WO2024078451A1 - 重质油改质减黏工艺 - Google Patents

重质油改质减黏工艺 Download PDF

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WO2024078451A1
WO2024078451A1 PCT/CN2023/123583 CN2023123583W WO2024078451A1 WO 2024078451 A1 WO2024078451 A1 WO 2024078451A1 CN 2023123583 W CN2023123583 W CN 2023123583W WO 2024078451 A1 WO2024078451 A1 WO 2024078451A1
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Prior art keywords
step reaction
solvent
heavy oil
oil fraction
reaction
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PCT/CN2023/123583
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English (en)
French (fr)
Inventor
王丽涛
王路海
刘银东
袁佩青
韩爽
张博
许倩
曹玉亭
宋海朋
于志敏
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中国石油天然气股份有限公司
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Publication of WO2024078451A1 publication Critical patent/WO2024078451A1/zh

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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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/24—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen-generating compounds
    • C10G45/28—Organic compounds; Autofining
    • 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
    • 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
    • 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
    • C10G67/14—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 including at least two different refining steps in the absence of hydrogen
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process

Definitions

  • the invention relates to the technical field of heavy oil modification and viscosity reduction, and in particular to a heavy oil modification and viscosity reduction process.
  • Visbreaking is a mature thermal processing technology that does not produce coke. It is generally used to treat heavy oil with high viscosity. Its main purpose is to improve the fluidity of heavy oil, improve the pour point and viscosity.
  • the oil after viscosity reduction treatment can provide raw materials for catalytic cracking or coking processes, and can also be used to produce fuel oil that meets certain specifications.
  • the current visbreaking process generally has the problem of difficulty in balancing the viscosity reduction depth and the stability of the modified oil.
  • the cracking products obtained after high-temperature cracking of heavy oil often need to be further hydrogenated. Due to the high cost of hydrogen sources and hydrogenation processes, its industrial application is limited.
  • the purpose of the present invention is to overcome the problem in the prior art that it is difficult to balance the viscosity reduction depth and oil product stability, and to provide a heavy oil modification and viscosity reduction process.
  • the present invention provides a heavy oil modification and viscosity reduction process, wherein the process comprises the following steps:
  • reaction product (2) reacting the heavy oil fraction, solvent and hydrogen donor to obtain a reaction product; wherein the reaction is selected from a one-step reaction or a two-step reaction;
  • the one-step reaction comprises contacting the heavy oil fraction, a solvent and a hydrogen donor, and reacting them under a supercritical environment at least reaching the supercritical temperature of the solvent to obtain a reaction product;
  • the two-step reaction comprises firstly mixing the heavy oil fraction and a solvent, and carrying out a first step reaction under a supercritical environment at least reaching the solvent to obtain an intermediate product; and then contacting the intermediate product with a hydrogen donor and an optional supplementary solvent to carry out a second step reaction to obtain a reaction product;
  • the heavy oil reforming and viscosity reduction process provided in the present invention can ensure the stability of the reformed oil while improving the viscosity reduction cracking depth, has a simple process flow, low production cost, and is suitable for industrial promotion.
  • FIG1 is a graph showing the stability test results of the modified oil prepared in Example 1 of the present invention.
  • FIG2 is a graph showing the stability test results of the modified oil prepared in Example 2 of the present invention.
  • FIG3 is a graph showing the stability test results of the modified oil prepared in Example 3 of the present invention.
  • FIG4 is a graph showing the stability test results of the modified oil prepared in Example 4 of the present invention.
  • FIG5 is a graph showing the stability test results of the modified oil prepared in Example 5 of the present invention.
  • FIG6 is a graph showing the stability test results of the modified oil prepared in Comparative Example 1 of the present invention.
  • FIG. 7 is a graph showing the stability test results of the modified oil prepared in Comparative Example 2 of the present invention.
  • any values of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values.
  • the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article.
  • the first aspect of the present invention provides a heavy oil modification and viscosity reduction process, wherein the process comprises the following steps:
  • reaction product (2) reacting the heavy oil fraction, the solvent and the hydrogen donor to obtain a reaction product; wherein the reaction is selected from a one-step reaction or a two-step reaction;
  • the one-step reaction comprises contacting the heavy oil fraction, a solvent and a hydrogen donor, and reacting them under a supercritical environment at least reaching the supercritical temperature of the solvent to obtain a reaction product;
  • the two-step reaction comprises firstly mixing the heavy oil fraction and a solvent, and carrying out a first step reaction under a supercritical environment at least reaching the solvent to obtain an intermediate product; and then contacting the intermediate product with a hydrogen donor and an optional supplementary solvent to carry out a second step reaction to obtain a reaction product;
  • step (1)
  • the heavy oil is selected from one or more of paraffin-based crude oil, intermediate-based crude oil and naphthenic crude oil having a solidification point above 30°C.
  • the cutting temperature of heavy oil can be adjusted according to the specific type of heavy oil.
  • the cutting temperature of the light oil fraction and the heavy oil fraction is 350-540°C, preferably 420-520°C.
  • the cutting temperature of the light oil fraction and the heavy oil fraction is 280-540°C, preferably 300-500°C.
  • the cutting temperature of the light oil fraction and the heavy oil fraction is 200-500°C, preferably 200-450°C.
  • the cutting of the heavy oil is carried out in a distillation tower.
  • the present invention does not specifically limit the operation of the distillation tower, and the operation can be carried out according to conventional operations in the art.
  • step (2)
  • the solvent is selected from monocyclic cycloalkanes and/or monocyclic aromatic hydrocarbons; wherein the monocyclic cycloalkanes are selected from cyclopentane and/or cyclohexane, and the monocyclic aromatic hydrocarbons are selected from one or more of benzene, toluene, and xylene.
  • the hydrogen donor is selected from cycloalkyl aromatic hydrocarbons; wherein the cycloalkyl aromatic hydrocarbons are selected from one or more of tetralin, decalin, and dihydroanthracene.
  • the mass ratio of the heavy oil fraction to the solvent is 1:0.5-5, preferably 1:1-3; the hydrogen donor accounts for 0.1-10% of the mass of the heavy oil fraction, preferably 0.3-2%.
  • the heavy oil fraction, solvent and hydrogen donor are fed separately; wherein the feed temperature of the heavy oil fraction is 40-150°C, preferably 60-120°C; the feed temperature of the solvent is room temperature, preferably 10-40°C; the feed temperature of the hydrogen donor is room temperature, preferably 10-40°C.
  • the solvent is divided into at least a part A solvent and a part B solvent, and the part A solvent accounts for 5%-50% by mass of the heavy oil fraction, preferably 10%-30%;
  • the solvent of part A is mixed with the heavy oil fraction and the hydrogen donor and then preheated to a temperature ⁇ 350°C, preferably 300-330°C; the solvent of part B is preheated alone, and the preheating temperature of the solvent of part B is 5-40°C higher than the temperature of the cracking reaction.
