CN110283341B - Petroleum-based COPNA resin and preparation method and application thereof - Google Patents
Petroleum-based COPNA resin and preparation method and application thereof Download PDFInfo
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- CN110283341B CN110283341B CN201910589067.6A CN201910589067A CN110283341B CN 110283341 B CN110283341 B CN 110283341B CN 201910589067 A CN201910589067 A CN 201910589067A CN 110283341 B CN110283341 B CN 110283341B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2391/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
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- C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
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Abstract
The invention provides a petroleum-based COPNA resin and a preparation method and application thereof, and relates to the technical field of COPNA resin, wherein the petroleum-based COPNA resin is mainly obtained by crosslinking a petroleum extraction isolate and plant starch, so that the technical problem that the preparation cost of the COPNA resin is higher due to higher cost because the conventional COPNA resin is mainly prepared from crosslinking agents such as terephthalyl alcohol, benzyl alcohol, terephthalyl aldehyde, benzaldehyde or paraformaldehyde as raw materials is solved.
Description
Technical Field
The invention relates to the technical field of COPNA resin, in particular to petroleum-based COPNA resin and a preparation method and application thereof.
Background
Condensed polycyclic aromatic hydrocarbon (COPNA) resin is a novel thermosetting polymer resin which takes a Condensed polycyclic structure as a main body. COPNA resin has good heat resistance, high compressive strength, certain magnetism, excellent corrosion resistance and conductivity, and is widely noticed as a novel carbon material.
The conventional COPNA resin is mainly prepared by heating and polycondensing aromatic compounds such as naphthalene, anthracene and the like, aromatic derivatives such as heavy residual oil, asphalt or coal tar and the like, and crosslinking agents such as terephthalyl alcohol, benzyl alcohol, terephthalyl aldehyde, benzaldehyde or paraformaldehyde and the like, and the preparation cost of the COPNA resin is higher due to the higher cost of the crosslinking agents.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
One of the purposes of the invention is to provide a petroleum-based COPNA resin with low cost of a cross-linking agent.
The second object of the present invention is to provide a method for preparing the petroleum-based COPNA resin.
The third purpose of the present invention is to provide the application of the petroleum-based COPNA resin.
The fourth object of the present invention is to provide a magnetic material, a heat-resistant material, a pressure-resistant material, a corrosion-resistant material or a conductive material prepared from the petroleum-based COPNA resin as a raw material.
The petroleum-based COPNA resin provided by the invention is mainly obtained by crosslinking petroleum extraction isolate and plant starch.
Further, the amount of the plant starch is 10-55 wt%, preferably 17-36 wt% of the petroleum extraction isolate;
preferably, the plant starch is selected from at least one of corn starch, bean starch, tapioca starch, potato starch and lotus root starch.
Further, the petroleum extraction isolate is petroleum asphalt extraction isolate and/or FCC oil slurry extraction isolate;
preferably, the petroleum asphalt extraction isolate is a component with thermal weight loss of more than 80% concentrated between 350 ℃ and 510 ℃ after the petroleum asphalt component in the petroleum refining process is subjected to weight removal and light removal treatment;
preferably, the FCC slurry oil extraction isolate is a 2-4 ring polycyclic aromatic hydrocarbon component obtained after the FCC slurry oil is extracted and separated, and the initial weight loss temperature is more than 200 ℃, the temperature of 95 wt% weight loss is less than 500 ℃, and the weight loss between 300 ℃ and 400 ℃ is more than 75 wt%.
Further, the petroleum-based COPNA resin is mainly obtained by crosslinking petroleum extraction isolate and plant starch under the action of a catalyst.
Further, the amount of the catalyst is 2-30 wt%, preferably 4-12 wt% of the petroleum extraction isolate;
preferably, the catalyst comprises a protic acid;
preferably, the catalyst comprises at least one of p-toluenesulfonic acid, benzenesulfonic acid, sulfuric acid, nitric acid, and aluminum chloride.
The preparation method of the petroleum-based COPNA resin provided by the invention comprises the following steps:
and uniformly mixing the petroleum extraction isolate, the plant starch and an optional catalyst to obtain a raw material mixture, and heating the raw material mixture to enable the petroleum extraction isolate and the plant starch to generate a cross-linking reaction to obtain the petroleum-based COPNA resin.
Further, dissolving the petroleum extraction isolate, the plant starch and the optional catalyst in a solvent, uniformly mixing, and then removing the solvent to obtain a raw material mixture;
preferably, the solvent is an organic solvent;
preferably, the organic solvent includes at least one of acetone, petroleum ether, benzene, and toluene;
preferably, the solvent is used in an amount of 10 to 90 wt%, preferably 30 to 60 wt%, of the petroleum extract isolate.
Further, the raw material mixture is heated in an air atmosphere, a far-infrared air atmosphere, or an inert gas atmosphere, preferably in an air atmosphere or a far-infrared atmosphere.
Further, heating the raw material mixture to 100-250 ℃ for reaction for 2-8h to obtain B-stage petroleum-based COPNA resin;
preferably, the B-stage petroleum-based COPNA resin is heated to 300-500 ℃ and reacts for 2-8h to obtain the C-stage petroleum-based COPNA resin.
