Inferior oil hydro-upgrading method and system
阅读说明：本技术 一种劣质油临氢改质方法和系统 (Inferior oil hydro-upgrading method and system ) 是由 董明 龙军 侯焕娣 申海平 李吉广 许可 陶梦莹 赵飞 王翠红 佘玉成 于 2019-09-27 设计创作，主要内容包括：本发明涉及一种劣质油临氢高效改质方法和系统,该方法包括：将劣质油与第一分离产物混合后首先进行萃取分离,得到改质油和残渣,所得残渣外甩或进行转化反应,所得改质油进入减压蒸馏分离单元,分离得到的特定组分与循环残渣混合进行转化,转化反应产物进行分离处理,分离所得第一分离产物循环回萃取分离单元。本发明提供的方法和系统在外甩残渣尽可能少的情况下可维持系统长时间的运转,多产重改质油并少产气体实现劣质油高效改质。(The invention relates to a high-efficiency hydro-upgrading method and a system for inferior oil, wherein the method comprises the following steps: mixing the inferior oil and the first separation product, then firstly carrying out extraction separation to obtain modified oil and residue, throwing the obtained residue outwards or carrying out conversion reaction, introducing the obtained modified oil into a reduced pressure distillation separation unit, mixing the separated specific components with the circulating residue for conversion, carrying out separation treatment on the conversion reaction product, and recycling the separated first separation product to the extraction separation unit. The method and the system provided by the invention can maintain the long-time operation of the system under the condition of reducing the outward thrown residues as much as possible, produce heavy modified oil more and produce less gas to realize the high-efficiency modification of inferior oil.)
1. A hydro-upgrading method for inferior oil comprises the following steps:
(1) mixing inferior oil serving as a modified raw material with a first separation product, and then, introducing the mixture into a solvent extraction unit for extraction separation to obtain modified oil and residue, wherein the inferior oil contains asphaltene;
(2) carrying out conversion reaction on the residue obtained in the step (1); or, throwing the residue obtained in the step (1) outwards; or, carrying out conversion reaction on part of the residue obtained in the step (1), and throwing out the rest of the residue; wherein the residue after the conversion reaction is a circulating residue;
(3) sending the modified oil obtained in the step (1) into a reduced pressure distillation separation unit, and separating to obtain a light fraction, a heavy fraction and specific components, wherein the specific components at least comprise a fraction at 450-500 ℃, and the aromatic hydrocarbon content is more than 70%, and the sum of the tricyclic aromatic hydrocarbon and tetracyclic aromatic hydrocarbon content is more than 40%;
(4) carrying out conversion reaction on the specific components obtained in the step (3) and the circulating residue in a conversion reactor under the hydrogen condition to obtain a conversion product; the conversion reaction has an asphaltene conversion of 20 to 70 wt%, the conversion reaction having an asphaltene conversion (weight of asphaltene component in the feed to the conversion unit-weight of asphaltene component in the conversion product)/weight of asphaltene component in the feed to the conversion unit x 100 wt%; the conversion rate of the conversion reaction is 15-60 wt%, the conversion rate of the conversion reaction is (weight of component with distillation range above 524 ℃ in the modified raw material-weight of component with distillation range above 524 ℃ in the converted product)/weight of component with distillation range above 524 ℃ in the modified raw material x 100 wt%; the mass ratio of the specific component to the circulating residue is 0.1-1.0;
(5) separating the conversion product obtained in the step (4) to obtain at least a first separated product; wherein the content of components with distillation range below 350 ℃ is not more than 5 wt%, and the content of components with distillation range between 350 ℃ and 524 ℃ is not less than 20 wt% in the first separated product.
2. The process for hydro-upgrading poor oil according to claim 1, wherein in the step (1), the extraction and separation are carried out under the conditions of pressure of 3-12 MPa, temperature of 55-300 ℃, and extraction solvent C3-C7A hydrocarbon, the weight ratio of the extraction solvent to the first separation product being (1-7): 1.
3. the process for the hydro-upgrading of poor oils according to claim 1, characterized in that in step (1) the softening point of the residue is less than 160 ℃.
4. The method of claim 1, wherein in step (1), the low-grade oil is selected from at least one of a low-grade crude oil, a heavy oil, deoiled bitumen, a coal derived oil, a shale oil, and a petrochemical waste oil.
5. The process for the hydroupgrading of low-quality oil according to claim 1, wherein the low-quality oil meets one or more criteria selected from the group consisting of an API gravity of less than 27, a distillation range of greater than 350 ℃, a bitumen component content of greater than 2 wt.%, and a heavy metal content of greater than 100 μ g/g, based on the total weight of nickel and vanadium.
6. The process for hydroupgrading of poor oils according to claim 1, characterized in that in step (2) part of the residue is converted as recycled residue and the remaining part of the residue is thrown off, wherein the proportion of recycled residue is more than 80% by weight.