  • the A part solvent is mixed with the heavy oil fraction, which can play the role of diluting the heavy oil fraction, reducing the difficulty of transporting the heavy oil fraction, increasing the linear speed of the heavy oil fraction in the preheating furnace, and reducing the risk of coking.
  • the temperature of the A part solvent and the heavy oil fraction after preheating is lower than 350°C, and the temperature of the B part solvent after preheating under the one-step reaction pressure is higher than the temperature of the one-step reaction.
  • the two streams After the two streams are mixed, they enter the reactor of the one-step reaction together. The temperature difference between the two streams can reduce the risk of coking on the heavy oil fraction preheating furnace wall, pipeline and reactor wall, and extend the operation cycle of the device.
  • the reaction conditions of the one-step reaction include: the one-step reaction temperature is 320-430°C, preferably 380-420°C; the one-step reaction pressure is 6-15MPa, preferably 8-12MPa; the one-step reaction time is 1-60min, preferably 1-30min.
  • the mass ratio of the heavy oil fraction to the solvent is 1:0.5-5, preferably 1:1-3.
  • the heavy oil fraction and the solvent are fed separately; preferably, the feed temperature of the heavy oil fraction is 40-150°C, preferably 60-120°C; the feed temperature of the solvent is room temperature, preferably 10-40°C.
  • the solvent in the first step reaction, is divided into at least a C-part solvent and a D-part solvent; wherein the C-part solvent accounts for 5%-50% of the mass of the heavy oil fraction, preferably 10-30%; wherein the C-part solvent is mixed with the heavy oil fraction and preheated to a temperature ⁇ 350°C, preferably 300-330°C; the D-part solvent is preheated alone, and the preheating temperature of the D-part solvent is 5-40°C higher than the temperature of the cracking reaction.
  • the reaction conditions of the first step reaction include: the first step reaction temperature is 320-430°C, preferably 380-420°C; the first step reaction pressure is 6-15MPa, preferably 8-12MPa; the first step reaction time is 1-45min, preferably 1-20min.
  • the hydrogen donor accounts for 0.1-10% by mass, preferably 0.3-2% by mass of the heavy oil fraction.
  • the intermediate product in the second step reaction, is contacted with a hydrogen donor to cause a second step reaction to obtain a reaction product.
  • the intermediate product in the second step reaction, is contacted with a hydrogen donor and a supplementary solvent to undergo a second step reaction to obtain a reaction product.
  • adding a supplementary solvent in the second step reaction can play a role in enhancing mass transfer, improve the reaction efficiency and shorten the reaction time of the second step reaction while ensuring a considerable viscosity reduction effect and product stability.
  • the solvent in the first step reaction and the supplementary solvent in the second step reaction are independently selected from monocyclic cycloalkanes and/or monocyclic aromatic hydrocarbons, preferably independently selected from one or more of cyclopentane, cyclohexane, benzene, toluene and xylene.
  • the solvent in the first step reaction and the supplementary solvent in the second step reaction may be the same or different. For ease of operation, they are preferably the same.
  • the supplementary solvent in the second step reaction is mixed with the hydrogen donor and then fed, and the feeding temperature after mixing is 320-430°C, preferably 400-420°C.
  • the feed temperature after the supplementary solvent and the hydrogen donor are mixed in the second step reaction is preferably equal to the reaction temperature of the second step reaction.
  • the supplementary solvent in the second step reaction accounts for 5%-25%, preferably 10%-20% of the mass of the heavy oil fraction.
  • the reaction conditions of the second step reaction include: the second step reaction temperature is 320-430°C, preferably 380-420°C; the second step reaction pressure is 6-15MPa, preferably 8-12MPa; the second step reaction time is 1-30min, preferably 1-15min.
  • the first step reaction and the second step reaction are carried out in a shell-and-tube reactor.
  • the first step reaction and the second step reaction can be carried out in one reactor or in two reactors.
  • the one tube-in-tube fixed bed reactor can be divided into two reaction zones by controlling the feeding position of the hydrogen supply agent and/or the supplementary solvent in the second step reaction.
  • the hydrogen donor can saturate the polycyclic aromatic carbon radicals by providing active hydrogen, so that the condensation reaction in the thermal cracking process of heavy oil is partially inhibited. It should be pointed out that the presence of the hydrogen donor in the cracking system can not only saturate the aromatic carbon radicals, but also saturate the alkyl carbon radicals that initiate the thermal cracking reaction network, resulting in a decrease in the radical concentration. This greatly prolongs the initiation time of thermal cracking and reduces the efficiency of the thermal cracking reaction. Therefore, the traditional method of directly adding hydrogen donor components to the viscosity-reducing raw materials and simultaneously performing thermal cracking generally causes the initiation and chain propagation efficiency of the heavy oil thermal cracking network to lag.
  • Adding the hydrogen donor in the later stage of the reaction does not affect the radical concentration of hydrocarbons generated in the early cracking reaction, and secondly, the added hydrogen donor can be fully used to saturate the polycyclic aromatic carbon radicals that have a tendency to condense and produce coke, without causing unnecessary waste.
  • step (3)
  • the separation is flash evaporation, wherein the flash evaporation is performed in a flash evaporator.
  • the present invention does not specifically limit the operation of the flash evaporator, and the operation can be performed according to conventional operations in the art.
  • the recovered solvent is returned to step (2) for recycling.
  • the recovered solvent can be separated and then returned to the first step reaction and the second step reaction for recycling.
  • step (4)
  • the cracked product before mixing the light oil fraction and the cracked product, is pretreated to obtain a pretreated product; and the light oil fraction and the pretreated product are mixed to obtain a modified oil.
  • the pretreatment includes: first distilling the cracking product to obtain light oil and heavy oil; wherein the cutting temperature of the light oil and the heavy oil is 200-280°C; then settling the light oil to remove diolefins; and then mixing the settled light oil with the heavy oil to obtain a pretreated product.
  • the dienes can be removed through sedimentation treatment, thereby preventing the dienes from self-aggregation and precipitation during storage, thereby affecting the storage stability of the modified oil.
  • the sedimentation treatment includes standing and filtration, wherein the standing is performed at room temperature for 4-10 days, preferably 5-7 days; the filtration is performed at room temperature, and the present invention does not specifically limit the filtration method.
  • the modified oil has a stability of level 1-2, and a kinematic viscosity at 50° C. of ⁇ 300 mm 2 /s, preferably 50-200 mm 2 /s.
  • the light oil fraction and the cracking product or the pre-treated product are mixed, which can further reduce the viscosity of the modified oil and improve the stability of the modified oil.
