CN112391200A - Method for hydrogenating ethylene cracking tar - Google Patents
Method for hydrogenating ethylene cracking tar Download PDFInfo
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- CN112391200A CN112391200A CN202011138359.7A CN202011138359A CN112391200A CN 112391200 A CN112391200 A CN 112391200A CN 202011138359 A CN202011138359 A CN 202011138359A CN 112391200 A CN112391200 A CN 112391200A
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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
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the technical field of petrochemical industry, in particular to a method for hydrogenating ethylene cracking tar, which comprises the steps of mixing a metal sulfide catalyst and the ethylene cracking tar to obtain raw oil, adding the catalyst to the raw oil to mix, mixing the obtained first mixture with hydrogen to be conveyed into a suspension bed reactor to react, mixing the obtained second mixture with the hydrogen to be conveyed into the suspension bed reactor to react, carrying out atmospheric and vacuum separation on the obtained hydrogenation product, carrying out vacuum tower separation on the obtained light gasoline and diesel oil component containing aromatic hydrocarbon, and taking the separated mixture with the distillation range of more than 480 ℃ as residual oil of the ethylene cracking tar to be used for recycling the initial raw oil. The invention can realize the full-component hydro-conversion of the raw material, has high yield of the light component rich in light aromatic hydrocarbon, can realize the 'dry-pressing and clean' of the ethylene cracking tar, successfully avoids the problem of asphaltene coking, converts the tar into the monocyclic aromatic hydrocarbon with high added value, and has very good economic benefit.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a method for hydrogenating ethylene cracking tar.
Background
The ethylene tar is a high-temperature condensation product of a raw material and a product of an ethylene cracking raw material in a steam cracking process, the main component of the ethylene tar is an aromatic hydrocarbon compound, the main component is a mixture of polycyclic aromatic hydrocarbons with more than 90 percent of aromatic hydrocarbon, the side chain is short, the carbon-hydrogen ratio is high, the ash content is low, the heavy metal content is very low, the composition of the ethylene tar varies with different cracking raw materials and cracking conditions, and the yield is 15 to 20 percent of the ethylene yield. The ethylene tar is used for producing carbon black in China, most of the ethylene tar is mainly used as fuel oil to be burnt, however, the ethylene tar is not easy to burn, has low heat value, is easy to generate black smoke and coking during burning, has low utilization degree, causes resource waste and pollutes the environment. The high-efficiency processing of ethylene cracking tar has the disadvantages of high overall utilization difficulty, low utilization rate and low economic benefit.
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.
The content of the double-ring aromatic hydrocarbon and the polycyclic aromatic hydrocarbon in the ethylene cracking tar is higher than 90 percent, and the national demand for the single-ring aromatic hydrocarbon is great. The new process is developed to produce light aromatic hydrocarbon by hydrocracking the double-ring or condensed-ring aromatic hydrocarbon in the ethylene cracking tar, so that the high-value utilization of the ethylene cracking tar can be realized, and the supply pressure of the light aromatic hydrocarbon in China can be reduced.
At present, the hydrocracking of ethylene cracking tar is reported less. 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.
Disclosure of Invention
The invention provides a method for hydrogenating ethylene cracking tar, which overcomes the defects of the prior art and can effectively solve the problems that the ethylene cracking tar cannot be fully hydrogenated and utilized, cokes, blocks a reactor bed layer and inactivates a catalyst in the prior hydrogenation of the ethylene cracking tar.
The technical scheme of the invention is realized by the following measures: a method for hydrogenating ethylene cracking tar is carried out according to the following steps: step one, taking ethylene cracking tar as raw oil, and mixing a metal sulfide catalyst with the raw oil according to the mass ratio of 0.0001: 1-1: 19 to obtain a first mixture, wherein the metal sulfide catalyst accounts for 0.01-5.0% of the first mixture in the first mixture; mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 10-25 MPa of pressure, no less than 8MPa of hydrogen partial pressure and 300-400 ℃ 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 25MPa of pressure, no less than 8MPa of hydrogen partial pressure and 400 ℃ to 500 ℃ 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 the gasoline and diesel oil component which is rich in light aromatic hydrocarbons and has the distillation range of below 360 ℃, wherein the wax oil component with the distillation range of between 360 ℃ and 480 ℃ is obtained by separation and is sent out, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of ethylene cracking tar 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 higher than that of the second suspension bed reactor.