The third purpose of the invention is to provide the application of the petroleum-based COPNA resin in magnetic materials, heat-resistant materials, pressure-resistant materials, corrosion-resistant materials or conductive materials.
The fourth object of the present invention is to provide a magnetic material, a heat-resistant material, a pressure-resistant material, a corrosion-resistant material or a conductive material prepared from the petroleum-based CONPA resin provided by the present invention.
The petroleum-based COPNA resin provided by the invention takes cheap and easily available plant starch as a cross-linking agent, the plant starch is rich in hydroxyl functional groups, the cross-linking effect is good, the preparation cost of the COPNA resin can be obviously reduced, the basic performance of the COPNA resin can be effectively improved, and the application range of the COPNA resin is expanded.
The preparation process of the petroleum-based COPNA resin provided by the invention is simple, the operation is convenient, the preparation cost of the petroleum-based COPNA resin can be effectively reduced, and the application range of the COPNA resin is expanded.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to one aspect of the present invention, there is provided a petroleum-based COPNA resin obtained by crosslinking a petroleum extract isolate with a vegetable starch.
The existing cross-linking agent for preparing the COPNA resin is selected from benzene dimethanol, benzyl alcohol, terephthalaldehyde, benzaldehyde or paraformaldehyde, and the price is high, so that the cost of the COPNA resin is high, and the application range of the COPNA resin is limited.
The petroleum-based COPNA resin provided by the invention takes cheap and easily available plant starch as a cross-linking agent, the plant starch is rich in hydroxyl functional groups, the cross-linking effect is good, the preparation cost of the COPNA resin can be obviously reduced, the basic performance of the COPNA resin can be effectively improved, and the application range of the COPNA resin is expanded.
In a preferred embodiment of the invention, the vegetable starch is used in an amount of 10-55 wt% of the petroleum extract isolate.
The basic performance of the petroleum-based COPNA is improved by controlling the dosage of the plant starch to be 10-55 wt% of the petroleum extraction isolate so as to improve the crosslinking degree of the petroleum extraction isolate and the plant starch, and particularly when the dosage of the plant starch is 17-36 wt% of the petroleum extract, the plant starch is not wasted, and the basic performance of the obtained petroleum-based COPNA is more excellent.
Typically, but not by way of limitation, the vegetable starch is used in an amount of 10 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 52 wt%, or 55 wt% of the petroleum extract isolate.
In a preferred embodiment of the present invention, the plant starch is selected from one or more of corn starch, bean starch, tapioca starch, potato starch and lotus root starch. That is, the plant starch may be any one of corn starch, bean starch, tapioca starch, potato starch or lotus root starch, or a mixture of any two of the above starches, such as a mixture of corn starch and bean starch or a mixture of bean starch and tapioca starch, or a mixture of any three or more of the above starches, such as a mixture of corn starch, bean starch and tapioca starch, or a mixture of bean starch, tapioca starch, potato starch and lotus root starch.
In a preferred embodiment of the invention, the petroleum extract isolate is a petroleum pitch extract isolate and/or a FCC oil slurry extract isolate.
The term "and/or" as used herein means that the petroleum extract isolate can be either a petroleum pitch extract isolate or a FCC oil slurry extract isolate, or a mixture of a petroleum pitch extract isolate and a FCC oil slurry extract isolate.
In a preferred embodiment of the invention, the petroleum asphalt extraction isolate is a component with the thermal weight loss of more than 80 percent concentrated between 350 ℃ and 510 ℃ after the petroleum asphalt component in the petroleum refining process is subjected to weight removal and light removal treatment. The petroleum asphalt extraction isolate has a relatively regular and uniform structure, the structure regularity of the COPNA resin obtained after the petroleum asphalt extraction isolate is crosslinked with plant starch is high, the viscosity of the B-stage petroleum-based COPNA resin is high, the content of beta resin is high, and the carbonization yield of the C-stage petroleum-based COPNA resin is high.
In a preferred embodiment of the invention, the FCC slurry oil extraction isolate is a 2-4 ring polycyclic aromatic hydrocarbon component obtained after the FCC slurry oil is extracted and separated, and the initial weight loss temperature is more than 200 ℃, the temperature of 95 wt% weight loss is less than 500 ℃, and the weight loss between 300 ℃ and 400 ℃ is more than 75 wt%. The FCC slurry oil extraction isolate has a relatively regular and uniform structure, the structure regularity of the COPNA resin obtained after cross-linking with the plant starch is high, the viscosity of the B-stage petroleum-based COPNA resin is high, the content of beta resin is high, and the carbonization yield of the obtained C-stage petroleum-based COPNA resin is high.
In addition, the 2-4 ring condensed ring aromatic hydrocarbon component comprises one or more of a 2 ring condensed ring aromatic hydrocarbon component, a 3 ring condensed ring aromatic hydrocarbon component and a 4 ring condensed ring aromatic hydrocarbon component.
In a preferred embodiment of the invention, the petroleum-based COPNA resin is obtained by crosslinking a petroleum extract isolate with a vegetable starch in the presence of a catalyst.
