CN112391201B - Method for mixing ethylene cracking tar with naphthenic base heavy oil or residual oil thereof - Google Patents
Method for mixing ethylene cracking tar with naphthenic base heavy oil or residual oil thereof Download PDFInfo
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- CN112391201B CN112391201B CN202011140576.XA CN202011140576A CN112391201B CN 112391201 B CN112391201 B CN 112391201B CN 202011140576 A CN202011140576 A CN 202011140576A CN 112391201 B CN112391201 B CN 112391201B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention relates to the technical field of petrochemical industry, in particular to a method for mixing ethylene cracking tar with naphthenic base heavy oil or residual oil thereof, which comprises the following steps: mixing ethylene cracking tar with naphthenic heavy oil or residual oil thereof and a catalyst to obtain a first mixture, conveying the first mixture and hydrogen into a first suspension bed reactor for reaction, mixing the obtained second mixture and hydrogen into a second suspension bed reactor for reaction, separating the obtained hydrogenation product at normal pressure and reduced pressure to obtain gasoline and diesel oil components rich in aromatic hydrocarbon, separating the gasoline and diesel oil components in a reduced pressure tower to obtain a mixture with a distillation range of more than 480 ℃ as residual oil of the naphthenic heavy oil, and recycling the residual oil used for the raw oil in the first step. The invention can realize the high-efficiency hydrogenation full conversion of the full components of the mixed raw materials, prepare the gasoline and diesel oil rich in light aromatic hydrocarbon, successfully avoid the problem of asphaltene coking, realize the clean, high-efficiency and high-value utilization of the ethylene cracking tar with low additional value, the naphthenic base heavy oil and the residual oil thereof, and improve the economic benefit of the reaction.
Description
Technical Field
The invention relates to the technical field of petrochemical engineering, in particular to a method for mixing ethylene cracking tar with naphthenic base heavy oil or residual oil thereof.
Background
The light aromatic hydrocarbon mainly comprises benzene, toluene and xylene, and is an important basic chemical raw material. With the development of industry and the improvement of living standard of human beings, the industries of synthetic fiber, synthetic plastic and synthetic rubber are rapidly developed, the demand of light aromatic hydrocarbon is increased year by year, and the current situation of short supply and demand is generated. At present, the annual consumption of light aromatic hydrocarbon in China exceeds 20 Mt, wherein paraxylene is mainly used, and the light aromatic hydrocarbon accounts for about 45 percent of the total amount of the light aromatic hydrocarbon. In 2012, the apparent consumption of Paraxylene (PX) in China is 13.85 Mt, and the self-sufficiency rate of domestic products is only 56%. For a long time, the production of light aromatics in China is mainly obtained by using straight-run gasoline and naphtha through a noble metal platinum reforming process and a process for preparing ethylene through steam cracking, and the yield of benzene and derivatives thereof is limited to a great extent due to insufficient supply of raw materials.
In the process of ethylene production, 15 to 20 percent of ethylene cracking tar is by-produced due to high-temperature condensation of raw materials and products. The main component of the ethylene cracking tar is aromatic hydrocarbon compounds, mainly a mixture of aromatic hydrocarbons with more than two rings and condensed rings, the content of the aromatic hydrocarbons reaches more than 90 percent, and the content of asphaltene is high. The domestic part of ethylene tar is used for producing carbon black, most of the ethylene tar is mainly used as fuel oil to be burnt, the utilization degree is not high, and resource waste and environmental pollution are caused. In addition, the naphthenic heavy oil in China has rich resources and reserves, and has the characteristics of high content of naphthenic hydrocarbon and aromatic hydrocarbon, low content of asphaltene, high density, high viscosity and the like, so the transportation is difficult, and the processing difficulty is very high. Because of the defects of the performance indexes, the yield of the heavy fuel oil with low added value produced by the naphthenic base heavy oil is high, and the yield of the light fuel oil with high added value produced by the naphthenic base heavy oil is low. Therefore, there is a need to develop a clean, efficient and high-value utilization technology for processing ethylene cracking tar and naphthenic heavy oil into light aromatic hydrocarbons.
