Treatment method and system for inferior oil
阅读说明：本技术 一种劣质油的处理方法和系统 (Treatment method and system for inferior oil ) 是由 魏晓丽 陈学峰 龚剑洪 侯焕娣 申海平 张执刚 张策 梁家林 戴立顺 张久顺 侯 于 2019-03-04 设计创作，主要内容包括：本发明涉及一种劣质油的处理方法和系统,该方法包括：将劣质油引入转化反应单元在临氢条件下进行转化反应,所得转化产物进行分离,得到重馏分；将所得重馏分引入萃取分离单元与萃取溶剂接触并进行萃取分离,得到改质油和残渣；将所得改质油进行加氢改质,得到气体产物、加氢改质轻油和加氢改质重油；将所得加氢改质重油引入变径稀相输送床反应器底部与第一催化裂化催化剂接触并进行第一催化裂化反应；将所得加氢改质轻油引入等径稀相输送床反应器与第二催化裂化催化剂接触并进行第二催化裂化反应。本发明的方法和系统具有高丙烯和高辛烷值汽油的产率。(The invention relates to a method and a system for treating inferior oil, wherein the method comprises the following steps: introducing the inferior oil into a conversion reaction unit to carry out conversion reaction under the hydrogen condition, and separating the obtained conversion product to obtain heavy fraction; introducing the obtained heavy fraction into an extraction separation unit to contact with an extraction solvent and carrying out extraction separation to obtain modified oil and residue; carrying out hydro-upgrading on the obtained upgraded oil to obtain a gas product, hydro-upgraded light oil and hydro-upgraded heavy oil; introducing the obtained hydrogenation modified heavy oil into the bottom of a variable-diameter dilute phase conveying bed reactor to contact with a first catalytic cracking catalyst and carrying out a first catalytic cracking reaction; and introducing the obtained hydro-modified light oil into an equal-diameter dilute phase conveying bed reactor to contact with a second catalytic cracking catalyst and carrying out a second catalytic cracking reaction. The process and system of the present invention have high yields of propylene and high octane gasoline.)
1. A method of treating poor quality oil, the method comprising:
introducing the inferior oil into a conversion reaction unit to carry out conversion reaction under the hydrogen condition, and separating the obtained conversion product to obtain heavy fraction with the distillation range of more than 350 ℃;
introducing the obtained heavy fraction into an extraction separation unit to contact with an extraction solvent and carrying out extraction separation to obtain modified oil and residue;
introducing the obtained modified oil into a hydro-modifying unit for hydro-modifying to obtain a gas product, hydro-modified light oil and hydro-modified heavy oil;
introducing the obtained hydro-modified heavy oil into the bottom of a variable-diameter dilute-phase conveying bed reactor to contact with a first catalytic cracking catalyst and carry out a first catalytic cracking reaction to obtain a first catalyst to be generated and a first reaction product; the reducing dilute phase transport bed reactor comprises a first reaction zone and a second reaction zone from bottom to top, and the inner diameter of the second reaction zone is larger than that of the first reaction zone;
introducing the obtained hydro-modified light oil into an equal-diameter dilute phase transport bed reactor to contact with a second catalytic cracking catalyst and carry out a second catalytic cracking reaction to obtain a second spent catalyst and a second reaction product;
and regenerating the first catalyst to be regenerated and the second catalyst to be regenerated, and returning the regenerated catalysts to the reducing dilute phase conveying bed reactor and the equal-diameter dilute phase conveying bed reactor.
2. The process of claim 1, wherein said low grade oil comprises at least one selected from the group consisting of low grade crude oil, heavy oil, deoiled bitumen, coal derived oil, shale oil and petrochemical waste oil.
3. The process of claim 1 wherein the low quality oil meets one or more criteria selected from the group consisting of an API degree of less than 27, a distillation range of greater than 350 ℃, an asphaltene content of greater than 2 wt.%, and a heavy metal content of greater than 100 micrograms/gram based on the total weight of nickel and vanadium.
4. The process of claim 1, wherein the conversion reaction unit comprises a conversion reactor, the conversion reactor being a fluidized bed reactor;
the conversion reaction is carried out in the presence or absence of a conversion catalyst containing at least one selected from the group consisting of group VB metal compounds, group VIB metal compounds and group VIII metal compounds;
the conversion reaction conditions include: the temperature is 380-470 ℃, the hydrogen partial pressure is 10-25 MPa, and the volume space velocity of the inferior oil is 0.01-2 hours-1The volume ratio of the hydrogen to the poor-quality oil is 500-5000, and the amount of the conversion catalyst is 10-50000 micrograms/g based on the weight of the poor-quality oil and calculated by the metal in the conversion catalyst.
5. The process of claim 1, wherein the conditions of the extractive separation comprise: the pressure is 3-12 MPa, the temperature is 55-300 ℃, and the extraction solvent is C3-C7The weight ratio of the hydrocarbon, the extraction solvent and the heavy fraction is (1-7): 1.
6. the process of claim 1, wherein the conditions for hydro-upgrading comprise: the hydrogen partial pressure is 5.0-20.0 MPa, the reaction temperature is 330--1The volume ratio of hydrogen to oil is 300-3000;
the catalyst used by the hydrogenation upgrading unit comprises a hydrofining catalyst and a hydrocracking catalyst, wherein the hydrofining catalyst comprises a carrier and an active metal component, and the active metal component is selected from VIB group metals and/or VIII group non-noble metals; the hydrocracking catalyst comprises zeolite, alumina, at least one group VIII metal component and at least one group VIB metal component.
7. The process of claim 6 wherein the hydrocracking catalyst comprises 3 to 60 wt% zeolite, 10 to 80 wt% alumina, 1 to 15 wt% nickel oxide and 5 to 40 wt% tungsten oxide based on the dry weight of the hydrocracking catalyst.