By adding the catalyst, the crosslinking reaction efficiency of the petroleum extraction isolate and the plant starch can be effectively improved, and the crosslinking reaction temperature is reduced, so that the preparation cost of the petroleum-based COPNA resin is further reduced.
In a preferred embodiment of the invention, the catalyst is used in an amount of 2 to 30 wt% of the petroleum extract isolate.
The catalyst is used in 2-30 wt% of the petroleum extractive isolate to reach high catalytic efficiency and short crosslinking reaction time, and especially when the catalyst is used in 4-15 wt% of the petroleum extractive isolate, the catalyst has high catalytic efficiency and short crosslinking reaction time.
Typically, but not by way of limitation, the catalyst is used in an amount of 2 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt% of the petroleum extract isolate.
In a preferred embodiment of the present invention, the catalyst is protonic acid to improve the efficiency of the cross-linking reaction between the petroleum extract isolate and the plant starch and to shorten the reaction time.
In a preferred embodiment of the present invention, the catalyst is selected from one or more of p-toluenesulfonic acid, benzenesulfonic acid, sulfuric acid, nitric acid and aluminum chloride. That is, the catalyst may be any one of p-toluenesulfonic acid, benzenesulfonic acid, sulfuric acid, nitric acid and aluminum chloride, or may be a mixture of any two of the above substances, such as a mixture of p-toluenesulfonic acid and benzenesulfonic acid, or a mixture of sulfuric acid and aluminum chloride, or may be a mixture of any three or more of the above substances, such as a mixture of p-toluenesulfonic acid, benzenesulfonic acid and sulfuric acid, or a mixture of p-toluenesulfonic acid, benzenesulfonic acid, sulfuric acid and aluminum chloride.
According to a second aspect of the present invention, there is provided a method for preparing the above petroleum-based COPNA resin, comprising the steps of:
and uniformly mixing the petroleum extraction isolate, the plant starch and an optional catalyst to obtain a raw material mixture, and heating the raw material mixture to enable the petroleum extraction isolate and the plant starch to generate a cross-linking reaction to obtain the petroleum-based COPNA resin.
The preparation method of the petroleum-based COPNA resin provided by the invention has the advantages of simple process and convenience in operation, and can effectively reduce the preparation cost of the petroleum-based COPNA resin and expand the application range of the COPNA resin.
In a preferred embodiment of the present invention, the petroleum extract isolate, the plant starch and optionally the catalyst are dissolved in a solvent and mixed well, and then the solvent is removed to obtain a feedstock mixture.
The petroleum extraction separator, the plant starch and the optional catalyst are dissolved and uniformly mixed in the dissolving process, and then the solvent is removed, so that the petroleum extraction separator, the plant starch and the optional catalyst in the raw material mixture are dissolved and sufficiently mixed, the uniformity of mixing of all raw materials in the raw material mixture is improved, and the uniformity of the performance of the obtained petroleum-based COPNA resin is further improved.
In a preferred embodiment of the present invention, the solvent is an organic solvent, which is beneficial to improve the solubility of the petroleum extract isolate, the plant starch and the catalyst in the solvent, thereby being beneficial to more uniform mixing of the petroleum extract isolate, the plant starch and the catalyst in the solvent.
In a further preferred embodiment of the present invention, the organic solvent is selected from at least one of acetone, petroleum ether, benzene and toluene. That is, the organic solvent may be any one of acetone, petroleum ether, benzene and toluene, or a mixture of any two of acetone, petroleum ether, benzene and toluene, such as a mixture of acetone and petroleum ether, or a mixture of any three or four of acetone, petroleum ether, benzene and toluene, such as a mixture of acetone, petroleum ether and benzene, or a mixture of acetone, petroleum ether, benzene and toluene.
In a preferred embodiment of the present invention, the solvent is used in an amount of 10 to 90 wt% based on the petroleum extract isolate to reduce the waste of the solvent while ensuring that the solvent can dissolve the petroleum extract isolate, the vegetable starch and the catalyst, and more preferably in an amount of 30 to 60 wt% based on the petroleum extract isolate.
Typically, but not by way of limitation, the solvent is used in an amount of 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 70 wt%, 80 wt%, or 90 wt% of the petroleum extract isolate.
In a preferred embodiment of the present invention, the raw material mixture is heated in an air atmosphere, a far-infrared air atmosphere, or an inert gas atmosphere.
In a further preferred embodiment of the present invention, the heating of the raw material mixture under an air atmosphere includes one of charging the raw material mixture into a crucible, heating in an oven or a muffle furnace under an air atmosphere, charging the raw material mixture into a three-necked flask, heating on a heating mantle under an air atmosphere, or charging the raw material mixture into a hydrothermal synthesis vessel filled with air, heating in an oven.
In a further preferred embodiment of the present invention, the heating of the raw material mixture in the far-infrared air atmosphere includes charging the raw material mixture into a far-infrared oven for heating.
In a further preferred embodiment of the present invention, the heating of the raw material mixture under an inert gas atmosphere includes one of charging the raw material mixture into a crucible and heating in an oven or a muffle furnace filled with an inert gas, charging the raw material mixture into a three-necked flask and heating on a heating mantle filled with an inert gas, or charging the raw material mixture into a hydrothermal synthesis kettle filled with an inert gas and heating in an oven.