  • the heavy oil fraction and the C part of cyclohexane are mixed and preheated to 330° C. at 10 MPa, and then mixed with the D part of cyclohexane preheated to 422° C. at 10 MPa, and introduced into the shell-and-tube cracking reactor from the bottom of the shell-and-tube cracking reactor; the heavy oil fraction, the C part of cyclohexane and the D part of cyclohexane undergo a first step reaction in the shell-and-tube cracking reactor to obtain an intermediate product;
  • the mass ratio of the heavy oil fraction to cyclohexane (the sum of the mass of the cyclohexane in the C part and the cyclohexane in the D part) is 1:2, the cyclohexane in the C part accounts for 20% of the mass of the heavy oil fraction, the temperature of the first step reaction is 410°C, the pressure of the first step reaction is 10 MPa, and the reaction time of the first step is 10 min;
  • tetralin accounts for 0.5% of the mass of the heavy oil fraction
  • the supplementary cyclohexane accounts for 15% of the mass of the heavy oil fraction
  • the second step reaction temperature is 410°C
  • the second step reaction pressure is 10MPa
  • the second step reaction time is 5min;
  • the mass ratio of heavy oil fraction to cyclohexane is 1:2.2, tetralin accounts for 0.5% of the mass of heavy oil fraction, the temperature of the one-step reaction is 410°C, the pressure of the one-step reaction is 10 MPa, and the time of the one-step reaction is 15 min.
  • step (3) introducing the reaction product into a flash evaporator for flash evaporation to obtain a recovered solvent and a cracked product; introducing the obtained cracked product into a distillation tower for distillation, extracting a light oil with a boiling point of ⁇ 280°C from the top of the distillation tower, and extracting a heavy oil with a boiling point of >280°C from the bottom of the tower; returning the recovered cyclohexane to step (2) and step (3) for recycling; introducing the light oil into a settler for sedimentation treatment, standing at room temperature for 7 days, and then filtering, removing dienes and mixing with the heavy oil to obtain a pretreated product;
  • Chad crude oil paraffin-based crude oil with a freezing point higher than 30° C.
  • a distillation tower cutting it at a cutting temperature of 500° C. to obtain a light oil fraction with a boiling point of less than 500° C. and a heavy oil fraction with a boiling point of ⁇ 500° C.
  • the heavy oil fraction and the C part benzene are mixed and preheated to 330° C., and then mixed with the D part benzene preheated to 433° C. at 10 MPa, and introduced into the shell-and-tube cracking reactor from the bottom of the shell-and-tube cracking reactor; the heavy oil fraction, the C part benzene and the D part benzene undergo a first step reaction in the shell-and-tube cracking reactor to obtain an intermediate product;
  • the mass ratio of the heavy oil fraction to benzene (the sum of the mass of the benzene in the C part and the benzene in the D part) is 1:3, the benzene in the C part accounts for 10% of the mass of the heavy oil fraction, the temperature of the first step reaction is 425°C, the first step reaction pressure is 10 MPa, and the first step reaction time is 5 min;
  • tetralin accounts for 1.0% of the mass of the heavy oil fraction
  • supplementary benzene accounts for 10% of the mass of the heavy oil fraction
  • the second step reaction temperature is 425°C
  • the second step reaction pressure is 10MPa
  • the second step reaction time is 5min;
  • Russian crude oil (intermediate base crude oil) is introduced into a distillation tower and cut at a cutting temperature of 450° C. to obtain a light oil fraction with a boiling point of less than 450° C. and a heavy oil fraction with a boiling point of ⁇ 450° C.;
  • the heavy oil fraction and the C part of cyclohexane are mixed and preheated to 330° C., and then mixed with the D part of cyclohexane preheated to 428° C. at 10 MPa, and introduced into the shell-and-tube cracking reactor from the bottom of the shell-and-tube cracking reactor; the heavy oil fraction, the C part of cyclohexane and the D part of cyclohexane undergo a first step reaction in the shell-and-tube cracking reactor to obtain an intermediate product;
  • the mass ratio of the heavy oil fraction to cyclohexane (the sum of the mass of the cyclohexane in the C part and the cyclohexane in the D part) is 1:3, the cyclohexane in the C part accounts for 20% of the mass of the heavy oil fraction, the temperature of the first step reaction is 415°C, the pressure of the first step reaction is 10 MPa, and the reaction time of the first step is 8 min;
  • decalin accounts for 0.5% of the mass of the heavy oil fraction
  • the supplementary cyclohexane accounts for 15% of the mass of the heavy oil fraction
  • the second step reaction temperature is 415°C
  • the second step reaction pressure is 10MPa
  • the second step reaction time is 4min;
  • step (3) introducing the reaction product into a flash evaporator for flash evaporation to obtain a recovered solvent and a cracking product; introducing the obtained cracking product into a distillation tower for distillation, extracting a light oil with a boiling point of ⁇ 200°C from the top of the distillation tower, and extracting a heavy oil with a boiling point of >200°C from the bottom of the tower; returning the recovered cyclohexane to step (2) and step (3) for recycling; introducing the light oil into a settler for sedimentation treatment, standing at room temperature for 7 days, and then filtering, removing diolefins and mixing with the heavy oil to obtain a pretreated product.
  • Chad crude oil paraffin-based crude oil with a freezing point higher than 30° C.
  • a distillation tower cutting it at a cutting temperature of 500° C. to obtain a light oil fraction with a boiling point of less than 500° C. and a heavy oil fraction with a boiling point of ⁇ 500° C.
  • the heavy oil fraction and the C part of cyclohexane are mixed and preheated to 330° C., and then mixed with the D part of cyclohexane preheated to 433° C. at 10 MPa, and introduced into the shell-and-tube cracking reactor from the bottom of the shell-and-tube cracking reactor; the heavy oil fraction, the C part of cyclohexane and the D part of cyclohexane undergo a first step reaction in the shell-and-tube cracking reactor to obtain an intermediate product;
  • the mass ratio of the heavy oil fraction to cyclohexane (the sum of the mass of the cyclohexane in the C part and the cyclohexane in the D part) is 1:2, the cyclohexane in the C part accounts for 20% of the mass of the heavy oil fraction, the temperature of the first step reaction is 425°C, the pressure of the first step reaction is 10 MPa, and the reaction time of the first step is 5 min;
  • tetralin accounts for 1.0% of the mass of the heavy oil fraction
  • the second step reaction temperature is 425°C
  • the second step reaction pressure is 10MPa
  • the second step reaction time is 5min;
  • the mass ratio of heavy oil fraction to cyclohexane is 1:2.2, the temperature of the first step reaction is 410°C, the pressure of the first step reaction is 10 MPa, and the time of the first step reaction is 15 min.
  • step (3) introducing the reaction product into a flash evaporator for flash evaporation to obtain a recovered solvent and a cracked product; introducing the obtained cracked product into a distillation tower for distillation, extracting a light oil with a boiling point of ⁇ 280°C from the top of the distillation tower, and extracting a heavy oil with a boiling point of >280°C from the bottom of the tower; returning the recovered cyclohexane to step (2) and step (3) for recycling; introducing the light oil into a settler for sedimentation treatment, standing at room temperature for 7 days, and then filtering, removing dienes and mixing with the heavy oil to obtain a pretreated product;
  • the mass ratio of heavy oil fraction to cyclohexane is 1:2.2, tetralin accounts for 1.5% of the mass of heavy oil fraction, the temperature of the one-step reaction is 410°C, the pressure of the one-step reaction is 0.6MPa, and the time of the one-step reaction is 15min.