8. The treatment process according to claim 1, wherein the cut point of the hydroupgraded light oil and the hydroupgraded heavy oil is between 340-360 ℃, preferably between 345-355 ℃, more preferably 350 ℃.
9. The process of claim 1 wherein the ratio of the internal diameter of the second reaction zone to the first reaction zone is from 1.2 to 2.
10. The process of claim 1, wherein the conditions of the first reaction zone comprise: the reaction temperature is 500-620 ℃, the reaction time is 0.1-5 seconds, and the weight ratio of the catalyst to the oil is 5-15;
the conditions of the second reaction zone include: the reaction temperature is 450-550 ℃, and the reaction time is 1-20 seconds;
the conditions of the second catalytic cracking reaction include: the reaction temperature is 560 ℃ and 750 ℃, the reaction time is 1-10 seconds, and the weight ratio of the catalyst to the oil is 1-50;
the feed weight ratio of the hydro-upgrading light oil to the hydro-upgrading heavy oil is 0.01: 1-0.5: 1.
11. the process of claim 1 wherein the first and second catalytic cracking catalysts each independently comprise, on a dry basis and based on the weight of the catalytic cracking catalyst, from 1 to 60 wt% zeolite, from 5 to 99 wt% inorganic oxide, and from 0 to 70 wt% clay;
the zeolite comprises 50 to 100 wt% of a medium pore zeolite and 0 to 50 wt% of a large pore zeolite, based on the weight of the zeolite on a dry basis.
12. The processing method of claim 1, the method further comprising: returning the obtained residue to the conversion reaction unit for conversion reaction.
13. The process of claim 1, wherein the conversion rate of the conversion reaction is 30-70 wt%, the conversion rate of the conversion reaction is (weight of components with distillation range above 524 ℃ in the poor oil-weight of components with distillation range above 524 ℃ in the conversion product)/weight of components with distillation range above 524 ℃ in the poor oil x 100 wt%; and/or
In the heavy fraction, the content of components with the distillation range between 350 ℃ and 524 ℃ is 20-60 wt%.
14. A treatment system for inferior oil comprises a conversion reaction unit, an extraction separation unit, a hydrogenation modification unit, a variable-diameter dilute-phase transport bed reactor and an equal-diameter dilute-phase transport bed reactor, wherein the variable-diameter dilute-phase transport bed reactor comprises a first reaction zone and a second reaction zone from bottom to top, and the inner diameter of the second reaction zone is larger than that of the first reaction zone;
the conversion reaction unit is provided with an inferior oil inlet, a hydrogen inlet, a light fraction outlet and a heavy fraction outlet, the extraction separation unit is provided with an extraction solvent inlet, a raw material inlet, a modified oil outlet and a residue outlet, the hydrogenation modification unit is provided with a hydrogen inlet, a raw material inlet, a gas product outlet, a hydrogenation modified light oil outlet and a hydrogenation modified heavy oil outlet, the reducing dilute phase transport bed reactor is provided with a catalyst inlet, a raw material inlet and an oil agent outlet, and the equal-diameter dilute phase transport bed reactor is provided with a catalyst inlet, a raw material inlet and an oil agent outlet;
the heavy fraction outlet of the conversion reaction unit is communicated with the raw material inlet of the extraction separation unit, the modified oil outlet of the extraction separation unit is communicated with the raw material inlet of the hydrogenation modification unit, the hydrogenation modified heavy oil outlet of the hydrogenation modification unit is communicated with the raw material inlet of the reducing dilute-phase conveying bed reactor, and the raw material inlet of the constant-diameter dilute-phase conveying bed reactor is communicated with the hydrogenation modified light oil outlet of the hydrogenation modification unit.
Technical Field
The invention relates to a method and a system for treating inferior oil.
Background
Propylene is an important petrochemical industry base stock. At present, about 62% of propylene in the world comes from tubular furnace steam cracking technology, in ethylene production raw materials, naphtha accounts for 46%, ethane accounts for 34%, the amount of propylene produced by an ethylene device is gradually reduced along with the lightening of the ethylene raw materials, the steam cracking technology is improved day by day, and the steam cracking technology is a process of consuming a large amount of energy, is limited by the used high-temperature materials, and has little potential for further improvement.
In recent years, the quality of global gasoline for vehicles is rapidly improved, and the pace of upgrading the quality of oil products is obviously accelerated. At present, the quantity of catalytic cracking gasoline in China is about 70 percent of the total quantity of a gasoline pool, and the quality of the catalytic cracking gasoline plays a significant role in the overall level of the gasoline pool. The octane number RON of the catalytic cracking gasoline is 90-92 at most, the average octane number RON is 89-90, and the difference between the gasoline quality of the catalytic cracking gasoline and the gasoline quality of other developed countries is large, so that the octane number of the gasoline is improved, and the upgrading and updating of the gasoline are facilitated.
With the slow recovery of the world economy, the oil demand is slowly increased, and the supply and demand of the world oil market are basically kept loose. The international energy agency considers that, on the supply side, the crude oil production in non-european peck countries, represented by the united states, will continue to rise in the coming years, and the global crude oil demand will tend to tighten in 2022; on the demand side, the global crude oil demand will continuously rise in the next 5 years, and in 2019, 1 hundred million barrels per day will be broken through; the processing amount of unconventional oil and inferior heavy oil is increased year by year. Therefore, the method for producing the chemical raw materials such as the propylene and the high-octane gasoline to the maximum extent by utilizing the unconventional oil or the inferior oil is the key and key point for broadening the raw material sources for producing the propylene and the high-octane gasoline, adjusting the product structure, improving the quality and increasing the efficiency of petrochemical enterprises.