In the second step, the first mixture is reacted with hydrogen under the reaction conditions of 14MPa to 18MPa of pressure, 12MPa or more of partial pressure of hydrogen and 300 ℃ to 350 ℃.
In the third step, the second mixture is reacted with hydrogen under the reaction conditions of 14MPa to 18MPa of pressure, 12MPa or more of hydrogen partial pressure and 450 ℃ to 500 ℃.
In the first step, the metal sulfide catalyst contains at least one metal element selected from the group consisting of Fe, Co, Ni, Mo, and W.
In the first step, the metal sulfide catalyst contains a metal element of Mo.
The particle size of the metal sulfide catalyst is less than 200 meshes.
In the first step, the metal sulfide catalyst accounts for 1.0 to 2.0 percent of the mass of the raw oil; or/and, 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.
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 from 4 hours to 6 hours.
The invention can realize the full-component hydro-conversion of the raw material, has high yield of the light component rich in light aromatic hydrocarbon, can realize the 'dry-pressing and clean' of the ethylene cracking tar, successfully avoids the problem of asphaltene coking, converts the tar into the monocyclic aromatic hydrocarbon with high added value, and has very good economic benefit.
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 hydrogenating the ethylene cracking tar is carried out according to the following steps: step one, taking ethylene cracking tar as raw oil, and mixing a metal sulfide catalyst with the raw oil according to the mass ratio of 0.0001: 1-1: 19 to obtain a first mixture, wherein the metal sulfide catalyst accounts for 0.01-5.0% of the first mixture in the first mixture; mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 10-25 MPa of pressure, no less than 8MPa of hydrogen partial pressure and 300-400 ℃ 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 25MPa of pressure, no less than 8MPa of hydrogen partial pressure and 400 ℃ to 500 ℃ 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 the gasoline and diesel oil component which is rich in light aromatic hydrocarbons and has the distillation range of below 360 ℃, wherein the wax oil component with the distillation range of between 360 ℃ and 480 ℃ is obtained by separation and is sent out, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of ethylene cracking tar oil and is used for recycling the raw oil in the first step.
The invention adopts the tandem type suspension bed hydrogenation mixing process, has low requirements on raw materials, can carry out full-component hydrogenation conversion on the raw materials without carrying out special treatment on the ethylene cracking tar raw materials, has high yield of light components rich in light aromatic hydrocarbon, can realize 'dry-eating and clean-pressing' of the ethylene cracking tar, and has extremely high atomic economy.
Example 2: the method for hydrogenating the ethylene cracking tar is carried out according to the following steps: step one, taking ethylene cracking tar as raw oil, and mixing a metal sulfide catalyst with the raw oil according to a mass ratio of 0.0001:1 or 1:19 to obtain a first mixture, wherein the metal sulfide catalyst accounts for 0.01% or 5.0% of the first mixture in the first mixture; mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 10MPa or 25MPa of pressure, no less than 8MPa of hydrogen partial pressure and 300 ℃ or 400 ℃ 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 25MPa of pressure, no less than 8MPa of hydrogen partial pressure and 400 ℃ or 500 ℃ 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; and thirdly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain a gasoline and diesel oil component which is below the distillation range of 360 ℃ and rich in light aromatic hydrocarbons, wherein the wax oil component with the distillation range of 360 ℃ or 480 ℃ is obtained by separation and is delivered, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of ethylene cracking tar and is used for recycling the raw oil in the first step.
Example 3: as an optimization of the above embodiment, the first suspended bed reactor and the second suspended bed reactor adopt a series process.
Example 4: as an optimization of the above embodiment, the reaction temperature of the first suspended bed reactor is not higher than the reaction temperature of the second suspended bed reactor.