The content of bicyclic and fused aromatic hydrocarbons in the ethylene cracking tar is higher than 90%, the content of asphaltene is high, and the polarity is high; the naphthenic heavy oil has high naphthenic hydrocarbon and aromatic hydrocarbon content, low asphaltene content and low polarity. However, the demand for light aromatics in China is very short. Therefore, the new process is developed to produce the light aromatic hydrocarbon by hydrocracking the ethylene cracking tar and the naphthenic base heavy oil, so that the high-value utilization of the ethylene cracking tar and the naphthenic base heavy oil resources can be realized, rich and cheap raw materials can be provided for the production of the light aromatic hydrocarbon in China, and the supply pressure of the light aromatic hydrocarbon in China is reduced.
At present, the hydrocracking of ethylene cracking tar is reported less, and the research on the hydrocracking of naphthenic base heavy oil is not reported yet. Patent 200810228387.0 discloses a method for processing light fraction of ethylene tar sequentially through hydrogenation protection reaction zone, hydrogenation refining reaction zone and hydrocracking reaction zone to obtain gasoline and diesel oil fraction, while heavy fraction can only be used as general carbon fiber asphalt raw material. Patent 201711325715.4 discloses a start-up method of ethylene tar boiling bed-fixed bed combined process, which comprises vulcanizing a fixed bed hydrogenation unit, and using the material obtained in the reaction process of the fixed bed hydrogenation unit as the vulcanized oil in the start-up process of the boiling bed hydrogenation unit. In the hydrogenation process of the ethylene tar, a molded supported catalyst and a fixed bed reaction process are mostly adopted, only the hydrofining reaction of light components below 350 ℃ in the ethylene tar can be carried out, and the heavy components above 350 ℃ cannot be efficiently utilized. In addition, the ethylene tar has more asphaltene component content, and is easy to coke to cause the blockage of a reaction bed layer and the inactivation of a catalyst when being subjected to hydrofining in the process. Therefore, the prior art is not suitable for efficiently realizing the hydrogenation and lightening production of the whole fraction of the ethylene tar.
The suspension bed hydrogenation process is one of the ideal methods for realizing hydrogenation and lightening of heavy raw materials, and generally, the process comprises the steps of uniformly mixing a dispersed catalyst and raw oil to form slurry, then feeding the slurry and high-pressure hydrogen into a suspension bed reactor together to perform catalytic hydrocracking reaction under the hydrogen condition, and finally preparing a lightening product. In view of this, there is an urgent need in the art to develop a process for hydrocracking all components of ethylene pyrolysis tar, naphthenic heavy oil and residual oil thereof to obtain light aromatic hydrocarbons by using a suspension bed hydrogenation process of ethylene pyrolysis tar and naphthenic heavy oil. The process can solve the problems of coking, bed layer blockage and catalyst deactivation in the prior art, realize the hydrocracking production of light aromatic hydrocarbons by ethylene cracking tar and naphthenic heavy oil, and solve the problems of insufficient raw material supply and large aromatic hydrocarbon supply gap in light aromatic hydrocarbon production in China.
Disclosure of Invention
The invention provides a method for mixing ethylene cracking tar and naphthenic base heavy oil or residual oil thereof, overcomes the defects of the prior art, and can effectively solve the problems of reactor bed layer blockage and catalyst inactivation caused by incomplete hydrogenation and coking in the prior mixing process of the ethylene cracking tar and the naphthenic base heavy oil.