Chinese patent CN200910162163.9 discloses a method for processing inferior heavy oil by a combined process, which comprises subjecting inferior heavy oil raw material to solvent deasphalting to obtain deasphalted oil; preheating deasphalted oil, and then sequentially entering a first reaction zone and a second reaction zone of a catalytic conversion reactor to perform cracking reaction, hydrogen transfer reaction and isomerization reaction to obtain a catalytic wax oil product which accounts for 12-60% of the raw oil; and (3) hydrogenating the catalytic wax oil to obtain hydrogenated catalytic wax oil, introducing the hydrogenated catalytic wax oil into a catalytic conversion device, and further reacting to obtain a light fuel oil product. The method provided by the patent furthest produces propylene and high-octane gasoline from poor-quality raw oil.
WO2015084779a1 discloses a process for the production of propylene and high octane gasoline, especially propylene, using a combination of solvent deasphalting and high severity catalytic cracking. The method comprises the following steps: mixing the vacuum residue and the solvent, and then performing solvent deasphalting treatment; the deasphalted oil rich in solvent enters a heavy oil deep catalytic cracking device for deep cracking reaction after the solvent is separated, and a target product rich in propylene and high-octane gasoline, particularly propylene, is obtained. The patent method firstly carries out solvent deasphalting treatment on residual oil, and then realizes the high-efficiency conversion of deasphalted oil and the generation of propylene and high-octane gasoline through a combined process, but the deasphalted oil is not used and processed.
Chinese patent CN201410585111.3 discloses a method for treating heavy oil, which comprises subjecting a first heavy raw oil to fixed bed hydrogenation and fractionation to obtain fixed bed hydrogenation light oil and fixed bed hydrogenation residual oil; performing solvent deasphalting on the fixed bed hydrogenation residual oil to obtain deasphalted oil and deoiled asphalt; catalytically cracking the deasphalted oil and then fractionating to obtain products such as liquefied gas, gasoline and the like; hydrogenating and then fractionating hydrogenated raw oil containing deoiled asphalt, part or all of catalytic cracking heavy oil and second heavy raw oil; obtaining second hydrogenation light oil and second hydrogenation tail oil; at least part of the second hydrogenation tail oil returns to the catalytic cracking, and the gasoline yield can reach over 47 percent by the technical scheme.
In order to obtain more propylene and gasoline from inferior oil, the prior art adopts a technical method combining solvent deasphalting and hydrotreating to provide a high-quality raw material for catalytic cracking, but the yield of deasphalted oil is low, the yield is limited from the economical point of the whole process, and in addition, the deasphalted oil is not well utilized, so that the utilization rate of the inferior oil in the prior art is low, and more residues are still generated. Therefore, there is a need to develop a green and efficient conversion technology for producing propylene and gasoline from low-grade oil, which can increase the utilization rate of low-grade oil and simultaneously produce more products with high added values.
Disclosure of Invention
The invention aims to provide a method and a system for treating inferior oil, which have the yield of high propylene and high octane gasoline.
In order to achieve the above object, the present invention provides a method for treating inferior oil, comprising:
introducing the inferior oil into a conversion reaction unit to carry out conversion reaction under the hydrogen condition, and separating the obtained conversion product to obtain heavy fraction with the distillation range of more than 350 ℃;
introducing the obtained heavy fraction into an extraction separation unit to contact with an extraction solvent and carrying out extraction separation to obtain modified oil and residue;
introducing the obtained modified oil into a hydro-modifying unit for hydro-modifying to obtain a gas product, hydro-modified light oil and hydro-modified heavy oil;
introducing the obtained hydro-modified heavy oil into the bottom of a variable-diameter dilute-phase conveying bed reactor to contact with a first catalytic cracking catalyst and carry out a first catalytic cracking reaction to obtain a first catalyst to be generated and a first reaction product; the reducing dilute phase transport bed reactor comprises a first reaction zone and a second reaction zone from bottom to top, and the inner diameter of the second reaction zone is larger than that of the first reaction zone;
introducing the obtained hydro-modified light oil into an equal-diameter dilute phase transport bed reactor to contact with a second catalytic cracking catalyst and carry out a second catalytic cracking reaction to obtain a second spent catalyst and a second reaction product;
and regenerating the first catalyst to be regenerated and the second catalyst to be regenerated, and returning the regenerated catalysts to the reducing dilute phase conveying bed reactor and the equal-diameter dilute phase conveying bed reactor.
Optionally, the low-grade oil comprises at least one selected from the group consisting of low-grade crude oil, heavy oil, deoiled bitumen, coal-derived oil, shale oil, and petrochemical waste oil.
Optionally, the low quality oil meets one or more criteria selected from the group consisting of an API degree of less than 27, a distillation range of greater than 350 ℃, an asphaltene content of greater than 2 wt.%, and a heavy metal content of greater than 100 micrograms/gram, based on the total weight of nickel and vanadium.
Optionally, the conversion reaction unit comprises a conversion reactor, and the conversion reactor is a fluidized bed reactor;
the conversion reaction is carried out in the presence or absence of a conversion catalyst containing at least one selected from the group consisting of group VB metal compounds, group VIB metal compounds and group VIII metal compounds;
the conversion reaction conditions include: the temperature is 380-470 ℃, the hydrogen partial pressure is 10-25 MPa, and the volume space velocity of the inferior oil is 0.01-2 hours-1Hydrogen gasThe volume ratio of the catalyst to the poor-quality oil is 500-5000, and the dosage of the conversion catalyst is 10-50000 micrograms/gram based on the weight of the poor-quality oil and the metal in the conversion catalyst.