  • step (3) introducing the reaction product into a flash evaporator for flash evaporation to obtain a recovered solvent and a cracked product; introducing the obtained cracked product into a distillation tower for distillation, extracting a light oil with a boiling point of ⁇ 280°C from the top of the distillation tower, and extracting a heavy oil with a boiling point of >280°C from the bottom of the tower; returning the recovered cyclohexane to step (2) and step (3) for recycling; introducing the light oil into a settler for sedimentation treatment, standing at room temperature for 7 days, and then filtering, removing dienes and mixing with the heavy oil to obtain a pretreated product;
  • Table 1 Note: The "——” in Table 1 indicates that the viscosity of the sample to be tested is too high to be measured at the test temperature.
  • the method provided in the present invention can reduce the 50°C viscosity of the cracked product to below 200 mPa.s, which can meet the requirements of heavy oil transportation.
  • mixing the cracked product with the light oil fraction can further reduce the viscosity of the oil product.
  • Level 1 The spots are evenly spaced, with no rings inside;
  • Level 2 There are fine and fuzzy rings inside the spots
  • Level 3 There is a distinct thin ring inside the spot, which is slightly darker than the natural color
  • Grade 4 has a thicker ring than Grade 3, and is slightly darker than the natural color
  • Level 5 The ring inside the spot is almost solid or nearly solid, and the center of the ring is much darker than the background color.
  • Figures 1-7 are the stability test results of the modified oil prepared in Examples 1-5 and Comparative Examples 1-2, respectively.
  • the spots in Examples 1, 3, and 4 are uniform, there are no rings inside, and the stability is level 1.
  • the spots in Examples 2 and 5 are uniform, there are subtle and fuzzy color differences inside, and the stability is between level 1 and level 2.

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  • Engineering & Computer Science (AREA)
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Abstract

一种重质油改质减黏工艺：（1）将重质油进行切割，得到轻油馏分和重油馏分；（2）将重油馏分、溶剂和供氢剂进行反应，得到反应产物；反应选自一步反应或两步反应；一步反应包括将重油馏分、溶剂和供氢剂接触，在至少达到所述溶剂的超临界环境下进行反应；两步反应包括先将重油馏分和溶剂在至少达到溶剂的超临界环境下进行第一步反应，得到中间产物；然后再将中间产物与供氢剂和任选的补充溶剂接触，发生第二步反应；（3）将反应产物进行分离，得到回收溶剂和裂化产物；（4）将轻油馏分和裂化产物混合，得到改质油。该改质减黏工艺，可在提高减黏裂化深度的同时保证改质油的安定性，适合推广。

Description

重质油改质减黏工艺
相关申请的交叉引用
本申请要求2022年10月11日提交的中国专利申请202211243597.3的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及重质油改质减黏技术领域，具体涉及一种重质油改质减黏工艺。
背景技术
减黏裂化是一种成熟的不生成焦炭的热加工技术，一般用于处理黏度较大的重质油，主要目的是提高重质油的流动性，改善倾点和黏度，经过减黏处理后的油品可以为催化裂化或者焦化等工艺提供原料，也可以用于生产符合一定规格要求的燃料油。
目前的减黏裂化工艺普遍存在减黏深度和改质油安定性难以兼顾的问题。除此之外，重质油高温裂化后得到的裂化产物往往需要进一步进行加氢处理，受氢气来源和加氢工艺成本高的影响，其工业化应用受限。
因此，亟待提供一种既可提高减黏裂化深度又可保证减黏裂化后油品安定性的重质油改质减黏工艺。
发明内容
本发明的目的是为了克服现有技术存在的减黏深度和油品安定性难以兼顾的问题，提供一种重质油改质减黏工艺。
为了实现上述目的，本发明提供了一种重质油改质减黏工艺，其中，所述工艺包括以下步骤：
(1)将重质油进行切割，得到轻油馏分和重油馏分；其中，所述轻油馏分和重油馏分的切割温度为200-540℃；
(2)将所述重油馏分、溶剂和供氢剂进行反应，得到反应产物；其中，所述反应选自一步反应或两步反应；
其中，所述一步反应包括将所述重油馏分、溶剂和供氢剂接触，在至少达到所述溶剂的超临界环境下进行反应，得到反应产物；