The inert gas includes, but is not limited to, one or more of nitrogen, argon or helium, that is, the inert gas may be one of nitrogen, argon or helium, or a mixture of any two of the gases, such as a mixture of nitrogen and argon, or a mixture of nitrogen and helium, or a mixture of the three gases, such as a mixture of nitrogen, argon and helium.
In a further preferred embodiment of the present invention, heating the raw materials in an air atmosphere or far infrared air atmosphere can effectively lower the synthesis temperature of the petroleum-based COPNA resin in an inert gas atmosphere, thereby reducing the energy consumption and cost of the petroleum-based COPNA resin to some extent.
In a preferred embodiment of the invention, the raw material mixture is subjected to a crosslinking reaction in a hydrothermal kettle, which is more favorable for realizing high-temperature and high-pressure control, thereby being more favorable for catalytic synthesis of petroleum-based COPNA resin and obviously reducing the synthesis time of the petroleum-based CONPA resin.
In a preferred embodiment of the present invention, the raw material mixture is heated to 100 ℃ and 250 ℃ for reaction for 2-8h to obtain the B-staged petroleum-based COPNA resin.
Typically, but not by way of limitation, the temperature at which the feedstock mixture is heated to produce the B-stage petroleum-based COPNA resin is 100, 120, 150, 180, 200, 220, or 250 ℃ and the heating time is, for example, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, or 8 hours.
In a preferred embodiment of the present invention, the B-stage petroleum-based COPNA resin is heated to 300 ℃ and 500 ℃ for reaction for 2-8h to obtain the C-stage petroleum-based COPNA resin.
Typically, but not by way of limitation, the B-stage petroleum-based COPNA resin is heated to produce the C-stage petroleum-based COPNA resin at a temperature of 300, 320, 150, 380, 400, 420, 450, 480, or 500 ℃ for a time period of, for example, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, or 8 hours.
According to a third aspect of the present invention, the present invention provides the use of the above-mentioned petroleum-based COPNA resin in a magnetic material, a heat-resistant material, a pressure-resistant material, a corrosion-resistant material or an electrically conductive material.
In a fourth aspect of the present invention, the present invention provides a magnetic material, a heat-resistant material, a compression-resistant material, a corrosion-resistant material or a conductive material prepared from the petroleum-based CONPA resin provided by the present invention.
The technical solution provided by the present invention is further described below with reference to examples and comparative examples.
In the raw materials for preparing the petroleum-based CONPA resin, petroleum asphalt extraction isolate is a component in which the thermal weight loss of more than 80 percent is concentrated between 350 ℃ and 510 ℃ after the petroleum asphalt component in the petroleum refining process is subjected to weight removal and light removal; the FCC oil slurry extraction isolate is a 2-4 ring polycyclic aromatic hydrocarbon component obtained after the FCC oil slurry is extracted and separated, the initial weight loss temperature is more than 200 ℃, the weight loss temperature of 95 wt% is less than 500 ℃, the weight loss between 300 ℃ and 400 ℃ is over 75 wt%, and other raw materials are all commercial products unless specially stated.
Preparation of petroleum-based COPNA resin by using FCC (fluid catalytic cracking) slurry oil extraction isolate as raw material
Examples 1 to 1
Respectively weighing 50.0g of FCC slurry oil extraction isolate, 12.5g of corn starch cross-linking agent, 2.5g of p-toluenesulfonic acid catalyst and 20mL of toluene solvent, mixing the FCC slurry oil extraction isolate, the corn starch cross-linking agent, the p-toluenesulfonic acid catalyst and the toluene solvent in a 200mL crucible, stirring uniformly, transferring the mixture into a rotary evaporator to perform rotary evaporation at 115 ℃ to recover the toluene solvent, transferring a raw material mixture obtained after evaporation into a 150mL high-temperature high-pressure hydrothermal synthesis kettle, screwing down a kettle cover, placing the hydrothermal synthesis kettle in a 160 ℃ oven to process for 5 hours to obtain B-stage petroleum-based COPNA resin, wherein the number is B-C-1-1, cooling, taking part of the material to analyze, continuously placing the rest part of the material in a 350 ℃ muffle furnace to perform continuous processing for 4 hours to obtain C-stage petroleum-based COPNA resin, wherein the number is C-C-1-1.
Examples 1 to 2
Respectively weighing 50.0g of FCC slurry oil extraction isolate, 12.5g of cassava starch cross-linking agent, 2.5g of p-toluenesulfonic acid catalyst and 35mL of toluene solvent, mixing the FCC slurry oil extraction isolate, 12.5g of cassava starch cross-linking agent, 2.5g of p-toluenesulfonic acid catalyst and 35mL of toluene solvent in a 200mL crucible, uniformly stirring, transferring the mixture into a rotary evaporator to perform rotary evaporation at 115 ℃ to recover the toluene solvent, transferring the raw material mixture obtained after evaporation into a 150mL high-temperature high-pressure hydrothermal synthesis kettle, replacing air in the kettle with nitrogen, screwing down a kettle cover, placing the hydrothermal synthesis kettle in a 180 ℃ far infrared oven to perform treatment for 4h to obtain a B-stage petroleum-based COPNA resin, cooling the part of the material with the number of B-C-1-2, analyzing the part of the material with the number of B-C-1-2, and continuously treating the rest of the material in a 400 ℃ far infrared oven for 4h to obtain a C-stage petroleum-based COPNA resin with the number of C-1-2.