Optionally, the extraction separation conditions include: the pressure is 3-12 MPa, the temperature is 55-300 ℃, and the extraction solvent is C3-C7The weight ratio of the hydrocarbon, the extraction solvent and the heavy fraction is (1-7): 1.
optionally, the hydro-upgrading conditions include: the hydrogen partial pressure is 5.0-20.0 MPa, the reaction temperature is 330--1The volume ratio of hydrogen to oil is 300-3000;
the catalyst used by the hydrogenation upgrading unit comprises a hydrofining catalyst and a hydrocracking catalyst, wherein the hydrofining catalyst comprises a carrier and an active metal component, and the active metal component is selected from VIB group metals and/or VIII group non-noble metals;
the hydrocracking catalyst comprises zeolite, alumina, at least one group VIII metal component and at least one group VIB metal component;
optionally, the hydrocracking catalyst comprises 3-60 wt% zeolite, 10-80 wt% alumina, 1-15 wt% nickel oxide and 5-40 wt% tungsten oxide, based on the dry weight of the hydrocracking catalyst; the filling volume ratio of the hydrofining catalyst to the hydrocracking catalyst is 1-5: 1, according to the flow direction of reaction materials, the hydrofining catalyst is filled at the upstream of the hydrocracking catalyst.
Optionally, the cut point of the hydro-upgrading light oil and the hydro-upgrading heavy oil is between 340 ℃ and 360 ℃, preferably between 345 ℃ and 355 ℃, and more preferably 350 ℃.
Optionally, the ratio of the internal diameter of the second reaction zone to the first reaction zone is from 1.2 to 2.
Optionally, the conditions of the first reaction zone include: the reaction temperature is 500-620 ℃, the reaction time is 0.1-5 seconds, and the weight ratio of the catalyst to the oil is 5-15;
the conditions of the second reaction zone include: the reaction temperature is 450-550 ℃, and the reaction time is 1-20 seconds;
the conditions of the second catalytic cracking reaction include: the reaction temperature is 560 ℃ and 750 ℃, the reaction time is 1-10 seconds, and the weight ratio of the catalyst to the oil is 1-50;
the feed weight ratio of the hydro-upgrading light oil to the hydro-upgrading heavy oil is 0.01: 1-0.5: 1.
optionally, the first and second catalytic cracking catalysts each independently comprise, on a dry basis weight and based on the weight of the catalytic cracking catalyst, from 1 to 60 weight percent zeolite, from 5 to 99 weight percent inorganic oxide, and from 0 to 70 weight percent clay;
the zeolite comprises 50 to 100 wt% of a medium pore zeolite and 0 to 50 wt% of a large pore zeolite, based on the weight of the zeolite on a dry basis.
Optionally, the method further includes: returning the obtained residue to the conversion reaction unit for conversion reaction.
Optionally, the conversion rate of the conversion reaction is 30-70 wt%, and the conversion rate of the conversion reaction is (the weight of the component with the distillation range above 524 ℃ in the inferior oil-the weight of the component with the distillation range above 524 ℃ in the conversion product)/the weight of the component with the distillation range above 524 ℃ in the inferior oil x 100 wt%; and/or
In the heavy fraction, the content of components with the distillation range between 350 ℃ and 524 ℃ is 20-60 wt%.
The invention also provides a treatment system of inferior oil, which comprises a conversion reaction unit, an extraction separation unit, a hydrogenation modification unit, a variable-diameter dilute-phase conveying bed reactor and an equal-diameter dilute-phase conveying bed reactor, wherein the variable-diameter dilute-phase conveying bed reactor comprises a first reaction zone and a second reaction zone from bottom to top, and the inner diameter of the second reaction zone is larger than that of the first reaction zone;
the conversion reaction unit is provided with an inferior oil inlet, a hydrogen inlet, a light fraction outlet and a heavy fraction outlet, the extraction separation unit is provided with an extraction solvent inlet, a raw material inlet, a modified oil outlet and a residue outlet, the hydrogenation modification unit is provided with a hydrogen inlet, a raw material inlet, a gas product outlet, a hydrogenation modified light oil outlet and a hydrogenation modified heavy oil outlet, the reducing dilute phase transport bed reactor is provided with a catalyst inlet, a raw material inlet and an oil agent outlet, and the equal-diameter dilute phase transport bed reactor is provided with a catalyst inlet, a raw material inlet and an oil agent outlet;
the heavy fraction outlet of the conversion reaction unit is communicated with the raw material inlet of the extraction separation unit, the modified oil outlet of the extraction separation unit is communicated with the raw material inlet of the hydrogenation modification unit, the hydrogenation modified heavy oil outlet of the hydrogenation modification unit is communicated with the raw material inlet of the reducing dilute-phase conveying bed reactor, and the raw material inlet of the constant-diameter dilute-phase conveying bed reactor is communicated with the hydrogenation modified light oil outlet of the hydrogenation modification unit.
Compared with the prior art, the invention has the following advantages:
1. the method can process the inferior oil with high metal and high asphaltene content, realizes the high-efficiency lightening of the asphaltene by introducing the pre-conversion reaction of the inferior oil, and greatly reduces the residue amount.
2. The distillation range and the composition of the raw materials for extraction and separation are optimized, the extraction and separation process is easy to operate, and the physical properties of the residues obtained in the extraction and separation process are improved, so that the subsequent division of labor is facilitated.
3. Can provide high-quality raw materials without metal and asphaltene for catalytic cracking, and realize the maximum production of chemical raw materials.
4. The high-quality hydro-modified light oil obtained by the hydro-modifying unit can be used as a catalytic cracking feed to further produce propylene and high-octane gasoline, so that the pressure of surplus diesel markets and insufficient supply of propylene and high-octane gasoline is relieved.
5. Not only can realize the efficient green conversion of the low-quality oil, but also can realize the production of high value-added products, namely propylene and high-octane gasoline from the low-quality oil.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 includes a schematic flow diagram of an embodiment of the method of the present invention and a schematic structural diagram of an embodiment of the system of the present invention.