其中，所述两步反应包括先将所述重油馏分和溶剂混合，在至少达到所述溶剂的超临界环境下进行第一步反应，得到中间产物；然后再将所述中间产物与供氢剂和任选的补充溶剂接触，发生第二步反应，得到反应产物；
(3)将所述反应产物进行分离，得到回收溶剂和裂化产物；
(4)将所述轻油馏分和裂化产物混合，得到改质油。
本发明中提供的重质油改质减黏工艺，可以在确保提高减黏裂化深度的同时保证改质油的安定性，工艺流程简单，生产成本低，适合工业化推广。
附图说明
附图是用来提供对本发明的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本发明，但并不构成对本发明的限制。在附图中：
图1是本发明的实施例1所制备得到的改质油的稳定性测试结果图；
图2是本发明的实施例2所制备得到的改质油的稳定性测试结果图；
图3是本发明的实施例3所制备得到的改质油的稳定性测试结果图；
图4是本发明的实施例4所制备得到的改质油的稳定性测试结果图；
图5是本发明的实施例5所制备得到的改质油的稳定性测试结果图；
图6是本发明的对比例1所制备得到的改质油的稳定性测试结果图；
图7是本发明的对比例2所制备得到的改质油的稳定性测试结果图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明的第一方面提供了一种重质油改质减黏工艺，其中，所述工艺包括以下步骤：
(1)将重质油进行切割，得到轻油馏分和重油馏分；其中，所述轻油馏分和重油馏分的切割温度为200-540℃；
(2)将所述重油馏分、溶剂和供氢剂进行反应，得到反应产物；其中，所述反应选自一步反应或两步反应；
其中，所述一步反应包括将所述重油馏分、溶剂和供氢剂接触，在至少达到所述溶剂的超临界环境下进行反应，得到反应产物；
其中，所述两步反应包括先将所述重油馏分和溶剂混合，在至少达到所述溶剂的超临界环境下进行第一步反应，得到中间产物；然后再将所述中间产物与供氢剂和任选的补充溶剂接触，发生第二步反应，得到反应产物；
(3)将所述反应产物进行分离，得到回收溶剂和裂化产物；
(4)将所述轻油馏分和裂化产物混合，得到改质油。
在步骤(1)中：
在一个优选的实施方式中，所述重质油选自凝点在30℃以上的石蜡基原油、中间基原油和环烷基原油中的一种或多种。
其中，在本发明中，重质油的切割温度可根据重质油的具体类型进行调整。例如，当重质油为凝点在30℃以上的石蜡基原油时，轻油馏分和重油馏分的切割温度为350-540℃，优选为420-520℃。当重质油为中间基原油时，轻油馏分和重油馏分的切割温度为280-540℃，优选为300-500℃。当重质油为环烷基原油时，轻油馏分和重油馏分的切割温度为200-500℃，优选为200-450℃。
在一个优选的实施方式中，所述重质油的切割在蒸馏塔中进行。其中，本发明对蒸馏塔的操作不做特殊限定，按照本领域的常规操作进行即可。
在步骤(2)中：
在一个优选的实施方式中，所述溶剂选自单环环烷烃和/或单环芳烃；其中，所述单环环烷烃选自环戊烷和/或环己烷，所述单环芳烃选自苯、甲苯、二甲苯中的一种或多种。
在一个优选的实施方式中，所述供氢剂所述供氢剂选自环烷基芳烃；其中，所述环烷基芳烃选自四氢萘、十氢萘、二氢蒽中的一种或多种。
在一步反应中：
在一个优选的实施方式中，所述重油馏分和溶剂的质量比为1：0.5-5，优 选为1：1-3；所述供氢剂占所述重油馏分质量的0.1-10％，优选0.3-2％。
在一个优选的实施方式中，所述重油馏分、溶剂和供氢剂分别独自进料；其中，所述重油馏分的进料温度为40-150℃，优选为60-120℃；所述溶剂的进料温度为室温，优选为10-40℃；所述供氢剂的进料温度为室温，优选为10-40℃。
在一个优选的实施方式中，所述溶剂至少分为A部分溶剂和B部分溶剂，所述A部分溶剂占所述重油馏分质量的5％-50％，优选为10％-30％；
其中，所述A部分溶剂与所述重油馏分和供氢剂混合后预热到温度≤350℃，优选预热为300-330℃；所述B部分溶剂独自预热，所述B部分溶剂的预热温度比所述裂解反应的温度高5-40℃。
其中，在本发明中，将A部分溶剂与重油馏分混合，可以起到稀释重油馏分的作用，降低重油馏分的输送难度，提高重油馏分在预热炉里的线速度，降低结焦风险。A部分溶剂与重油馏分预热后的温度低于350℃，B部分溶剂在一步反应压力下预热后的温度高于一步反应的温度，两股物流混合后一起进入一步反应的反应器，两股物流之间的温度差，可降低重油馏分预热炉壁、管道和反应器器壁结焦风险，延长装置运行周期。
在一个优选的实施方式中，所述一步反应的反应条件包括：一步反应温度为320-430℃，优选为380-420℃；一步反应压力为6-15MPa，优选为8-12MPa；一步反应时间为1-60min，优选为1-30min。
在二步反应中：
在一个优选的实施方式中，在所述第一步反应中，所述重油馏分和溶剂的质量比为1：0.5-5，优选为1：1-3。
在一个优选的实施方式中，在所述第一步反应中，所述重油馏分和所述溶剂分别独自进料；优选地，所述重油馏分的进料温度为40-150℃，优选为60-120℃；所述溶剂的进料温度为室温，优选为10-40℃。
在一个优选的实施方式中，在所述第一步反应中，所述溶剂至少分为C部分溶剂和D部分溶剂；其中，所述C部分溶剂占所述重油馏分质量的5％-50％，优选为10-30％；其中，所述C部分溶剂与所述重油馏分混合后预热到温度≤350℃，优选预热到300-330℃；所述D部分溶剂独自预热，所述D部分溶剂的预热温度比所述裂解反应的温度高5-40℃。
在一个优选的实施方式中，所述第一步反应的反应条件包括：第一步反应温度为320-430℃，优选为380-420℃；第一步反应压力为6-15MPa，优选为8-12MPa；第一步反应时间为1-45min，优选为1-20min。
在一个优选的实施方式中，在所述第二步反应中，以第一步反应中的重油馏分计，所述供氢剂占所述重油馏分质量的0.1-10％，优选0.3-2％。
在一个优选的实施方式中，在所述第二步反应中，将所述中间产物与供氢剂接触，发生第二步反应，得到反应产物。
在一个优选的实施方式中，在所述第二步反应中，将所述中间产物与供氢剂和补充溶剂接触，发生第二步反应，得到反应产物。
其中，在本发明中，在第二步反应中添加补充溶剂，可以起到强化传质的作用，在保证相当的降黏效果和产物安定性的前提下，提高反应效率，缩短第二步反应的反应时间。
在一个优选的实施方式中，在所述第一步反应中的溶剂与在所述第二步反应中的补充溶剂分别独自选自单环环烷烃和/或单环芳烃，优选分别独自选自环戊烷、环己烷、苯、甲苯、二甲苯中的一种或多种。
其中，在本发明中，第一步反应中的溶剂与在第二步反应中的补充溶剂可以相同，也可以不相同，为方便操作，优选为相同。
在一个优选的实施方式中，在所述第二步反应中的补充溶剂与供氢剂混合后进料，混合后的进料温度为320-430℃，优选为400-420℃。
其中，在本发明中，在第二步反应中的补充溶剂与供氢剂混合后的进料温度优选等于第二步反应的反应温度。
在一个优选的实施方式中，以第一步反应中的重油馏分计，所述第二步反应中的补充溶剂占所述重油馏分质量的5％-25％、优选的10％-20％。