The technical scheme of the invention is realized by the following measures: a method for mixing ethylene cracking tar with naphthenic base heavy oil or residual oil thereof comprises the following steps: firstly, mixing ethylene cracking tar and naphthenic heavy oil or residual oil thereof which are mixed according to the mass ratio of 1:10 to 10:1 as raw oil, adding a catalyst which accounts for 0.01 to 5.0 percent of the mass of the raw oil and mainly contains molybdenum sulfide and the raw oil, and mixing to obtain a first mixture; secondly, mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 10MPa to 20MPa of pressure, no less than 8MPa of hydrogen partial pressure and 400 ℃ to 500 ℃ of temperature to obtain a second mixture, wherein the volume ratio of the hydrogen to the first mixture is 500-2000: 1, and the residence time of the first mixture in the first suspension bed reactor is 1-8 hours; thirdly, mixing the second mixture with hydrogen, feeding the mixture into a second suspension bed reactor, and reacting under the reaction conditions of 10MPa to 20MPa of pressure, no less than 8MPa of hydrogen partial pressure and 300 ℃ to 400 ℃ of temperature to obtain a hydrogenation product, wherein the volume ratio of the hydrogen to the mixture is 500-2000: 1, and the retention time of the mixture in the second suspension bed reactor is 1 hour to 8 hours; and fourthly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain gasoline and diesel oil components which are rich in light aromatic hydrocarbons and have the distillation range of less than 360 ℃, wherein the obtained wax oil components with the distillation range of 360 ℃ to 480 ℃ are delivered, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of naphthenic heavy oil and is used for recycling the raw oil in the first step.
The following is further optimization or/and improvement of the technical scheme of the invention:
the first suspended bed reactor and the second suspended bed reactor adopt a series process.
The reaction temperature of the first suspension bed reactor is not lower than that of the second suspension bed reactor.
In the second step, the first mixture is reacted with hydrogen under the reaction conditions of 12MPa to 16MPa of pressure, no less than 10MPa of hydrogen partial pressure and 450 ℃ to 500 ℃.
In the third step, the second mixture is reacted with hydrogen under the reaction conditions of a pressure of 12MPa to 16MPa, a hydrogen partial pressure of not less than 10MPa, and a temperature of 300 ℃ to 350 ℃.
In the first step, the mass ratio of the ethylene cracking tar to the naphthenic base heavy oil or the residual oil thereof is 1:3 to 3: 1.
In the first step, the catalyst mainly containing molybdenum sulfide accounts for 1.0-2.0% of the raw oil by mass percent.
The particle size of the catalyst containing molybdenum sulfide as main component is less than 200 meshes.
In the second step, the volume ratio of the hydrogen to the second mixture is 800 to 1200: 1; or/and, in the third step, the volume ratio of hydrogen to the second mixture is 800 to 1200: 1.
In the second step, the residence time of the first mixture in the first suspension bed reactor is 4 hours to 6 hours; and/or, in the third step, the residence time of the second mixture in the second suspended bed reactor is between 4 hours and 6 hours.
The invention can realize the high-efficiency hydrogenation full conversion of the full components of the mixed raw materials, prepare the gasoline and diesel oil rich in light aromatic hydrocarbon, successfully avoid the problem of asphaltene coking, realize the clean, high-efficiency and high-value utilization of the ethylene cracking tar with low additional value, the naphthenic base heavy oil and the residual oil thereof, and improve the economic benefit of the reaction.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the present invention are all mass percentages unless otherwise specified.
The invention is further described below with reference to the following examples:
example 1: the method for mixing the ethylene cracking tar with the naphthenic base heavy oil or the residual oil thereof comprises the following steps: firstly, mixing ethylene cracking tar and naphthenic heavy oil or residual oil thereof which are mixed according to the mass ratio of 1:10 to 10:1 as raw oil, adding a catalyst which accounts for 0.01 to 5.0 percent of the mass of the raw oil and mainly contains molybdenum sulfide and the raw oil, and mixing to obtain a first mixture; secondly, mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 10MPa to 20MPa of pressure, no less than 8MPa of hydrogen partial pressure and 400 ℃ to 500 ℃ of temperature to obtain a second mixture, wherein the volume ratio of the hydrogen to the first mixture is 500-2000: 1, and the residence time of the first mixture in the first suspension bed reactor is 1-8 hours; thirdly, mixing the second mixture with hydrogen, feeding the mixture into a second suspension bed reactor, and reacting under the reaction conditions of 10MPa to 20MPa of pressure, no less than 8MPa of hydrogen partial pressure and 300 ℃ to 400 ℃ of temperature to obtain a hydrogenation product, wherein the volume ratio of the hydrogen to the mixture is 500-2000: 1, and the retention time of the mixture in the second suspension bed reactor is 1 hour to 8 hours; and fourthly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain gasoline and diesel oil components which are rich in light aromatic hydrocarbons and have the distillation range of less than 360 ℃, wherein the obtained wax oil components with the distillation range of 360 ℃ to 480 ℃ are delivered, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of naphthenic heavy oil and is used for recycling the raw oil in the first step.