Description of the reference numerals
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Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for treating inferior oil, which comprises the following steps:
introducing the inferior oil into a conversion reaction unit to carry out conversion reaction under the hydrogen condition, and separating the obtained conversion product to obtain heavy fraction with the distillation range of more than 350 ℃;
introducing the obtained heavy fraction into an extraction separation unit to contact with an extraction solvent and carrying out extraction separation to obtain modified oil and residue;
introducing the obtained modified oil into a hydro-modifying unit for hydro-modifying to obtain a gas product, hydro-modified light oil and hydro-modified heavy oil;
introducing the obtained hydro-modified heavy oil into the bottom of a variable-diameter dilute-phase conveying bed reactor to contact with a first catalytic cracking catalyst and carry out a first catalytic cracking reaction to obtain a first catalyst to be generated and a first reaction product; the reducing dilute phase transport bed reactor comprises a first reaction zone and a second reaction zone from bottom to top, and the inner diameter of the second reaction zone is larger than that of the first reaction zone;
introducing the obtained hydro-modified light oil into an equal-diameter dilute phase transport bed reactor to contact with a second catalytic cracking catalyst and carry out a second catalytic cracking reaction to obtain a second spent catalyst and a second reaction product;
and regenerating the first catalyst to be regenerated and the second catalyst to be regenerated, and returning the regenerated catalysts to the reducing dilute phase conveying bed reactor and the equal-diameter dilute phase conveying bed reactor.
According to the present invention, low-grade oils are well known to those skilled in the art, and for example, the low-grade oils may include at least one selected from the group consisting of low-grade crude oil, heavy oil, deoiled bitumen, coal-derived oil, shale oil, and petrochemical waste oil. The heavy oil refers to distillate oil or residual oil with a boiling point above 350 ℃, and the distillate oil generally refers to fraction products obtained by atmospheric distillation and vacuum distillation of crude oil or secondary processing oil, such as heavy diesel oil, heavy gas oil, lubricating oil fraction or cracking raw materials and the like; residuum refers to the bottoms from atmospheric and vacuum distillation of crude oil, and atmospheric distillation bottoms are generally referred to as atmospheric residuum (typically, fractions boiling above 350 ℃), vacuum distillation bottoms are generally referred to as vacuum residuum (typically, fractions boiling above 500 ℃ or 524 ℃),the residual oil may be at least one selected from the group consisting of a topped crude oil, a heavy oil obtained from oil sand bitumen, and a heavy oil having a primary boiling point of greater than 350 ℃, the topped crude oil being an oil discharged from the bottom of a primary tower or the bottom of a flash tower when the crude oil is fractionated in an atmospheric and vacuum distillation process; the inferior crude oil is thick oil, which refers to crude oil with high content of asphaltene and colloid and high viscosity, and the density of the ground is generally more than 0.943 g/cm at 20 DEG C3The crude oil with the viscosity of the underground crude oil being more than 50 centipoises is called thick oil; the deasphalted oil is rich in asphaltene and rich in aromatic components, which are obtained by contacting, dissolving and separating raw oil with a solvent and at the bottom of an extraction tower in a solvent deasphalting device, and can be divided into propane deasphalted asphalt, butane deoiled asphalt, pentane deoiled asphalt and the like according to the difference of the types of the solvents; the coal derived oil is a liquid fuel obtained by taking coal as a raw material and performing chemical processing, and can be at least one selected from coal liquefied oil generated by coal liquefaction and coal tar generated by coal pyrolysis; shale oil is brown sticky paste obtained by low-temperature dry distillation of oil shale, and has pungent odor and high nitrogen content; the petrochemical waste oil may be at least one selected from the group consisting of petrochemical waste oil sludge, petrochemical oil residue, and refined products thereof. Other low quality oils known to those skilled in the art may also be used alone or in combination as low quality oils for the conversion reaction and the present invention is not further described herein. The low quality oil preferably meets one or more criteria selected from the group consisting of an API degree of less than 27, a distillation range of greater than 350 ℃ (preferably greater than 500 ℃, more preferably greater than 524 ℃), an asphaltene content of greater than 2 wt.% (preferably greater than 5 wt.%, more preferably greater than 10 wt.%, even more preferably greater than 15 wt.%), and a heavy metal content of greater than 100 micrograms/gram, based on the total weight of nickel and vanadium.
According to the invention, the conversion reaction is essentially a thermal conversion reaction, which means that the poor oil is thermally converted in the presence of hydrogen and conversion products are obtained which contain at least heavy fractions and which may also contain light fractions having a lower distillation range than the heavy fractions.
In one embodiment, the conversion reaction unit comprises a conversion reactor, and the conversion reaction can be carried out in a fluidized bed reactor by using a solid-liquid suspension as a catalyst, so that the conversion reactor can be a fluidized bed reactor, and the fluidized bed reactor is a reactor in which reaction raw materials and the catalyst are reacted in a flowing state, and generally comprises a slurry bed reactor, a suspended bed reactor and a fluidized bed reactor, and the slurry bed reactor is preferred in the invention.
In one embodiment, the conversion reaction is carried out in the presence or absence of a conversion catalyst comprising at least one member selected from the group consisting of a group VB metal compound, a group VIB metal compound, and a group VIII metal compound; preferably at least one of Mo compound, W compound, Ni compound, Co compound, Fe compound, V compound and Cr compound, for example at least one selected from molybdenum naphthenate, nickel naphthenate, ammonium molybdate, organic molybdenum, organic vanadium and hematite; the conditions of the conversion reaction may include: the temperature is 380-470 ℃, preferably 400-440 ℃, the hydrogen partial pressure is 10-25 MPa, preferably 13-20 MPa, and the volume space velocity of the inferior oil is 0.01-2 hours-1Preferably 0.1 to 1.0 hour-1The volume ratio of the hydrogen to the poor-quality oil is 500-5000, preferably 800-2000, and the amount of the conversion catalyst is 10-50000 micrograms/g, preferably 30-25000 micrograms/g based on the weight of the poor-quality oil and the metal in the conversion catalyst.