According to the invention, two suspension bed reactors connected in series are adopted, and the temperature of the first suspension bed reactor is lower than that of the second suspension bed reactor, so that hydrocracking of ethylene cracking tar is realized in two steps to produce the light component rich in monocyclic aromatic hydrocarbon. The first suspension bed reactor carries out low-temperature hydrogenation saturation reaction of ethylene cracking tar. The ethylene cracking tar contains a large amount of bicyclic and fused-ring aromatic hydrocarbons, and low temperature is favorable for hydrogenation saturation to generate a monocyclic compound through hydrogenation saturation of the bicyclic or fused-ring aromatic hydrocarbons based on thermodynamic hydrogenation consideration. The second suspension bed reactor carries out high-temperature cracking reaction, from the thermodynamic perspective, the high temperature is favorable for hydrocracking, and the hydrocracking of the monocyclic aromatic hydrocarbon obtained in the first reactor is realized in the second suspension bed reactor to generate monocyclic light aromatic hydrocarbon. The two-step process can ensure that the two-step reactions of aromatic hydrocarbon hydrogenation saturation and hydrocracking in the ethylene cracking tar can be carried out under the optimal reaction conditions, thereby being beneficial to improving the yield of light aromatic hydrocarbon generated by hydrocracking the ethylene cracking tar.
Meanwhile, in the suspension bed hydrogenation process adopted by the invention, the metal sulfide catalyst can be highly dispersed in the ethylene cracking tar raw material and is in a suspension state in the reactor, and can be fully contacted with the ethylene cracking tar raw material to generate a hydrocracking reaction, so that the rapid conversion of the difficult-to-hydrogenate asphaltene and colloid components in the ethylene cracking tar is promoted, the problems of coking, reactor bed layer blockage, catalyst inactivation and the like in the prior art are avoided effectively, and the high-efficiency rapid conversion of the full components of the ethylene cracking tar is realized.
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 14MPa to 18MPa, a hydrogen partial pressure of not less than 12MPa, and a temperature of 300 ℃ to 350 ℃.
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 14MPa to 18MPa, a hydrogen partial pressure of not less than 12MPa, and a temperature of 450 ℃ to 500 ℃.
Example 7: as an optimization of the above embodiment, in the first step, the metal element in the metal sulfide catalyst is at least one of Fe, Co, Ni, Mo, and W.
Example 8: in the first step of optimization of the above embodiment, the metal sulfide catalyst contains Mo as a metal element.
Example 9: as an optimization of the above example, the particle size of the metal sulfide catalyst is less than 200 mesh.
Example 10: as the optimization of the above embodiment, in the first step, the mass percentage of the metal sulfide catalyst in the raw oil is 1.0% to 2.0%; or/and, 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 suspended 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 from 4 hours to 6 hours.
Example 12: the method for hydrogenating the ethylene cracking tar is carried out according to the following steps: step one, mixing a molybdenum sulfide catalyst and raw oil according to the mass ratio of 0.0001:1 by taking ethylene cracking tar as the raw oil to obtain a first mixture, wherein the molybdenum sulfide catalyst accounts for 0.01% of the first mixture in the first mixture; mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of pressure of 25MPa, hydrogen partial pressure of not less than 23MPa and temperature of 400 ℃ 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 25MPa of pressure, no less than 23MPa of hydrogen partial pressure and 500 ℃ of temperature to obtain a hydrogenation product, wherein the volume ratio of the hydrogen to the mixture is 2000:1, 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 a gasoline and diesel oil component which is below the distillation range of 360 ℃ and rich in light aromatic hydrocarbons, wherein the wax oil component with the distillation range of 360 ℃ or 480 ℃ is obtained by separation and is delivered, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of ethylene cracking tar and is used for recycling the raw oil in the first step.
Example 13: the method for hydrogenating the ethylene cracking tar is carried out according to the following steps: step one, mixing a molybdenum sulfide catalyst and raw oil according to a mass ratio of 1:19 by taking ethylene cracking tar as raw oil to obtain a first mixture, wherein the molybdenum sulfide catalyst accounts for 5.0% of the first mixture in the first mixture; 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 300 ℃ 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 400 ℃ 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 1 hour; and thirdly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain a gasoline and diesel oil component which is below the distillation range of 360 ℃ and rich in light aromatic hydrocarbons, wherein the wax oil component with the distillation range of 360 ℃ or 480 ℃ is obtained by separation and is delivered, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of ethylene cracking tar and is used for recycling the raw oil in the first step.