在一个优选的实施方式中，所述第二步反应的反应条件包括：第二步反应温度为320-430℃，优选为380-420℃；第二步反应压力为6-15MPa，优选为8-12MPa；第二步反应时间为1-30min，优选为1-15min。
在一个优选的实施方式中，所述第一步反应和第二步反应在列管式反应器中进行。
其中，在本发明中，第一步反应和第二步反应可以在一个反应器中进行，也可以在两个反应器中进行。当第一步反应和第二步反应在一个反应器中进行时，可通过控制第二步反应中供氢剂和/或补充溶剂的进料位置，将一个列管式固定床反应器分成两个反应区。
供氢剂通过提供活泼氢能饱和稠环芳碳自由基，使得重油热裂化过程中的缩合反应受到部分抑制。需要指出的是，供氢剂在裂化体系中的存在不仅能够饱和芳碳自由基，同时也能饱和引发热裂化反应网络的烷基碳自由基，造成自由基浓度下降。这使得使得热裂化的引发时间大幅延长，降低了热裂化反应效率。因此传统的在减黏原料中直接添加供氢组分同步进行热裂化的方式普遍造成重油热裂化网络的引发和链传播效率滞后。而在反应后期再加入供氢剂，一方面不影响前期裂化反应中烃产生的自由基浓度，第二是所添加的供氢剂可充分用以饱和有缩合生焦倾向的稠环芳炭自由基，不会造成无谓浪费。
在步骤(3)中：
在一个优选的实施方式中，所述分离为闪蒸；其中，所述闪蒸在闪蒸器中进行。本发明对闪蒸器的操作不做特殊限定，按照本领域的常规操作进行即可。
在一个优选的实施方式中，将所述回收溶剂返回步骤(2)循环使用。在两步反应中，当第一步反应中的溶剂与在所述第二步反应中的补充溶剂不相同时，可将回收溶剂进行分离，然后分别返回第一步反应和第二步反应中循环使用。
在步骤(4)中：
在一个优选的实施方式中，在将所述轻油馏分和裂化产物混合前，对所述裂化产物进行预处理，得到预处理产物；将所述轻油馏分和预处理产物混合，得到改质油。
在一个优选的实施方式中，所述预处理包括：先将所述裂解产物进行精馏，得到轻质油和重质油；其中，所述轻质油和重质油的切割温度为200-280℃；然后将所述轻质油进行沉降，以脱除二烯烃；之后将完成沉降后的轻质油与重质油进行混合，得到预处理产物。
其中，在本发明中，经过沉降处理，可以脱除二烯烃，避免二烯烃在放置过程中自聚沉淀，影响改质油的储存稳定性。
在一个优选的实施方式中，所述沉降处理包括静置和过滤，其中，所述静置在室温下进行，静置时间为4-10天，优选为5-7天；所述过滤在室温下进行，本发明对过滤方式不做特殊限定。
在一个优选的实施方式中，所述改质油所述改质油的稳定性为1-2级，50℃运动黏度为≤300mm2/s，优选为50-200mm2/s。
其中，在本发明中，将轻油馏分和裂化产物或预处理产物进行混合，可进一步降低改质油的黏度，提高改质油的稳定性。
以下将通过实施例对本发明进行详细描述。
实施例1
(1)将加拿大油砂沥青(环烷基油)引入蒸馏塔中，进行切割，切割温度为420℃，得到沸点＜420℃的轻油馏分和沸点≥420℃的重油馏分；
(2)将上述重油馏分和C部分环己烷混合后在10MPa下预热到330℃，然后与在10MPa下预热到422℃的D部分环己烷混合，从列管式裂化反应器的底部引入列管式裂化反应器；重油馏分、C部分环己烷和D部分环己烷在列管式裂化反应器内发生第一步反应，得到中间产物；
其中，重油馏分和环己烷(C部分环己烷和D部分环己烷的质量之和)的质量比为1：2，C部分环己烷占重油馏分质量的20％，第一步反应的温度为410℃，第一步反应压力为10MPa，第一步反应时间为10min；
(3)将补充环己烷与四氢萘混合后在10MPa下加热到410℃，从列管式裂化反应器的中上部引入列管式裂化反应器，与中间产物接触，发生第二步反应，得到反应产物；
其中，四氢萘占重油馏分质量的0.5％，补充环己烷占重油馏分质量的15％，第二步反应温度为410℃，第二步反应压力为10MPa，第二步反应反应时间为5min；
(4)将上述反应产物引入闪蒸器中进行闪蒸，得到回收溶剂和裂化产物；将得到的裂化产物引入精馏塔中进行精馏，从精馏塔塔顶采出沸点≤280℃的轻质油，从塔底采出沸点＞280℃的重质油；将回收环己烷返回步骤(2)和步骤(3)循环利用；将上述轻质油引入沉降器中，进行沉降处理，室温下静置7天，之后进行过滤，脱除二烯烃后与重质油混合，得到预处理产物。
(5)将上述轻油馏分和预处理产物混合，得到改质油。
实施例2
(1)将加拿大油砂沥青(环烷基油)引入蒸馏塔中，进行切割，切割温度为420℃，得到沸点＜420℃的轻油馏分和沸点≥420℃的重油馏分；
(2)将上述重油馏分加热到330℃，将四氢萘加热到330℃，将环己烷在10MPa下加热到415℃；加热后的重油馏分、环己烷和四氢萘从列管式裂化反应器的底部引入列管式裂化反应器，发生一步反应，得到反应产物；
其中，重油馏分和环己烷的质量比为1：2.2，四氢萘占重油馏分质量的0.5％，一步反应的温度为410℃，一步反应压力为10MPa，一步反应时间为15min；
(3)将上述反应产物引入闪蒸器中进行闪蒸，得到回收溶剂和裂化产物；将得到的裂化产物引入精馏塔中进行精馏，从精馏塔塔顶采出沸点≤280℃的轻质油，从塔底采出沸点＞280℃的重质油；将回收环己烷返回步骤(2)和步骤(3)循环利用；将上述轻质油引入沉降器中，进行沉降处理，室温下静置7天，之后进行过滤，脱除二烯烃后与重质油混合，得到预处理产物；
(4)将上述轻油馏分和预处理产物混合，得到改质油。
实施例3
(1)将乍得原油(凝点高于30℃的石蜡基原油)引入蒸馏塔中，进行切割，切割温度为500℃，得到沸点＜500℃的轻油馏分和沸点≥500℃的重油馏分；
(2)将上述重油馏分和C部分苯混合后预热到330℃，然后与在10MPa下预热到433℃的D部分苯混合，从列管式裂化反应器的底部引入列管式裂化反应器；重油馏分、C部分苯和D部分苯在列管式裂化反应器内发生第一步反应，得到中间产物；
其中，重油馏分和苯(C部分苯和D部分苯的质量之和)的质量比为1：3，C部分苯占重油馏分质量的10％，第一步反应的温度为425℃，第一步反应压力为10MPa，第一步反应时间为5min；
(3)将补充苯与四氢萘混合后在10MPa下加热到425℃，从列管式裂化反应器的中上部引入列管式裂化反应器，与中间产物接触，发生第二步反应，得到反应产物；
其中，四氢萘占重油馏分质量的1.0％，补充苯占重油馏分质量的10％，第二步反应温度为425℃，第二步反应压力为10MPa，第二步反应反应时间为5min；
(4)将上述反应产物引入闪蒸器中进行闪蒸，得到回收溶剂和裂化产物；将回收溶剂返回步骤(2)和步骤(3)循环利用；
(5)将上述裂化产物和轻馏分油混合，得到改质油。
实施例4
(1)将俄罗斯原油(中间基原油)引入蒸馏塔中，进行切割，切割温度为450℃，得到沸点＜450℃的轻油馏分和沸点≥450℃的重油馏分；
(2)将上述重油馏分和C部分环己烷混合后预热到330℃，然后与在10MPa下预热到428℃的D部分环己烷混合，从列管式裂化反应器的底部引入列管式裂化反应器；重油馏分、C部分环己烷和D部分环己烷在列管式裂化反应器内发生第一步反应，得到中间产物；
其中，重油馏分和环己烷(C部分环己烷和D部分环己烷的质量之和)的质量比为1：3，C部分环己烷占重油馏分质量的20％，第一步反应的温度为415℃，第一步反应压力为10MPa，第一步反应时间为8min；
(3)将补充环己烷与十氢萘混合后在10MPa下加热到415℃，从列管式裂化反应器的中上部引入列管式裂化反应器，与中间产物接触，发生第二步反应，得到反应产物；