According to the invention, by adopting a serial-type suspension bed hydrogenation mixing process, the raw materials are completely converted into the components rich in light aromatic hydrocarbons through hydrogenation, special treatment on ethylene cracking tar, naphthenic heavy oil and residual oil thereof is not required, high-efficiency hydrogenation complete conversion on the components of the mixed raw materials can be realized, the gasoline and diesel oil rich in light aromatic hydrocarbons can be prepared, clean, high-efficiency and high-value utilization of the ethylene cracking tar with low added value, the naphthenic heavy oil and the residual oil thereof is realized, and the economic benefit of the reaction is improved.
Example 2: the method for mixing the ethylene cracking tar with the naphthenic base heavy oil or the residual oil thereof comprises the following steps: firstly, mixing ethylene cracking tar and naphthenic base heavy oil or residual oil thereof which are mixed according to the mass ratio of 1:10 or 10:1 as raw oil, adding a catalyst which accounts for 0.01 percent or 5.0 percent of the mass of the raw oil and mainly contains molybdenum sulfide, and mixing the catalyst with the raw oil to obtain a first mixture; secondly, mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 10MPa or 20MPa of pressure, no less than 8MPa of hydrogen partial pressure and 400 ℃ or 500 ℃ of temperature to obtain a second mixture, wherein the volume ratio of the hydrogen to the first mixture is 500 or 2000:1, and the residence time of the first mixture in the first suspension bed reactor is 1 hour or 8 hours; thirdly, mixing the second mixture with hydrogen, feeding the mixture into a second suspension bed reactor, and reacting under the reaction conditions of 10MPa or 20MPa of pressure, no less than 8MPa of hydrogen partial pressure and 300 ℃ or 400 ℃ of temperature to obtain a hydrogenation product, wherein the volume ratio of the hydrogen to the mixture is 500 or 2000:1, and the retention time of the mixture in the second suspension bed reactor is 1 hour or 8 hours; thirdly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain gasoline and diesel oil components which are rich in light aromatic hydrocarbons and have a distillation range below 360 ℃; and fourthly, separating the gasoline and diesel oil components in a vacuum tower, separating to obtain wax oil components with the distillation range of 360 ℃ or 480 ℃ for delivery, and using the mixture with the distillation range of more than 480 ℃ as residual oil of the naphthenic base heavy oil for recycling the raw oil in the first step.
Example 3: as an optimization of the above example, the first suspended bed reactor and the second suspended bed reactor adopt a series process.
Example 4: as an optimization of the above example, the reaction temperature of the first suspension bed reactor was not lower than that of the second suspension bed reactor.
By adopting a first suspended bed reactor and a second suspended bed reactor which are connected in series, the temperature of the first suspended bed reactor is not lower than that of the second suspended bed reactor. The first suspension bed reactor is mainly used for carrying out high-temperature hydrocracking on the polycyclic aromatic hydrocarbon in the mixed raw material to generate a light component rich in monocyclic aromatic hydrocarbon; and the second suspension bed reactor is mainly used for completing the low-temperature hydrogenation saturation of monocyclic aromatic hydrocarbon in the light component generated by the first suspension bed reactor to generate light aromatic hydrocarbon. The invention can effectively avoid the process problems of raw material coking, reactor bed layer blockage, pressure drop and the like, and can ensure that the hydrocracking and aromatic hydrocarbon saturation reaction can be carried out under the optimal environmental condition, thereby being beneficial to improving the yield of light aromatic hydrocarbon of ethylene cracking tar, naphthenic base heavy oil and residual oil thereof.
Example 5: as an optimization of the above embodiment, in the second step, the first mixture is reacted with hydrogen under reaction conditions of a pressure of 12MPa to 16MPa, a hydrogen partial pressure of not less than 10MPa, and a temperature of 450 ℃ to 500 ℃.