Example 14: the method for hydrogenating the ethylene cracking tar is carried out according to the following steps: step one, mixing a molybdenum sulfide catalyst and raw oil according to a mass ratio of 1:79 by taking ethylene cracking tar as raw oil to obtain a first mixture, wherein the molybdenum sulfide catalyst accounts for 1.25% of the first mixture in percentage by mass; 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, no less than 12MPa of hydrogen partial pressure and 350 ℃ 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 16MPa of pressure, 12MPa or more of hydrogen partial pressure and 450 ℃ of temperature 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 a gasoline and diesel oil component which is below the distillation range of 360 ℃ and rich in light aromatic hydrocarbons, wherein the wax oil component with the distillation range of 360 ℃ or 480 ℃ is obtained by separation and is delivered, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of ethylene cracking tar and is used for recycling the raw oil in the first step.
Example 15: the method for hydrogenating the ethylene cracking tar is carried out according to the following steps: step one, taking ethylene cracking tar as raw oil, and mixing a tungsten sulfide catalyst with the raw oil according to a mass ratio of 1:99 to obtain a first mixture, wherein the tungsten sulfide catalyst accounts for 1.0% of the first mixture in the first mixture; 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, no less than 12MPa of hydrogen partial pressure and 320 ℃ 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 of hydrogen partial pressure and 430 ℃ 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 a gasoline and diesel oil component which is below the distillation range of 360 ℃ and rich in light aromatic hydrocarbons, wherein the wax oil component with the distillation range of 360 ℃ or 480 ℃ is obtained by separation and is delivered, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of ethylene cracking tar and is used for recycling the raw oil in the first step.
Example 16: the method for hydrogenating the ethylene cracking tar is carried out according to the following steps: step one, mixing an iron sulfide catalyst and raw oil according to a mass ratio of 1:49 by taking ethylene cracking tar as raw oil to obtain a first mixture, wherein the iron sulfide catalyst accounts for 2.0% of the first mixture in the first mixture; mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 18MPa of pressure, 16MPa or more of hydrogen partial pressure and 370 ℃ 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 18MPa of pressure, 16MPa or more of hydrogen partial pressure and 480 ℃ 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 6 hours; and thirdly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain a gasoline and diesel oil component which is below the distillation range of 360 ℃ and rich in light aromatic hydrocarbons, wherein the wax oil component with the distillation range of 360 ℃ or 480 ℃ is obtained by separation and is delivered, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of ethylene cracking tar and is used for recycling the raw oil in the first step.
Example 17: the method for hydrogenating the ethylene cracking tar is carried out according to the following steps: step one, mixing a cobalt molybdenum sulfide catalyst and raw oil according to a mass ratio of 1:49 by taking ethylene cracking tar as the raw oil to obtain a first mixture, wherein the cobalt molybdenum sulfide catalyst accounts for 2.0% of the first mixture in the first mixture; mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of pressure of 22MPa, hydrogen partial pressure of not less than 20MPa and temperature of 390 ℃ to obtain a second mixture, wherein the volume ratio of the hydrogen to the first mixture is 600:1, and the residence time of the first mixture in the first suspension bed reactor is 2 hours; thirdly, mixing the second mixture with hydrogen, feeding the mixture into a second suspension bed reactor, and reacting under the reaction conditions of pressure of 22MPa, hydrogen partial pressure of not less than 20MPa and temperature of 480 ℃ to obtain a hydrogenation product, wherein the volume ratio of the hydrogen to the mixture is 600:1, and the retention time of the mixture in the second suspension bed reactor is 2 hours; and thirdly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain a gasoline and diesel oil component which is below the distillation range of 360 ℃ and rich in light aromatic hydrocarbons, wherein the wax oil component with the distillation range of 360 ℃ or 480 ℃ is obtained by separation and is delivered, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of ethylene cracking tar and is used for recycling the raw oil in the first step.
Example 18: the method for hydrogenating the ethylene cracking tar is carried out according to the following steps: step one, mixing a nickel-molybdenum sulfide catalyst and raw oil according to a mass ratio of 1:49 by taking ethylene cracking tar as the raw oil to obtain a first mixture, wherein the nickel-molybdenum sulfide catalyst accounts for 2.0% of the first mixture in the first mixture; mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 12MPa of pressure, no less than 10MPa of hydrogen partial pressure and 310 ℃ of temperature to obtain a second mixture, wherein the volume ratio of the hydrogen to the first mixture is 1600:1, and the residence time of the first mixture in the first suspension bed reactor is 7 hours; thirdly, mixing the second mixture with hydrogen, feeding the mixture into a second suspension bed reactor, and reacting under the reaction conditions of 12MPa of pressure, 10MPa of hydrogen partial pressure and 410 ℃ 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 7 hours; and thirdly, carrying out atmospheric and vacuum separation on the hydrogenation product to obtain a gasoline and diesel oil component which is below the distillation range of 360 ℃ and rich in light aromatic hydrocarbons, wherein the wax oil component with the distillation range of 360 ℃ or 480 ℃ is obtained by separation and is delivered, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of ethylene cracking tar and is used for recycling the raw oil in the first step.