其中，十氢萘占重油馏分质量的0.5％，补充环己烷占重油馏分质量的15％，第二步反应温度为415℃，第二步反应压力为10MPa，第二步反应反应时间为4min；
(4)将上述反应产物引入闪蒸器中进行闪蒸，得到回收溶剂和裂化产物；将得到的裂化产物引入精馏塔中进行精馏，从精馏塔塔顶采出沸点≤200℃的轻质油，从塔底采出沸点＞200℃的重质油；将回收环己烷返回步骤(2)和步骤(3)循环利用；将上述轻质油引入沉降器中，进行沉降处理，室温下静置7天，之后进行过滤，脱除二烯烃后与重质油混合，得到预处理产物。
(5)将上述轻油馏分和预处理产物混合，得到改质油。
实施例5
(1)将乍得原油(凝点高于30℃的石蜡基原油)引入蒸馏塔中，进行切割，切割温度为500℃，得到沸点＜500℃的轻油馏分和沸点≥500℃的重油馏分；
(2)将上述重油馏分和C部分环己烷混合后预热到330℃，然后与在10MPa下预热到433℃的D部分环己烷混合，从列管式裂化反应器的底部引入列管式裂化反应器；重油馏分、C部分环己烷和D部分环己烷在列管式裂化反应器内发生第一步反应，得到中间产物；
其中，重油馏分和环己烷(C部分环己烷和D部分环己烷的质量之和)的质量比为1：2，C部分环己烷占重油馏分质量的20％，第一步反应的温度为425℃，第一步反应压力为10MPa，第一步反应时间为5min；
(3)将四氢萘在10MPa下加热到425℃，从列管式裂化反应器的中上部引入列管式裂化反应器，与中间产物接触，发生第二步反应，得到反应产物；
其中，四氢萘占重油馏分质量的1.0％，第二步反应温度为425℃，第二步反应压力为10MPa，第二步反应反应时间为5min；
(4)将上述反应产物引入闪蒸器中进行闪蒸，得到回收溶剂和裂化产物；将回收溶剂返回步骤(2)和步骤(3)循环利用；
(5)将上述裂化产物和轻馏分油混合得到改质油。
对比例1
(1)将加拿大油砂沥青引入蒸馏塔中，进行切割，切割温度为420℃，得到沸点＜420℃的轻油馏分和沸点≥420℃的重油馏分；
(2)将上述重油馏分加热到330℃，将环己烷在10MPa下加热到415℃，加热后的重油馏分和环己烷从列管式裂化反应器的底部引入列管式裂化反应器，发生一步反应，得到反应产物；
其中，重油馏分和环己烷的质量比为1：2.2，一步反应的温度为410℃，一步反应压力为10MPa，一步反应时间为15min；
(3)将上述反应产物引入闪蒸器中进行闪蒸，得到回收溶剂和裂化产物；将得到的裂化产物引入精馏塔中进行精馏，从精馏塔塔顶采出沸点≤280℃的轻质油，从塔底采出沸点＞280℃的重质油；将回收环己烷返回步骤(2)和步骤(3)循环利用；将上述轻质油引入沉降器中，进行沉降处理，室温下静置7天，之后进行过滤，脱除二烯烃后与重质油混合，得到预处理产物；
(4)将上述轻油馏分和预处理产物混合，得到改质油。
对比例2
(1)将加拿大油砂沥青引入蒸馏塔中，进行切割，切割温度为420℃，得到沸点＜420℃的轻油馏分和沸点≥420℃的重油馏分；
(2)将上述重油馏分加热到330℃，将四氢萘加热到330℃，将环己烷在0.6MPa下加热到415℃；加热后的重油馏分、环己烷和四氢萘从列管式裂化反应器的底部引入列管式裂化反应器，发生一步反应，得到反应产物；
其中，重油馏分和环己烷的质量比为1：2.2，四氢萘占重油馏分质量的1.5％，一步反应的温度为410℃，一步反应压力为0.6MPa，一步反应时间为15min；
(3)将上述反应产物引入闪蒸器中进行闪蒸，得到回收溶剂和裂化产物；将得到的裂化产物引入精馏塔中进行精馏，从精馏塔塔顶采出沸点≤280℃的轻质油，从塔底采出沸点＞280℃的重质油；将回收环己烷返回步骤(2)和步骤(3)循环利用；将上述轻质油引入沉降器中，进行沉降处理，室温下静置7天，之后进行过滤，脱除二烯烃后与重质油混合，得到预处理产物；
(4)将上述轻油馏分和预处理产物混合，得到改质油。
测试例1
对实施例1-5和对比例1-2中得到的重油馏分、裂化产物和改质油按照GB/T269进行运动黏度测试，测试结果如表1和表2所示：
表1


注：表1中的——表示在测试温度下，由于待测样品的黏度太高无法进行测
定。
表2
由表1可知，本发明中提供的方法可将裂化产物的50℃黏度降低在200mPa.s以下，可以满足重油运输的要求。由表2可知，将裂化产物与轻油馏分混合，可进一步降低油品的黏度。
测试例2
对实施例1-5和对比例1-2中得到的改质油按照ASTM D4740-04(2014)中规定的斑点测试实验进行稳定性测试，稳定性评级标准如下。
1级：斑点均匀，内部无环状物；
2级：斑点内部有细微而模糊的环状物；
3级：斑点内部有明显的薄的环状物，比本色稍微黑一点；
4级：有比三级等级更浓的环状物，亦比本色稍黑；
5级：斑点内部环状物几乎为固体或近于固体，环心比本底色黑的多。
其中，图1-7分别为实施例1-5和对比例1-2中所制备得到的改质油的稳定性测试结果，通过分析图1-7可知，实施例1、3、4中斑点均匀，内部无环状物，稳定性为1级，实施例2、5中斑点均匀，内部有细微而模糊的颜色差异，稳定性介于1级、2级之间。对比例1中有细微而模糊的环状物，中心部位颜色较深，稳定性为2级。对比例2中有三级等级更浓的环状物，亦比本色稍黑，稳定性为3级。
结合黏度测试和稳定性测试的结果可知，在高于溶剂超临界的条件下，将供氢剂引入重油馏分裂解反应中，能同时满足重油馏分减黏和改质油稳定性的要求，是一种兼顾了裂化深度和产品稳定性的改质技术。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (24)

  1. 一种重质油改质减黏工艺，其特征在于，所述工艺包括以下步骤：
    (1)将重质油进行切割，得到轻油馏分和重油馏分；其中，所述轻油馏分和重油馏分的切割温度为200-540℃；
    (2)将所述重油馏分、溶剂和供氢剂进行反应，得到反应产物；其中，所述反应选自一步反应或两步反应；
    其中，所述一步反应包括将所述重油馏分、溶剂和供氢剂接触，在至少达到所述溶剂的超临界环境下进行反应，得到反应产物；在所述一步反应中，所述溶剂至少分为A部分溶剂和B部分溶剂；所述A部分溶剂占所述重油馏分质量的5％-50％；所述A部分溶剂与所述重油馏分和供氢剂混合后预热到温度≤350℃；所述B部分溶剂独自预热，所述B部分溶剂的预热温度比所述裂解反应的温度高5-40℃；
    其中，所述两步反应包括先将所述重油馏分和溶剂混合，在至少达到所述溶剂的超临界环境下进行第一步反应，得到中间产物；然后再将所述中间产物与供氢剂和任选的补充溶剂接触，发生第二步反应，得到反应产物；
    (3)将所述反应产物进行分离，得到回收溶剂和裂化产物；
    (4)将所述轻油馏分和裂化产物混合，得到改质油。
  2. 根据权利要求1所述的工艺，其中，所述重质油选自凝点在30℃以上的石蜡基原油、中间基原油和环烷基原油中的一种或多种。
  3. 根据权利要求2所述的工艺，其中，所述重质油为凝点在30℃以上的石蜡基原油，所述切割温度为350-540℃。
  4. 根据权利要求2所述的工艺，其中，所述重质油为中间基原油，所述切割温度为280-540℃。
  5. 根据权利要求2所述的工艺，其中，所述重质油为环烷基原油，所述切 割温度为200-500℃。