Example 6: as an optimization of the above embodiment, in the third step, the second mixture is reacted with hydrogen under reaction conditions of a pressure of 12MPa to 16MPa, a hydrogen partial pressure of not less than 10MPa, and a temperature of 300 ℃ to 350 ℃.
Example 7: as optimization of the above examples, in the first step, the mass ratio of the ethylene cracking tar to the naphthenic heavy oil or its residual oil is 1:3 to 3: 1.
Example 8: in the optimization of the above embodiment, in the first step, the mass percentage of the catalyst mainly containing molybdenum sulfide in the raw oil is 1.0% to 2.0%.
Example 9: as an optimization of the above example, the particle size of the molybdenum sulphide based catalyst was less than 200 mesh.
Example 10: as an optimization of the above embodiment, in the second step, the volume ratio of hydrogen to the second mixture is 800 to 1200: 1; or/and, in the third step, the volume ratio of hydrogen to the second mixture is 800 to 1200: 1.
Example 11: as an optimization of the above example, in the second step, the residence time of the first mixture in the first suspension bed reactor is 4 to 6 hours; and/or, in the third step, the residence time of the second mixture in the second suspended bed reactor is between 4 hours and 6 hours.
Example 12: the method for mixing the ethylene cracking tar with the naphthenic base heavy oil or the residual oil thereof comprises the following steps: firstly, mixing ethylene cracking tar and naphthenic base heavy oil or residual oil thereof which are mixed according to the mass ratio of 3:1 as raw oil, adding a catalyst which accounts for 2.0 percent of the mass of the raw oil and mainly contains molybdenum sulfide, and mixing the catalyst with the raw oil to obtain a first mixture; secondly, mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 16MPa of pressure, 14MPa or more of hydrogen partial pressure and 450 ℃ of temperature to obtain a second mixture, wherein the volume ratio of the hydrogen to the first mixture is 1200:1, and the residence time of the first mixture in the first suspension bed reactor is 6 hours; thirdly, mixing the second mixture with hydrogen, feeding the mixture into a second suspension bed reactor, and reacting under the reaction conditions of 16MPa of pressure, 14MPa or more of hydrogen partial pressure and 350 ℃ to obtain a hydrogenation product, wherein the volume ratio of the hydrogen to the mixture is 1200:1, and the retention time of the mixture in the second suspension bed reactor is 6 hours; and thirdly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain gasoline and diesel oil components which are rich in light aromatic hydrocarbons and have the distillation range of below 360 ℃, wherein the wax oil components with the distillation range of between 360 ℃ and 480 ℃ are obtained by separation and are externally conveyed, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of naphthenic heavy oil and is used for recycling the raw oil in the first step.
Example 13: the method for mixing the ethylene cracking tar with the naphthenic base heavy oil or the residual oil thereof comprises the following steps: firstly, mixing ethylene cracking tar and naphthenic base heavy oil or residual oil thereof which are mixed according to the mass ratio of 1:10 as raw oil, adding a catalyst which accounts for 0.01 percent of the mass of the raw oil and mainly contains molybdenum sulfide, and mixing the catalyst with the raw oil to obtain a first mixture; secondly, mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 20MPa of pressure, 18MPa or more of hydrogen partial pressure and 500 ℃ of temperature to obtain a second mixture, wherein the volume ratio of the hydrogen to the first mixture is 2000:1, and the residence time of the first mixture in the first suspension bed reactor is 8 hours; thirdly, mixing the second mixture with hydrogen, feeding the mixture into a second suspension bed reactor, and reacting under the reaction conditions of 20MPa of pressure, 18MPa of hydrogen partial pressure and 400 ℃ of temperature to obtain a hydrogenation product, wherein the volume ratio of the hydrogen to the mixture is 1200:1, and the retention time of the mixture in the second suspension bed reactor is 8 hours; and thirdly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain gasoline and diesel oil components which are rich in light aromatic hydrocarbons and have the distillation range of below 360 ℃, wherein the wax oil components with the distillation range of between 360 ℃ and 480 ℃ are obtained by separation and are externally conveyed, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of naphthenic heavy oil and is used for recycling the raw oil in the first step.