In one embodiment, when the process of the present invention is carried out in a conversion reaction unit, it is generally carried out as follows: the poor oil, hydrogen and the conversion catalyst enter a conversion reactor of a conversion reaction unit for reaction, and the reaction product is separated into a gas product and a liquid product to finally obtain heavy fraction with the distillation range of more than 350 ℃.
According to the present invention, the extraction separation is used for separating the easily processable modified oil in the heavy fraction, and the residue is thrown out or returned to carry out the conversion reaction, the extraction separation can be carried out in an extraction solvent under a certain temperature and a certain pressure, preferably the extraction solvent and the heavy fraction are in countercurrent contact for extraction, and the extraction separation can be carried out in any extraction device, such as an extraction tower, and the conditions of the extraction separation comprise: the pressure is 3-12 MPa, preferably 3.5-10 MPa, the temperature is 55-300 deg.C, preferablySelecting at 70-220 deg.C with extraction solvent C3-C7A hydrocarbon, preferably C3-C5Alkane and C3-C5At least one of olefins, more preferably C3-C4Alkane and C3-C4At least one olefin, the weight ratio of the extraction solvent to the heavy fraction being (1-7): 1, preferably (1.5-5): 1. other conventional extraction methods can be adopted by the person skilled in the art for extraction, and the description of the invention is omitted.
In one embodiment, when the process of the present invention is carried out in an extractive separation unit, the heavy fraction having a distillation range of greater than 350 ℃ obtained from the conversion reaction unit is sent to the extractive separation unit for countercurrent contact with an extraction solvent for extractive separation to obtain an upgraded oil and a residue. The residue can be returned to the conversion reaction unit for further conversion reaction, and the modified oil is sent to the hydro-upgrading unit.
According to the present invention, the hydro-upgrading can be carried out in any manner known in the art, without particular limitation, and can be carried out in any hydrogenation apparatus known in the art (e.g., fixed bed reactor, fluidized bed reactor), which can be reasonably selected by one skilled in the art. The hydro-upgrading conditions may include: the hydrogen partial pressure is 5.0-20.0 MPa, the preferential pressure is 8-15 MPa, the reaction temperature is 330-450 ℃, the preferential pressure is 350-420 ℃, and the volume space velocity is 0.1-3 hours-1Preferably 0.3 to 1.5 hours-1The volume ratio of hydrogen to oil is 300-3000, preferably 800-1500; the catalyst used in the hydroupgrading unit includes a hydrorefining catalyst and a hydrocracking catalyst, and as the hydrorefining catalyst and the hydrocracking catalyst, for example, any catalyst conventionally used in the art for this purpose may be used or may be produced according to any production method conventionally known in the art, and the amount of the catalyst used in the hydroupgrading step may be referred to the conventional knowledge in the art and is not particularly limited. Specifically, the hydrorefining catalyst may comprise a carrier and an active metal component, and more specifically, as the active metal component, for example, a metal of group VIB of the periodic Table of elements and a non-metal of group VIII of the periodic Table of elementsNoble metals and the like, particularly a combination of nickel and tungsten, a combination of nickel, tungsten and cobalt, a combination of nickel and molybdenum, or a combination of cobalt and molybdenum. These active metal components may be used singly or in combination in any ratio. Examples of the carrier include alumina, silica, and amorphous silica-alumina. These carriers may be used singly or in combination in any ratio. The respective contents of the carrier and the active metal component are not particularly limited in the present invention, and conventional knowledge in the art can be referred to. The hydrocracking catalyst generally contains a cracking functional component, such as a zeolite, and specifically, the hydrocracking catalyst may include a zeolite, alumina, at least one group VIII metal component and at least one group VIB metal component, and the zeolite may be a Y-type zeolite. The hydrocracking catalyst may comprise 3-60 wt% zeolite, 10-80 wt% alumina, 1-15 wt% nickel oxide and 5-40 wt% tungsten oxide based on the dry weight of the hydrocracking catalyst, although other compositions of hydrocracking catalysts may be employed by those skilled in the art. The invention has no special requirements on the loading sequence and the loading proportion of the hydrofining catalyst and the hydrocracking catalyst, for example, the hydrofining catalyst and the hydrocracking catalyst can be loaded in any ratio in a mixing way or loaded upstream and downstream, and the hydrofining catalyst is preferably loaded upstream of the hydrocracking catalyst, for example: the filling volume ratio of the hydrofining catalyst to the hydrocracking catalyst can be 1-5: 1, according to the flow direction of reaction materials, the hydrofining catalyst is filled at the upstream of the hydrocracking catalyst.
According to the invention, the hydro-upgrading light oil and the hydro-upgrading heavy oil are separated according to the distillation range, for example, the cut points of the hydro-upgrading light oil and the hydro-upgrading heavy oil are between 340 and 360 ℃, preferably between 345 and 355 ℃, and more preferably 350 ℃, and the distillation ranges of the hydro-upgrading light oil and the hydro-upgrading heavy oil can be partially overlapped according to the result of actual separation.
In one embodiment, when the process of the present invention is carried out in a hydro-upgrading unit, the upgraded oil from the extractive separation unit is reacted in the hydro-upgrading unit, and the resulting hydro-upgraded heavy oil and hydro-upgraded light oil are sent to different reactors, respectively.
The invention adopts the reducing dilute phase transport bed reactor and the equal-diameter dilute phase transport bed reactor as the catalytic cracking reactor to carry out catalytic cracking reaction, the two reactors are arranged in parallel, the structure of the specific reactor is not specially limited, for example, the ratio of the inner diameter of the second reaction zone to the inner diameter of the first reaction zone of the reducing dilute phase transport bed reactor can be 1.2-2.