Examples 1 to 3
Respectively weighing 50.0g of FCC slurry oil extraction isolate, 12.5g of potato starch cross-linking agent, 2.5g of p-toluenesulfonic acid catalyst and 25mL of toluene solvent, mixing in a 200mL crucible, stirring uniformly, transferring to a rotary evaporator for rotary evaporation at 115 ℃ to recover the toluene solvent, transferring the raw material mixture obtained after evaporation to the 200mL crucible, placing the crucible in a far infrared oven at 200 ℃ for treatment for 4h to obtain B-stage petroleum-based COPNA resin, cooling the No. B-C-3, taking part of the material for analysis, placing the rest in a far infrared oven at 300 ℃ for continuous treatment for 4h to obtain C-stage petroleum-based COPNA resin, the No. C-C-3.
Examples 1 to 4
Respectively weighing 50.0g of FCC slurry oil extraction isolate, 12.5g of lotus root starch cross-linking agent, 2.5g of p-toluenesulfonic acid catalyst and 40mL of toluene solvent, mixing the mixture in a 200mL crucible, stirring uniformly, transferring the mixture to a rotary evaporator to perform rotary evaporation at 115 ℃ to recover the toluene solvent, transferring the evaporated raw material mixture to the 200mL crucible, placing the crucible in a far infrared oven at 180 ℃ under a nitrogen atmosphere to perform treatment for 6 hours to obtain B-stage petroleum-based COPNA resin, cooling the B-C-1-4 to obtain a part of the material for analysis, continuously placing the rest part in a far infrared baking oven at 400 ℃ under a nitrogen atmosphere to perform treatment for 6 hours to obtain C-stage petroleum-based COPNA resin, wherein the C-C-1-4 is the number.
Examples 1 to 5
Respectively weighing 50.0g of extract separated from FCC slurry oil, 12.5g of corn starch cross-linking agent, 2.5g of p-toluenesulfonic acid catalyst and 30mL of toluene solvent, mixing the mixture in a 200mL crucible, stirring uniformly, transferring the mixture to a rotary evaporator to perform rotary evaporation at 115 ℃ to recover the toluene solvent, transferring the evaporated raw material mixture to a 200mL three-neck flask, stirring the three-neck flask at 180 ℃ in nitrogen atmosphere for 5 hours to obtain B-stage petroleum-based COPNA resin, wherein the number is B-C-1-5, cooling, taking part of the material to analyze, continuously placing the rest part in a roasting furnace at 400 ℃ in air atmosphere for continuous treatment for 5 hours to obtain C-stage petroleum-based COPNA resin, wherein the number is C-C-1-5.
Examples 1 to 6
Respectively weighing 50.0g of FCC slurry oil extraction isolate, 10.0g of corn starch cross-linking agent, 3.75g of p-toluenesulfonic acid catalyst and 30mL of toluene solvent, mixing the mixture in a 200mL crucible, stirring uniformly, transferring the mixture to a rotary evaporator for rotary evaporation at 115 ℃ to recover the toluene solvent, transferring the evaporated raw material mixture to a 150mL high-temperature high-pressure hydrothermal synthesis kettle, replacing the air in the kettle with argon, placing the hydrothermal kettle in a 200 ℃ far infrared oven for treatment for 8h to obtain B-stage petroleum-based COPNA resin, wherein the number is B-C-1-6, cooling, taking part of the material for analysis, continuously placing the rest in a roasting furnace at 500 ℃ in an air atmosphere for continuous treatment for 5h to obtain C-stage petroleum-based COPNA resin, wherein the number is C-C-1-6.
Examples 1 to 7
Respectively weighing 50.0g of FCC slurry oil extraction isolate, 8.5g of corn starch cross-linking agent, 2g of p-toluenesulfonic acid catalyst and 15mL of toluene solvent, mixing the FCC slurry oil extraction isolate, 8.5g of corn starch cross-linking agent, 2g of p-toluenesulfonic acid catalyst and 15mL of toluene solvent in a 200mL crucible, uniformly stirring, transferring the mixture into a rotary evaporator, carrying out rotary evaporation at 115 ℃ to recover the toluene solvent, transferring a raw material mixture obtained after evaporation into a 150mL high-temperature high-pressure hydrothermal synthesis kettle, replacing air in the kettle with argon, placing the hydrothermal kettle in a 200 ℃ far infrared oven for treatment for 8h to obtain B-stage petroleum-based COPNA resin, wherein the number is B-C-1-7, cooling, taking part of the material for analysis, continuously placing the rest in a roasting furnace at 500 ℃ for continuous treatment for 5h to obtain C-stage-based petroleum COPNA resin, wherein the number is C-C-1-7.