  6. 根据权利要求1或2所述的工艺，其中，所述溶剂选自单环环烷烃和/或单环芳烃。
  7. 根据权利要求6所述的工艺，其中，所述单环环烷烃选自环戊烷和/或环己烷，所述单环芳烃选自苯、甲苯、二甲苯中的一种或多种。
  8. 根据权利要求1所述的工艺，其中，所述供氢剂选自环烷基芳烃。
  9. 根据权利要求8所述的工艺，其中，所述环烷基芳烃为四氢萘、十氢萘、二氢蒽中的一种或多种。
  10. 根据权利要求1所述的工艺，其中，在所述一步反应中，所述重油馏分和溶剂的质量比为1：0.5-5，所述供氢剂占所述重油馏分质量的0.1-10％。
  11. 根据权利要求1所述的工艺，其中，在所述一步反应中，所述重油馏分、溶剂和供氢剂分别独自进料；其中，所述重油馏分的进料温度为40-150℃，所述溶剂的进料温度为室温，所述供氢剂的进料温度为室温。
  12. 根据权利要求1所述的工艺，其中，所述A部分溶剂占所述重油馏分质量的10％-30％；
    其中，所述A部分溶剂与所述重油馏分和供氢剂混合后预热为300-330℃。
  13. 根据权利要求1所述的工艺，其中，所述一步反应的反应条件包括：一步反应温度为320-430℃，一步反应压力为6-15MPa，一步反应时间为1-60min。
  14. 根据权利要求13所述的工艺，其中，所述一步反应的反应条件包括： 一步反应温度为380-420℃，一步反应压力为8-12MPa，一步反应时间为1-30min。
  15. 根据权利要求1所述的工艺，其中，在所述第一步反应中，所述重油馏分和溶剂的质量比为1：0.5-5。
  16. 根据权利要求1所述的工艺，其中，在所述第一步反应中，所述重油馏分和所述溶剂分别独自进料；
    其中，所述重油馏分的进料温度为40-150℃，所述溶剂的进料温度为室温。
  17. 根据权利要求1所述的工艺，其中，在所述第一步反应中，所述溶剂至少分为C部分溶剂和D部分溶剂；其中，所述C部分溶剂占所述重油馏分质量的5％-50％；
    其中，所述C部分溶剂与所述重油馏分混合后预热到温度≤350℃；所述D部分溶剂独自预热，所述D部分溶剂的预热温度比所述裂解反应的温度高5-40℃。
  18. 根据权利要求1所述的工艺，其中，所述第一步反应的反应条件包括：第一步反应温度为320-430℃，第一步反应压力为6-15MPa，第一步反应时间为1-45min。
  19. 根据权利要求18所述的工艺，其中，所述第一步反应的反应条件包括：第一步反应温度为380-420℃，第一步反应压力为8-12MPa，第一步反应时间为1-20min。
  20. 根据权利要求1所述的工艺，其中，在所述第二步反应中，以第一步反应中的重油馏分计，所述供氢剂占所述重油馏分质量的0.1-10％。
  21. 根据权利要求1所述的工艺，其中，在所述第二步反应中，将所述中间产物与供氢剂和补充溶剂接触，发生第二步反应，得到反应产物；
    其中，在所述第一步反应中的溶剂与在所述第二步反应中的补充溶剂分别 独自选自单环环烷烃和/或单环芳烃；
    以第一步反应中的重油馏分计，所述第二步反应中的补充溶剂占所述重油馏分质量的5％-25％。
  22. 根据权利要求1所述的工艺，其中，所述第二步反应的反应条件包括：第二步反应温度为320-430℃，第二步反应压力为6-15MPa，第二步反应时间为1-30min。
  23. 根据权利要求22所述的工艺，其中，所述第二步反应的反应条件包括：第二步反应温度为380-420℃，第二步反应压力为8-12MPa，第二步反应时间为1-15min。
  24. 根据权利要求1所述的工艺，其中，所述改质油的稳定性为1-2级，50℃运动黏度≤300mm2/s，优选为50-200mm2/s。
PCT/CN2023/123583 2022-10-11 2023-10-09 重质油改质减黏工艺 WO2024078451A1 (zh)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4294686A (en) * 1980-03-11 1981-10-13 Gulf Canada Limited Process for upgrading heavy hydrocarbonaceous oils
JP2005307103A (ja) * 2004-04-26 2005-11-04 Idemitsu Kosan Co Ltd 重質油の水素化精製方法
US20140262947A1 (en) * 2013-03-14 2014-09-18 Exxonmobil Research And Engineering Company Fixed bed hydrovisbreaking of heavy hydrocarbon oils
CN110551525A (zh) * 2018-05-31 2019-12-10 中国石油化工股份有限公司 一种催化裂化柴油生产btx馏分的方法
CN113214864A (zh) * 2020-07-10 2021-08-06 中国石油大学(北京) 一种馏分油超/亚临界流体强化加氢组合方法
KR20210153959A (ko) * 2020-06-11 2021-12-20 단국대학교 산학협력단 중질유에 포함된 중금속을 촉매로 사용하는 중질유 경질화 처리 방법
CN114479929A (zh) * 2020-10-27 2022-05-13 中国石油天然气股份有限公司 原油连续改质减粘工艺

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4294686A (en) * 1980-03-11 1981-10-13 Gulf Canada Limited Process for upgrading heavy hydrocarbonaceous oils
JP2005307103A (ja) * 2004-04-26 2005-11-04 Idemitsu Kosan Co Ltd 重質油の水素化精製方法
US20140262947A1 (en) * 2013-03-14 2014-09-18 Exxonmobil Research And Engineering Company Fixed bed hydrovisbreaking of heavy hydrocarbon oils
CN110551525A (zh) * 2018-05-31 2019-12-10 中国石油化工股份有限公司 一种催化裂化柴油生产btx馏分的方法
KR20210153959A (ko) * 2020-06-11 2021-12-20 단국대학교 산학협력단 중질유에 포함된 중금속을 촉매로 사용하는 중질유 경질화 처리 방법
CN113214864A (zh) * 2020-07-10 2021-08-06 中国石油大学(北京) 一种馏分油超/亚临界流体强化加氢组合方法
CN114479929A (zh) * 2020-10-27 2022-05-13 中国石油天然气股份有限公司 原油连续改质减粘工艺

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