According to the present invention, the conditions of the catalytic cracking reaction may be selected as desired, for example, the conditions of the first reaction zone may include: the reaction temperature is 500-620 ℃, the reaction pressure is 0.2-1.2 MPa, the reaction time is 0.1-5 seconds, and the weight ratio of the solvent to the oil is 5-15; the conditions of the second reaction zone may include: the reaction temperature is 450-550 ℃, the reaction pressure is 0.2-1.2 MPa, and the reaction time is 1-20 seconds; the conditions of the second catalytic cracking reaction may include: the reaction temperature is 560-750 ℃, the reaction temperature is preferably 580-730 ℃, the reaction temperature is more preferably 600-700 ℃, the reaction time is 1-10 seconds, the reaction time is preferably 2-5 seconds, and the weight ratio of the catalyst to the oil is 1-50, preferably 5-30; the feed weight ratio of the hydroupgraded light oil to the hydroupgraded heavy oil may be 0.01: 1-0.5: 1.
according to the invention, the catalytic cracking reactor may also be injected with steam, preferably in the form of atomized steam. The weight ratio of the injected steam to the hydroupgraded heavy oil (hydroupgraded light oil) may be 0.01 to 1, preferably 0.05 to 0.5.
In the catalytic cracking of the present invention, the spent catalyst and the reaction product are generally separated to obtain the spent catalyst and the reaction product, then the obtained reaction product is subjected to a subsequent separation system (for example, a cyclone separator) to separate fractions such as dry gas, liquefied gas, gasoline and diesel oil, then the dry gas and the liquefied gas are further separated by a gas separation device to obtain ethylene, propylene and the like, and the method for separating ethylene, propylene and the like from the reaction product is similar to the conventional technical method in the art, and the present invention is not limited thereto, and is not described in detail herein.
According to the invention, the method of the invention also preferably comprises: regenerating the spent catalyst; and preferably at least a part of the catalytic cracking catalyst is regenerated, for example, the whole of the catalyst may be regenerated catalyst.
According to the invention, the method of the invention also preferably comprises: the regenerated catalyst obtained by regeneration is stripped (generally by steam stripping) to remove impurities such as gas.
According to the invention, in the regeneration process, oxygen-containing gas is generally introduced from the bottom of the regenerator, the oxygen-containing gas can be air, for example, after being introduced into the regenerator, the catalyst to be generated is contacted with oxygen for scorching and regeneration, the gas-solid separation is carried out on the upper part of the regenerator on the flue gas generated after the scorching and regeneration of the catalyst, and the flue gas enters a subsequent energy recovery system.
According to the invention, the regeneration operation conditions of the spent catalyst can be as follows: the regeneration temperature is 550-750 ℃, preferably 600-730 ℃, and more preferably 650-700 ℃; the gas superficial linear velocity is 0.5 to 3 m/s, preferably 0.8 to 2.5 m/s, more preferably 1 to 2 m/s, and the average residence time of the spent catalyst is 0.6 to 3 minutes, preferably 0.8 to 2.5 minutes, more preferably 1 to 2 minutes.
The catalytic cracking catalyst is well known to those skilled in the art in accordance with the present invention, and conventional options may be employed in the present invention, for example, the first catalytic cracking catalyst and the second catalytic cracking catalyst may each independently comprise from 1 to 60 wt% zeolite, from 5 to 99 wt% inorganic oxide, and from 0 to 70 wt% clay, on a dry basis and based on the weight of the catalytic cracking catalyst; the zeolite is taken as an active component, preferably the zeolite is selected from medium-pore zeolite and/or large-pore zeolite, and the medium-pore zeolite accounts for 50-100 wt% of the total weight of the zeolite, preferably the medium-pore zeolite accounts for 70-100 wt% of the total weight of the zeolite, and the large-pore zeolite accounts for 0-50 wt% of the total weight of the zeolite, preferably the large-pore zeolite accounts for 0-30 wt% of the total weight of the zeolite. The medium pore size zeolite and the large pore size zeolite are defined by the convention in the art, i.e., the medium pore size zeolite has an average pore size of 0.5 to 0.6 nm and the large pore size zeolite has an average pore size of 0.7 to 1.0 nm. For example, the large pore zeolite may be selected from a mixture of one or more of the group of zeolites consisting of rare earth Y (rey), rare earth hydrogen Y (rehy), ultrastable Y obtained by different methods, high silicon Y. In the middle ofThe porous zeolite may be selected from zeolites having an MFI structure, such as ZSM-series zeolites and/or ZRP zeolites, and the above-mentioned intermediate pore zeolites may also be modified with non-metallic elements such as phosphorus and/or transition metal elements such as iron, cobalt, nickel, as described in more detail in U.S. Pat. No. 5,232,675, and the ZSM-series zeolites may be selected from one or more mixtures of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other zeolites of similar structure, as described in more detail in U.S. Pat. No. 3,702,886. In the present invention, the inorganic oxide is preferably selected from silicon dioxide (SiO) as a binder2) And/or aluminum oxide (Al)2O3). In the present invention, the clay is preferably selected from kaolin and/or halloysite as a matrix (i.e., carrier).