Example 14: the method for mixing the ethylene cracking tar with the naphthenic base heavy oil or the residual oil thereof comprises the following steps: firstly, mixing ethylene cracking tar and naphthenic base heavy oil or residual oil thereof which are mixed according to the mass ratio of 10:1 as raw oil, adding a catalyst which accounts for 5.0 percent of the mass of the raw oil and mainly contains molybdenum sulfide, and mixing the catalyst with the raw oil to obtain a first mixture; secondly, mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 10MPa of pressure, no less than 8MPa of hydrogen partial pressure and 400 ℃ of temperature to obtain a second mixture, wherein the volume ratio of the hydrogen to the first mixture is 500:1, and the residence time of the first mixture in the first suspension bed reactor is 1 hour; thirdly, mixing the second mixture with hydrogen, feeding the mixture into a second suspension bed reactor, and reacting under the reaction conditions of 10MPa of pressure, no less than 8MPa of hydrogen partial pressure and 300 ℃ of temperature to obtain a hydrogenation product, wherein the volume ratio of the hydrogen to the mixture is 500:1, and the retention time of the mixture in the second suspension bed reactor is 8 hours; and thirdly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain gasoline and diesel oil components which are rich in light aromatic hydrocarbons and have the distillation range of below 360 ℃, wherein the wax oil components with the distillation range of between 360 ℃ and 480 ℃ are obtained by separation and are externally conveyed, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of naphthenic heavy oil and is used for recycling the raw oil in the first step.
Example 15: the method for mixing the ethylene cracking tar with the naphthenic base heavy oil or the residual oil thereof comprises the following steps: firstly, mixing ethylene cracking tar and naphthenic base heavy oil or residual oil thereof which are mixed according to the mass ratio of 1:1 as raw oil, adding a catalyst which accounts for 1.25 percent of the mass of the raw oil and mainly contains molybdenum sulfide, and mixing the catalyst with the raw oil to obtain a first mixture; secondly, mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 15MPa of pressure, 13MPa or more of hydrogen partial pressure and 450 ℃ of temperature to obtain a second mixture, wherein the volume ratio of the hydrogen to the first mixture is 1000:1, and the residence time of the first mixture in the first suspension bed reactor is 5 hours; thirdly, mixing the second mixture with hydrogen, feeding the mixture into a second suspension bed reactor, and reacting under the reaction conditions of 15MPa of pressure, 13MPa or more of hydrogen partial pressure and 350 ℃ to obtain a hydrogenation product, wherein the volume ratio of the hydrogen to the mixture is 1000:1, and the retention time of the mixture in the second suspension bed reactor is 5 hours; and thirdly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain gasoline and diesel oil components which are rich in light aromatic hydrocarbons and have the distillation range of below 360 ℃, wherein the wax oil components with the distillation range of between 360 ℃ and 480 ℃ are obtained by separation and are externally conveyed, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of naphthenic heavy oil and is used for recycling the raw oil in the first step.
