction process to obtain an intermediate fraction with a molecular weight range of 470-1000.

2. The method according to claim 1, characterized in that The heavy residual oil in step (1) is one or more fractions of catalytic cracking slurry, ethylene tar, first-line oil slurry, and second-line oil slurry with a temperature greater than 300° C. and less than 560° C.

3. The method according to claim 1, characterized in that The linear oxygen-containing polymer in step (1) is a polyaldehyde and / or polyol polymer, preferably one or more selected from trioxymethylene, triphenylmethylene, polyglyoxal, polyethylene glycol, and polypropylene glycol; Preferably, the cross-linking agent is a mixture of triphenylmethylene oxide and polyethylene glycol, and the mass ratio of triphenylmethylene oxide to polyethylene glycol is 1:1-1:

4.

4. The method according to claim 1, characterized in that: The strongly acidic proton acid in step (1) is a sulfonic proton acid, preferably one or more selected from benzenesulfonic acid, 1-methyl-4-benzenesulfonic acid, 1,3-m-toluenesulfonic acid, and 1,3,5-trimethylbenzenesulfonic acid.

5. The method according to claim 1, characterized in that In the reaction system of step (1), the amount of the crosslinking agent used is 5-15wt% of the weight of the raw material heavy residual oil, and the amount of the catalyst used is 3-10wt% of the weight of the raw material heavy residual oil.

6. The method according to claim 1, characterized in that The reaction temperature of step (1) is 100-140° C., and the reaction time is 30-100 min.

7. The method according to claim 1, characterized in that Step (2) comprises the following steps: The COPNA resin obtained in step (1) first enters a first supercritical extraction tower for supercritical extraction, and a light component is obtained at the top of the tower, and a heavy component is obtained at the bottom of the tower; the light component then enters a second supercritical extraction tower for supercritical extraction, and a light component and a catalyst component are obtained at the top of the tower, and an intermediate component with a molecular weight of 470-1000 is obtained at the bottom of the tower; The extractant used in the first supercritical extraction tower is one or more selected from n-hexane, carbon disulfide, acetonitrile, xylene, nitrogen methyl pyrrolidone, and pyridine, and the agent-oil ratio is 3:1-10:1; the first supercritical extraction tower adopts infrared heating, wherein the top temperature is 380-420°C, the middle temperature is 360-390°C, the bottom temperature is 330-360°C, and the extraction pressure is 4-8MPa; The extractant used in the second supercritical extraction tower is one or more selected from n-pentane, acetone, n-hexane, carbon disulfide, and acetonitrile, and the agent-to-oil ratio is 4:1-9:1; the second supercritical extraction tower adopts infrared heating, wherein the top temperature is 270-310°C, the middle temperature is 240-270°C, the bottom temperature is 210-240°C, and the extraction pressure is 0.5-2MPa.

8. The method according to claim 7, characterized in that The extractant used in the first supercritical extraction column is a mixed solvent of acetonitrile and pyridine, and the mass ratio of acetonitrile to pyridine is 3:1-5:1; Preferably, the top temperature of the first supercritical extraction tower is 385°C, the middle temperature is 375°C, the bottom temperature is 350°C, and the extraction pressure is 5 MPa.

9. The method according to claim 7, characterized in that: The extractant used in the second supercritical extraction tower is a mixture of n-hexane and carbon disulfide, and the mass ratio of n-hexane to carbon disulfide is 4:1-7:1; Preferably, the top temperature of the second supercritical extraction tower is 285°C, the middle temperature is 255°C, the bottom temperature is 220°C, and the extraction pressure is 1.5 MPa.

10. A COPNA resin, characterized in that The method is prepared by any one of claims 1 to 9.

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