In one embodiment, when the process of the present invention is carried out in a catalytic cracking reactor, it is generally carried out as follows: the catalytic cracking catalyst enters a pre-lifting section of a first reaction zone of the variable-diameter dilute-phase conveying bed reactor, flows upwards under the action of a pre-lifting medium, preheated hydrogenation modified heavy oil and atomized steam are injected into the first reaction zone of the variable-diameter dilute-phase conveying bed reactor together, and contact with a regenerated catalyst to perform catalytic cracking reaction and simultaneously flow upwards, and enter a second reaction zone to continue reaction, and the reacted material flow enters a cyclone separator through a reactor outlet; the preheated hydro-upgrading light oil and atomized steam are injected into an equal-diameter dilute phase transport bed reactor together, contact with a regenerated catalyst to perform catalytic cracking reaction and flow upwards at the same time, and the reacted material flow enters a cyclone separator through an outlet of the reactor; leading the separated reaction oil gas out of the device, and further separating to obtain fractions such as propylene, high-octane gasoline and the like; the separated spent catalyst enters a regenerator for coke burning regeneration, and the regenerated catalyst with recovered activity returns to the reducing dilute phase conveying bed reactor and the equal-diameter dilute phase conveying bed reactor for recycling.
According to the invention, the conversion rate of the conversion reaction can be 30-70 wt%, the conversion rate of the conversion reaction is (weight of component with distillation range above 524 ℃ in inferior oil-weight of component with distillation range above 524 ℃ in conversion product)/weight of component with distillation range above 524 ℃ in inferior oil x 100 wt%; and/or the fraction of the heavy fraction may have a fraction of between 20 and 60 wt.% of components having a distillation range between 350 and 524 ℃. The invention can maintain the long-time operation of the system under the condition of reducing the outward throwing of the residue as much as possible and improving the resource utilization rate, the conversion reactor and the extraction separation unit are the key for determining whether the system can operate for a long time, the conversion rate of the conversion reactor is as high as possible under the condition of system stability, light fractions less than 350 ℃ in the first separation product entering the extraction separation unit are not too much, otherwise, the light fractions pollute the solvent, black oil is generated in the extraction separation process, heavy fractions with the distillation range of 350 ℃ and 524 ℃ are more, otherwise, the residue is not easy to flow and the conversion reaction is not easy to be carried out in the conversion reactor. The conversion rate of the conversion reaction is high, coke is easy to form, and the system running time is reduced, and the conversion rate is low, the outward throwing residue is easy to be too much, and the unit time modification efficiency is reduced.
The invention also provides a treatment system of inferior oil, which comprises a conversion reaction unit, an extraction separation unit, a hydrogenation modification unit, a variable-diameter dilute-phase conveying bed reactor and an equal-diameter dilute-phase conveying bed reactor, wherein the variable-diameter dilute-phase conveying bed reactor comprises a first reaction zone and a second reaction zone from bottom to top, and the inner diameter of the second reaction zone is larger than that of the first reaction zone;
the conversion reaction unit is provided with an inferior oil inlet, a hydrogen inlet, a light fraction outlet and a heavy fraction outlet, the extraction separation unit is provided with an extraction solvent inlet, a raw material inlet, a modified oil outlet and a residue outlet, the hydrogenation modification unit is provided with a hydrogen inlet, a raw material inlet, a gas product outlet, a hydrogenation modified light oil outlet and a hydrogenation modified heavy oil outlet, the reducing dilute phase transport bed reactor is provided with a catalyst inlet, a raw material inlet and an oil agent outlet, and the equal-diameter dilute phase transport bed reactor is provided with a catalyst inlet, a raw material inlet and an oil agent outlet;
the heavy fraction outlet of the conversion reaction unit is communicated with the raw material inlet of the extraction separation unit, the modified oil outlet of the extraction separation unit is communicated with the raw material inlet of the hydrogenation modification unit, the hydrogenation modified heavy oil outlet of the hydrogenation modification unit is communicated with the raw material inlet of the reducing dilute-phase conveying bed reactor, and the raw material inlet of the constant-diameter dilute-phase conveying bed reactor is communicated with the hydrogenation modified light oil outlet of the hydrogenation modification unit.
According to the invention, the equipment used for catalytic cracking can comprise components such as oil separating equipment and a stripper besides two reactors, wherein the oil separating equipment can be a settler with a cyclone separator, and other conventional components can be arranged as required by a person skilled in the art, and the invention is not described in detail.
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
As shown in fig. 1, the poor oil is transferred to the
The pre-lifting medium enters the bottom of a first reaction zone 1 of the reducing dilute phase transport bed reactor through a pipeline 14, the regenerated catalyst from a pipeline 12 enters the first reaction zone 1 after being regulated by a regeneration slide valve 13, and then moves upwards and quickly along the reactor under the lifting action of the pre-lifting medium, the preheated hydro-upgrading heavy oil is injected into the first reaction zone 1 through a pipeline 16 and atomized steam from a pipeline 15, and is mixed with the existing material flow of the first reaction zone 1, the raw oil is subjected to cracking reaction on the hot catalyst, moves upwards and quickly, and enters a second reaction zone 26 to continue to perform catalytic cracking reaction; the pre-lifting medium enters the bottom of the equal-diameter dilute phase conveying bed reactor 27 through a pipeline 29, the regenerated catalyst from a pipeline 28 enters the equal-diameter dilute phase conveying bed reactor 27 and then moves upwards in an accelerated manner along the reactor under the lifting action of the pre-lifting medium, the preheated hydro-upgrading light oil is injected into the equal-diameter dilute phase conveying bed reactor 27 through a pipeline 18 and atomized steam from a pipeline 17 and is mixed with the existing material flow of the equal-diameter dilute phase conveying bed reactor 27, and the hydro-upgrading light oil is subjected to cracking reaction on the hot catalyst; the reaction products generated by the two reactors and the inactivated spent catalyst enter a cyclone separator 6 in a settler 3 to realize the separation of the spent catalyst and the reaction products, the reaction products enter a gas collection chamber 7, and the fine catalyst powder returns to the settler. Spent catalyst in the settler flows to the stripping section 4 where it is contacted with steam from
The regenerated catalyst enters a degassing tank 5 through a
The following examples further illustrate the process but do not limit the invention.
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