Example 16: the method for mixing the ethylene cracking tar with the naphthenic base heavy oil or the residual oil thereof comprises the following steps: firstly, mixing ethylene cracking tar and naphthenic heavy oil or residual oil thereof which are mixed according to the mass ratio of 1:3 as raw oil, adding a catalyst which accounts for 1.0 percent of the mass of the raw oil and mainly contains molybdenum sulfide, and mixing the catalyst with the raw oil to obtain a first mixture; secondly, mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 14MPa of pressure, 12MPa of hydrogen partial pressure and 430 ℃ of temperature to obtain a second mixture, wherein the volume ratio of the hydrogen to the first mixture is 800:1, and the residence time of the first mixture in the first suspension bed reactor is 4 hours; thirdly, mixing the second mixture with hydrogen, feeding the mixture into a second suspension bed reactor, and reacting under the reaction conditions of 14MPa of pressure, 12MPa or more of hydrogen partial pressure and 320 ℃ of temperature to obtain a hydrogenation product, wherein the volume ratio of the hydrogen to the mixture is 800:1, and the retention time of the mixture in the second suspension bed reactor is 4 hours; and thirdly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain gasoline and diesel oil components which are rich in light aromatic hydrocarbons and have the distillation range of below 360 ℃, wherein the wax oil components with the distillation range of between 360 ℃ and 480 ℃ are obtained by separation and are externally conveyed, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of naphthenic heavy oil and is used for recycling the raw oil in the first step. The invention mixes ethylene cracking tar with naphthenic base heavy oil or residual oil thereof, mainly the naphthenic base heavy oil has low content of aromatic hydrocarbon, less content of asphaltene, weak polarity and poor compatibility with molybdenum sulfide base nano catalyst. Therefore, the naphthenic base heavy oil and residual oil thereof are subjected to hydrogenation lightening reaction independently, and the catalyst has poor solubility in the naphthenic base heavy oil, low dispersity and suspension property and low hydrogenation speed. The ethylene cracking tar has high aromatic hydrocarbon content, high asphaltene content, strong polarity and good compatibility with molybdenum sulfide-based nano catalyst, so the ethylene cracking tar is mixed with naphthenic heavy oil or residual oil thereof, and the gasoline and diesel oil component rich in light aromatic hydrocarbon is obtained by hydrocracking and then hydrogenating and saturating. In addition, the content of aromatic hydrocarbon in the ethylene cracking tar reaches 90 percent, so the ethylene cracking tar is a very good hydrogen donor, and is beneficial to promoting the quick hydrogenation and lightening of naphthenic base heavy oil and residual oil thereof.
Example 17: the method for mixing the ethylene cracking tar with the naphthenic base heavy oil or the residual oil thereof comprises the following steps: step one, mixing ethylene cracking tar and naphthenic base heavy oil or residual oil thereof which are mixed according to the mass ratio of 5:1 as raw oil, adding a catalyst which accounts for 3.0 percent of the mass of the raw oil and mainly contains molybdenum sulfide, and mixing the catalyst with the raw oil to obtain a first mixture; secondly, mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 16MPa of pressure, 14MPa of hydrogen partial pressure and 480 ℃ of temperature to obtain a second mixture, wherein the volume ratio of the hydrogen to the first mixture is 1600:1, and the retention time of the first mixture in the first suspension bed reactor is 6 hours; thirdly, mixing the second mixture with hydrogen, feeding the mixture into a second suspension bed reactor, and reacting under the reaction conditions of 16MPa of pressure, 14MPa of hydrogen partial pressure and 370 ℃ of temperature to obtain a hydrogenation product, wherein the volume ratio of the hydrogen to the mixture is 1600:1, and the retention time of the mixture in the second suspension bed reactor is 6 hours; and thirdly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain gasoline and diesel oil components which are rich in light aromatic hydrocarbons and have the distillation range of below 360 ℃, wherein the wax oil components with the distillation range of between 360 ℃ and 480 ℃ are obtained by separation and are externally conveyed, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of naphthenic heavy oil and is used for recycling the raw oil in the first step.
The mixing effect of the ethylene cracking tar and the naphthenic base heavy oil or the residual oil thereof obtained according to the embodiments 12 to 17 is shown in table 1, and it can be seen in table 1 that the conversion rate of asphaltenes can reach as high as 99.9% and the yield of gasoline and diesel oil rich in light aromatic hydrocarbons can reach as high as 61.1% after the two-step hydrocracking and hydrogenation saturation reaction of the mixed raw oil of the ethylene cracking tar and the naphthenic base heavy oil or the residual oil thereof. Therefore, the invention not only successfully avoids the problem of asphaltene coking, but also converts the asphaltene coking into the gasoline and diesel oil with high added value and rich light aromatic hydrocarbon, and has very good economic benefit and very good implementation effect.