Examples 1 to 8
Respectively weighing 50.0g of FCC slurry oil extraction isolate, 18g of corn starch cross-linking agent, 6g of p-toluenesulfonic acid catalyst and 40mL of toluene solvent, mixing the FCC slurry oil extraction isolate, the corn starch cross-linking agent, the p-toluenesulfonic acid catalyst and the toluene solvent in a 200mL crucible, stirring uniformly, transferring the mixture into a rotary evaporator, carrying out rotary evaporation at 115 ℃ to recover the toluene solvent, transferring a raw material mixture obtained after evaporation into a 150mL high-temperature high-pressure hydrothermal synthesis kettle, replacing air in the kettle with argon, placing the hydrothermal kettle in a far infrared oven at 200 ℃ for treatment for 8h to obtain B-stage petroleum-based COPNA resin, wherein the number is B-C-1-8, cooling, taking part of the material for analysis, continuously placing the rest part in a roasting furnace at 500 ℃ for treatment for 5h to obtain the C-stage PNA petroleum-based COPNA resin, wherein the number is C-C-1-8.
Comparative examples 1 to 1
Respectively weighing 50.0g of FCC slurry oil extraction isolate, 12.5g of p-xylylene glycol cross-linking agent and 2.5g of p-toluenesulfonic acid catalyst, mixing the components in a 200mL three-neck flask, uniformly stirring, heating at 160 ℃ in a nitrogen atmosphere for 5 hours to obtain a B-stage petroleum-based COPNA resin, cooling part of the material with the number of DB-C-1-1, analyzing the cooled part, and continuously placing the rest part in an official furnace at 350 ℃ for continuous treatment for 4 hours to obtain a C-stage petroleum-based COPNA resin with the number of DC-C-1-1.
Test example 1
The B-stage petroleum-based COPNA resin and the C-stage petroleum-based COPNA resin prepared in examples 1-1 to 1-8 and comparative example 1-1 were subjected to performance tests, the test results of which are shown in Table 1; the test method for beta resin content therein is ASTM D5294-1992; test method for Ash SH/T0422-2000; the method for testing the softening point is GB/T4507-1984; the residual carbon content and TGA (thermo-gravimetric Analysis) onset decomposition temperature of the cured product heated to 800 ℃ were determined by the conventional laboratory methods and will not be described in detail.
TABLE 1
As can be seen from the comparison between examples 1-1 to 1-8 and comparative example 1-1, the B-stage petroleum-based COPNA resin and C-stage petroleum-based COPNA resin prepared from FCC slurry extract isolates and vegetable starch in examples 1-1 to 1-8 have excellent basic properties, which are significantly better than those of comparative example 1-1.
Secondly, preparing petroleum-based COPNA resin by using petroleum asphalt extraction isolate as raw material
Example 2-1
Respectively weighing 50.0g of petroleum asphalt extraction isolate, 12.5g of corn starch cross-linking agent, 2.5g of p-toluenesulfonic acid catalyst and 20mL of toluene solvent, mixing the petroleum asphalt extraction isolate, 12.5g of corn starch cross-linking agent, 2.5g of p-toluenesulfonic acid catalyst and 20mL of toluene solvent in a 200mL crucible, uniformly stirring, transferring the mixture into a rotary evaporator to perform rotary evaporation at 115 ℃ to recover the toluene solvent, transferring a raw material mixture obtained after evaporation into a 150mL high-temperature high-pressure hydrothermal synthesis kettle, screwing down a kettle cover, placing the hydrothermal synthesis kettle in a 160 ℃ oven to perform treatment for 5 hours to obtain B-stage COPNA resin, cooling down the number B-C-2-1, taking part of the material to perform analysis, continuously placing the rest part in a 350 ℃ muffle furnace to perform continuous treatment for 4 hours to obtain C-stage COPNA resin, the number C-C-2-1.
Examples 2 to 2
Respectively weighing 50.0g of petroleum asphalt extraction isolate, 12.5g of cassava starch cross-linking agent, 2.5g of p-toluenesulfonic acid catalyst and 35mL of toluene solvent, mixing the petroleum asphalt extraction isolate, the cassava starch cross-linking agent, the p-toluenesulfonic acid catalyst and the toluene solvent in a 200mL crucible, uniformly stirring, transferring the mixture into a rotary evaporator to perform rotary evaporation at 115 ℃ to recover the toluene solvent, transferring a raw material mixture obtained after evaporation into a 150mL high-temperature high-pressure hydrothermal synthesis kettle, replacing air in the kettle with nitrogen, screwing a kettle cover, placing the hydrothermal synthesis kettle in a 180 ℃ far infrared oven to perform treatment for 4h to obtain a B-stage COPNA resin, cooling the number of the B-stage COPNA resin to obtain a part of material, analyzing the part of material, the number of the B-C-2-2, and continuously placing the rest part of the material in a 400 ℃ far infrared oven to perform treatment for 4h to obtain a C-stage COPNA resin, the number of the C-C-2-2.