In examples 12 to 18 of the present invention, the results of hydrogenation of ethylene cracking tar are shown in Table 1. Table 1 it can be seen that the present invention has very good implementation results. After two-step hydrogenation reaction of ethylene cracking tar, the conversion rate of asphaltene is as high as 99.9%, and the yield of light gasoline and diesel oil rich in aromatic hydrocarbon can be as high as 63.1%. The invention not only successfully avoids the problem of asphaltene coking, but also converts the asphaltene coking into monocyclic aromatic hydrocarbon with high added value, and has very good economic benefit.
In conclusion, the invention can realize the full-component hydro-conversion of the raw material, has high yield of the light component rich in the light aromatic hydrocarbon, can realize the 'dry-eating and clean-pressing' of the ethylene cracking tar, successfully avoids the problem of asphaltene coking, converts the tar into the monocyclic aromatic hydrocarbon with high added value, and has very good economic benefit.
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 hydrogenating ethylene cracking tar is characterized by comprising the following steps: step one, taking ethylene cracking tar as raw oil, and mixing a metal sulfide catalyst with the raw oil according to the mass ratio of 0.0001: 1-1: 19 to obtain a first mixture, wherein the metal sulfide catalyst accounts for 0.01-5.0% of the first mixture in the first mixture; mixing the first mixture and hydrogen, conveying the mixture into a first suspension bed reactor, and reacting under the reaction conditions of 10-25 MPa of pressure, no less than 8MPa of hydrogen partial pressure and 300-400 ℃ 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 25MPa of pressure, no less than 8MPa of hydrogen partial pressure and 400 ℃ to 500 ℃ 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 the gasoline and diesel oil component which is rich in light aromatic hydrocarbons and has the distillation range of below 360 ℃, wherein the wax oil component with the distillation range of between 360 ℃ and 480 ℃ is obtained by separation and is sent out, and the mixture with the distillation range of more than 480 ℃ is used as residual oil of ethylene cracking tar oil and is used for recycling the raw oil in the first step.
2. The method for hydrogenating ethylene cracking tar as claimed in claim 1, wherein the first suspended bed reactor and the second suspended bed reactor are connected in series.
3. The method for hydrogenating ethylene cracking tar as claimed in claim 1 or 2, wherein the reaction temperature of the first suspension bed reactor is not higher than the reaction temperature of the second suspension bed reactor.
4. The method for hydrogenating ethylene cracking tar as claimed in claim 1, 2 or 3, wherein the first mixture is reacted with hydrogen under the reaction conditions of 14MPa to 18MPa of pressure, 12MPa or more of partial pressure of hydrogen and 300 ℃ to 350 ℃ of temperature in the second step.
5. The method for hydrogenating ethylene cracking tar as recited in claim 1, 2, 3 or 4, wherein the second mixture is reacted with hydrogen under the reaction conditions of pressure of 14MPa to 18MPa, partial pressure of hydrogen of not less than 12MPa, and temperature of 450 ℃ to 500 ℃ in the third step.
6. The method for hydrogenating ethylene cracking tar according to claim 1, 2, 3, 4 or 5, wherein in the first step, the metal element in the metal sulfide catalyst is at least one of Fe, Co, Ni, Mo and W.
7. The method of mixing ethylene cracking tar with naphthenic base heavy oil or its residual oil according to claim 6, wherein the metal element Mo is contained in the metal sulfide catalyst in the first step.
8. The method of hydrogenating ethylene cracking tar according to any of the claims 1 to 7, characterized in that the particle size of the metal sulfide catalyst is less than 200 mesh.
9. The method for hydrogenating ethylene cracking tar according to any one of claims 1 to 8, wherein in the first step, the metal sulfide catalyst accounts for 1.0 to 2.0 percent of the raw oil by mass; or/and, 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.
10. The method for hydrogenating ethylene cracking tar according to any one of claims 1 to 9, wherein 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 from 4 hours to 6 hours.
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