In conclusion, the invention can realize high-efficiency hydrogenation full conversion of all components of the mixed raw materials, prepare the gasoline and diesel oil rich in light aromatic hydrocarbon, successfully avoid the problem of asphaltene coking, realize clean, high-efficiency and high-value utilization of the ethylene cracking tar with low additional value, the naphthenic base heavy oil and the residual oil thereof, and improve the economic benefit of the reaction.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Claims (10)
1. A method for mixing ethylene cracking tar with naphthenic base heavy oil or residual oil thereof is characterized by comprising the following steps: firstly, mixing ethylene cracking tar and naphthenic heavy oil or residual oil thereof which are mixed according to the mass ratio of 1:10 to 10:1 as raw oil, adding a catalyst which accounts for 0.01 to 5.0 percent of the mass of the raw oil and mainly contains molybdenum sulfide and the raw oil, and mixing to obtain a first mixture; secondly, mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 10MPa to 20MPa of pressure, no less than 8MPa of hydrogen partial pressure and 400 ℃ to 500 ℃ of temperature to obtain a second mixture, wherein the volume ratio of the hydrogen to the first mixture is 500-2000: 1, and the residence time of the first mixture in the first suspension bed reactor is 1-8 hours; thirdly, mixing the second mixture with hydrogen, feeding the mixture into a second suspension bed reactor, and reacting under the reaction conditions of 10MPa to 20MPa of pressure, no less than 8MPa of hydrogen partial pressure and 300 ℃ to 400 ℃ of temperature to obtain a hydrogenation product, wherein the volume ratio of the hydrogen to the second mixture is 500-2000: 1, and the retention time of the second mixture in the second suspension bed reactor is 1-8 hours; and fourthly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain gasoline and diesel oil components which are rich in light aromatic hydrocarbons and have the distillation range of less than 360 ℃, wherein the obtained wax oil components with the distillation range of 360 ℃ to 480 ℃ are delivered, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of naphthenic heavy oil and is used for recycling the raw oil in the first step.
2. The method for mixing ethylene cracking tar with naphthenic heavy oil or residual oil thereof according to claim 1, wherein the first suspension bed reactor and the second suspension bed reactor adopt a series process.
3. The method for mixing ethylene cracking tar with naphthenic heavy oil or residual oil thereof according to claim 1 or 2, wherein the reaction temperature of the first suspension bed reactor is not lower than that of the second suspension bed reactor.
4. The method for mixing ethylene cracking tar with naphthenic heavy oil or residue thereof according to claim 1 or 2, wherein the first mixture is reacted with hydrogen under the reaction conditions of 12 to 16MPa of pressure, 10MPa or more of hydrogen partial pressure and 450 to 500 ℃ of temperature in the second step.
5. The method for mixing ethylene cracking tar with naphthenic heavy oil or residue thereof according to claim 1 or 2, wherein the second mixture is reacted with hydrogen under the reaction conditions of a pressure of 12 to 16MPa, a hydrogen partial pressure of not less than 10MPa, and a temperature of 300 to 350 ℃ in the third step.
6. The method for mixing ethylene cracking tar with naphthenic base heavy oil or residue thereof according to claim 1 or 2, wherein the mass ratio of the ethylene cracking tar to the naphthenic base heavy oil or residue thereof in the first step is 1:3 to 3: 1.
7. The method for mixing ethylene cracking tar with naphthenic base heavy oil or residual oil thereof according to claim 1 or 2, wherein in the first step, the catalyst mainly containing molybdenum sulfide accounts for 1.0-2.0% of the raw oil by mass.
8. The method for mixing ethylene cracking tar with naphthenic heavy oil or residual oil thereof according to any one of claims 1 or 2, wherein the particle size of the catalyst mainly containing molybdenum sulfide is less than 200 mesh.
9. The method for mixing ethylene cracking tar with naphthenic heavy oil or residue thereof according to any one of claims 1 or 2, wherein in the second step, the volume ratio of hydrogen to the first mixture is 800 to 1200: 1; or/and, in the third step, the volume ratio of hydrogen to the second mixture is 800 to 1200: 1.
10. The method for mixing ethylene cracking tar with naphthenic heavy oil or residue thereof according to any one of claims 1 or 2, wherein in the second step, the residence time of the first mixture in the first suspension bed reactor is 4 to 6 hours; and/or, in the third step, the residence time of the second mixture in the second suspended bed reactor is between 4 hours and 6 hours.
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