Examples 2 to 3
Respectively weighing 50.0g of petroleum asphalt extraction isolate, 12.5g of potato starch cross-linking agent, 2.5g of p-toluenesulfonic acid catalyst and 25mL of toluene solvent, mixing in a 200mL crucible, stirring uniformly, transferring to a rotary evaporator for rotary evaporation at 115 ℃ to recover the toluene solvent, transferring the evaporated raw material mixture to the 200mL crucible, placing the crucible in a far infrared oven at 200 ℃ under an air atmosphere for 4h to obtain B-stage COPNA resin, cooling to obtain a part of material for analysis after numbering B-C-2-3, and continuously placing the rest in a far infrared oven at 300 ℃ under an air atmosphere for continuous treatment for 4h to obtain C-stage COPNA resin, numbering C-C-2-3.
Examples 2 to 4
Respectively weighing 50.0g of petroleum asphalt extraction isolate, 12.5g of lotus root starch cross-linking agent, 2.5g of p-toluenesulfonic acid catalyst and 40mL of toluene solvent, mixing in a 200mL crucible, stirring uniformly, transferring to a rotary evaporator for rotary evaporation at 115 ℃ to recover the toluene solvent, transferring the raw material mixture obtained after evaporation to the 200mL crucible, placing the crucible in a far infrared oven at 180 ℃ under a nitrogen atmosphere for treatment for 6h to obtain B-stage COPNA resin, cooling to obtain a part of material with the number of B-C-2-4, analyzing, placing the rest in a far infrared oven at 400 ℃ under a nitrogen atmosphere for continuous treatment for 6h to obtain C-stage COPNA resin with the number of C-C-2-4.
Examples 2 to 5
Respectively weighing 50.0g of petroleum asphalt extraction isolate, 12.5g of corn starch cross-linking agent, 2.5g of p-toluenesulfonic acid catalyst and 30mL of toluene solvent, mixing in a 200mL crucible, stirring uniformly, transferring to a rotary evaporator for rotary evaporation at 115 ℃ to recover the toluene solvent, transferring the evaporated raw material mixture to a 200mL three-neck flask, stirring the three-neck flask at 180 ℃ under nitrogen atmosphere for 5h to obtain B-stage COPNA resin, wherein the number is B-C-2-5, cooling, taking part of the material for analysis, continuously placing the rest in a roasting furnace under 400 ℃ under air atmosphere for continuous treatment for 5h to obtain C-stage COPNA resin, wherein the number is C-C-2-5.
Examples 2 to 6
Respectively weighing 50.0g of petroleum asphalt extraction isolate, 10.0g of corn starch cross-linking agent, 3.75g of p-toluenesulfonic acid catalyst and 30mL of toluene solvent, mixing the materials in a 200mL crucible, stirring uniformly, transferring the mixture to a rotary evaporator to perform rotary evaporation at 115 ℃ to recover the toluene solvent, transferring the evaporated raw material mixture to a 150mL high-temperature high-pressure hydrothermal synthesis kettle, replacing air in the kettle with argon, placing the hydrothermal kettle in a 200 ℃ far infrared oven to process for 8 hours to obtain B-order COPNA resin, wherein the number is B-C-2-6, cooling, taking part of the material to analyze, placing the rest part of the material in a roasting furnace at 500 ℃ to perform continuous treatment for 5 hours to obtain C-order COPNA resin, wherein the number is C-C-2-6.
Examples 2 to 7
Respectively weighing 50.0g of petroleum asphalt extraction isolate, 10g of corn starch cross-linking agent, 2g of p-toluenesulfonic acid catalyst and 15mL of toluene solvent, mixing the materials in a 200mL crucible, stirring uniformly, transferring the mixture to a rotary evaporator, carrying out rotary evaporation at 115 ℃ to recover the toluene solvent, transferring the evaporated raw material mixture to a 150mL high-temperature high-pressure hydrothermal synthesis kettle, replacing the air in the kettle with argon, placing the hydrothermal kettle in a 200 ℃ far infrared oven for treatment for 8h to obtain B-stage petroleum-based COPNA resin, wherein the number is B-C-2-7, cooling, taking part of the material for analysis, continuously placing the rest in a roasting furnace at 500 ℃ in an air atmosphere for continuous treatment for 5h to obtain C-stage petroleum-based COPNA resin, wherein the number is C-C-2-7.
Examples 2 to 8
Respectively weighing 50.0g of petroleum asphalt extraction isolate, 15g of corn starch cross-linking agent, 7.5g of p-toluenesulfonic acid catalyst and 40mL of toluene solvent, mixing the petroleum asphalt extraction isolate, 15g of corn starch cross-linking agent, 7.5g of p-toluenesulfonic acid catalyst and 40mL of toluene solvent together in a 200mL crucible, stirring uniformly, transferring the mixture into a rotary evaporator, carrying out rotary evaporation at 115 ℃ to recover the toluene solvent, transferring the raw material mixture obtained after evaporation into a 150mL high-temperature high-pressure hydrothermal synthesis kettle, replacing the air in the kettle with argon, placing the hydrothermal kettle in a far infrared oven at 200 ℃ for treatment for 8h to obtain B-stage petroleum-based COPNA resin, wherein the number is B-C-2-8, cooling, taking part of the material for analysis, continuously placing the rest in a roasting furnace at 500 ℃ for continuous treatment for 5h to obtain C-stage-based COPNA resin, wherein the number is C-C-2-8.
Comparative example 2-1
Respectively weighing 50.0g of petroleum asphalt extraction isolate, 12.5g of p-xylylene glycol cross-linking agent and 2.5g of p-toluenesulfonic acid catalyst, mixing in a 200mL three-neck flask, uniformly stirring, heating at 160 ℃ in nitrogen atmosphere for 5h to obtain B-stage COPNA resin, cooling DB-C-2-1 to obtain part of the material, analyzing, continuously placing the rest part in an official furnace at 350 ℃ for continuously treating for 4h to obtain C-stage COPNA resin, wherein the number is DC-C-2-1.
Test example 2
The B-stage petroleum-based COPNA resin and the C-stage petroleum-based COPNA resin prepared in examples 2-1 to 2-8 and comparative examples 1-2 were subjected to performance tests, the test results are shown in Table 2, wherein the performance test methods are the same as those of test example 1, and are not repeated herein.
TABLE 2
As can be seen from the comparison between examples 2-1 to 2-8 and comparative example 2-1, the B-stage petroleum-based COPNA resin and the C-stage petroleum-based COPNA resin prepared from examples 2-1 to 2-8 using the petroleum pitch extract and the vegetable starch as raw materials have excellent basic properties, which are significantly better than those of comparative example 2-1.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (17)
1. A petroleum-based COPNA resin is characterized in that the resin is mainly obtained by cross-linking petroleum extraction isolate and plant starch under the action of a catalyst;
the dosage of the plant starch is 10-55 wt% of the petroleum extraction isolate;
the plant starch is selected from at least one of corn starch, bean starch, cassava starch, potato starch and lotus root starch;
the petroleum extraction separator is petroleum asphalt extraction separator and/or FCC oil slurry extraction separator;
the petroleum asphalt extraction isolate is a component with the thermal weight loss of more than 80 percent concentrated between 350 ℃ and 510 ℃ after the petroleum asphalt component in the petroleum refining process is subjected to weight removal and light removal treatment;
the FCC oil slurry extraction isolate is a 2-4 ring polycyclic aromatic hydrocarbon component obtained after the FCC oil slurry is extracted and separated, and the initial weight loss temperature is more than 200 ℃, the temperature of 95 wt% weight loss is less than 500 ℃, and the weight loss between 300 ℃ and 400 ℃ is more than 75 wt%;
the catalyst comprises a protic acid.
2. The petroleum-based COPNA resin of claim 1, wherein the vegetable starch is present in an amount of 17-36 wt% of the petroleum extract isolate.
3. The petroleum-based COPNA resin of claim 1, wherein the catalyst is present in an amount of 2 to 30 wt% of the petroleum extract isolate.
4. The petroleum-based COPNA resin of claim 1, wherein the catalyst is present in an amount of 4 to 15 wt% of the petroleum extract isolate.
5. The petroleum-based COPNA resin of claim 1, wherein the catalyst comprises at least one of p-toluenesulfonic acid, benzenesulfonic acid, sulfuric acid, nitric acid, and aluminum chloride.
6. The method of any one of claims 1-5, comprising the steps of:
and uniformly mixing the petroleum extraction isolate, the plant starch and the catalyst to obtain a raw material mixture, and heating the raw material mixture to enable the petroleum extraction isolate and the plant starch to generate a cross-linking reaction to obtain the petroleum-based COPNA resin.
7. The method according to claim 6, wherein the petroleum extract isolate, the plant starch and the catalyst are dissolved in a solvent and mixed uniformly, and then the solvent is removed to obtain a raw material mixture.
8. The production method according to claim 7,
the solvent is an organic solvent.
9. The method according to claim 8,
the organic solvent includes at least one of acetone, petroleum ether, benzene, and toluene.
10. The production method according to claim 7,
the amount of the solvent is 10-90 wt% of the petroleum extraction isolate.
11. The method of claim 7, wherein the solvent is used in an amount of 30 to 60 wt% of the petroleum extract isolate.
12. The method according to claim 6, wherein the raw material mixture is heated in an air atmosphere, a far-infrared air atmosphere, or an inert gas atmosphere.
13. The method according to claim 6, wherein the raw material mixture is heated in an air atmosphere or a far-infrared air atmosphere.
14. The method as claimed in any one of claims 6 to 13, wherein the raw material mixture is heated to 100 ℃ and reacted at 250 ℃ for 2-8h to obtain the B-stage petroleum-based COPNA resin.
15. The method of claim 14,
heating the B-stage petroleum-based COPNA resin to 300-500 ℃ for reaction for 2-8h to obtain the C-stage petroleum-based COPNA resin.
16. Use of the petroleum-based COPNA resin according to any one of claims 1 to 5 for the preparation of magnetic, heat resistant, pressure resistant, corrosion resistant or electrically conductive materials.
17. A magnetic material, a heat-resistant material, a pressure-resistant material, a corrosion-resistant material or an electrically conductive material, which is produced using the petroleum-based CONPA resin according to any one of claims 1 to 5 as a raw material.
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