7. The process for the hydro-upgrading of poor oils according to claim 1, characterized in that in step (2) part of the residue is thrown out, the thrown-out residue representing less than 10% by weight of the upgrading feedstock.
8. The hydro-upgrading method of inferior oil according to claim 1, wherein in the step (4), the specific components enter a hydrotreating unit, are hydrofined and then are mixed with the residue to be recycled and turned into a conversion reactor for conversion reaction, the catalyst active metal component in the hydrotreating unit is selected from group VIB metals and/or group VIII non-noble metals, and the carrier is selected from one or more of alumina, silica and amorphous silica-alumina.
9. The process for hydro-upgrading poor oil according to claim 8, wherein the catalytically active metal component of the hydroprocessing unit is preferably a combination of nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum.
10. The process for hydro-upgrading poor oil according to claim 1, wherein in step (4), the conversion reactor is a fluidized bed reactor;
the conversion reaction is carried out in the presence or absence of a conversion catalyst, and the conversion catalyst contains at least one selected from group VB metal compounds, group VIB metal compounds and group VIII metal compounds;
the conversion reaction conditions include: the temperature is 360-440 ℃, the hydrogen partial pressure is 10-25 MPa, and the volume space velocity of the modified raw material is 0.01-2 hours-1The volume ratio of hydrogen to the upgrading feedstock was 500-.
11. The process for hydro-upgrading poor oils according to claim 1, characterized in that in step (5) the first separated product has a distillation range of less than 3 wt% of components below 350 ℃.
12. The process for hydro-upgrading poor oils according to claim 1, characterized in that in step (5) said separation treatment comprises:
(5-1) separating the conversion product obtained in the step (4) under the conditions of the pressure of 10-25 MPa and the temperature of 360-440 ℃ to obtain a gas component and a liquid component;
(5-2) separating the liquid component at a pressure of 0.1 to 5 MPa and a temperature of 150 ℃ and 390 ℃ to obtain the first separated product and the gas separated product.
13. The process for hydro-upgrading poor oils according to claim 12, characterized in that said step (5-1) is carried out under the operating conditions: the pressure is 13-20 MPa, and the temperature is 400-440 ℃; the operating conditions of the step (5-2) are as follows: the pressure is 0.1-4 MPa and the temperature is 200-370 ℃.
14. The process for hydro-upgrading poor oil according to claim 12, wherein the separation process further comprises:
(5-3) cutting the first separation product obtained in the step (5-2) to obtain naphtha and atmospheric gas oil; and/or
(5-4) returning the hydrogen-containing gas obtained in the step (5-1) to the step (4) for conversion reaction.
15. An inferior oil hydro-upgrading system comprises an extraction separation unit (3), a reduced pressure distillation separation unit (9), a conversion reactor (21) and a separation treatment unit (29);
the extraction separation unit (3) is provided with an extraction solvent inlet, an extraction raw material inlet, a modified oil outlet and a residue outlet; the vacuum distillation unit (9) is provided with a modified oil inlet, a light fraction outlet, a specific component outlet and a heavy fraction outlet; the conversion reactor (21) is provided with a reaction material inlet and a conversion product outlet, and the separation processing unit is provided with a processing raw material inlet and a first separation product outlet;
a conversion product outlet of the conversion reactor (21) is communicated with a processing raw material inlet of the separation processing unit, a first separation product outlet of the separation processing unit (22) is mixed with the inferior raw oil (1) and enters the extraction separation unit, and a residue outlet of the extraction separation unit (3) is connected with a reaction material inlet of the conversion reactor (21).
16. The system for hydroupgrading of poor oil according to claim 15, wherein the separation process unit comprises a high pressure separation unit (23) and a low pressure separation unit (29), the high pressure separation unit (23) being provided with a gas component outlet, a liquid component outlet and the process feedstock inlet, the low pressure separation unit (29) being provided with a low pressure feedstock inlet and the first separation product outlet, the liquid component outlet of the high pressure separation unit (23) being in communication with the feedstock inlet of the low pressure separation unit (29).
Technical Field
The invention relates to a method and a system for efficiently upgrading inferior oil in the presence of hydrogen.
Background
In recent years, the tendency of fossil fuels to deteriorate has been increasing year by year. Moreover, the production of low-quality fuel oils such as residual oils, poor crude oils, shale oils, oil sand heavy oils, and coal derived oils has increased year by year. Such poor oils are characterized by high density, high viscosity, high content of heteroatoms (sulfur, nitrogen, heavy metals) or high content of asphaltenes. In addition, the existing processing technology (such as delayed coking) developed aiming at the inferior oil has the problems of high coke yield, low energy effective utilization rate, poor economic benefit, non-environmental-friendly production process and the like. Therefore, further development of efficient and green upgrading technology for such inferior oil has become one of development direction and research focus of petrochemical industry.
CN200310104918.2 discloses a method for modifying inferior heavy oil and residual oil, which comprises the steps of firstly carrying out mild hydrocracking on the heavy oil and the residual oil by a suspension bed to enable most or all metal impurities to be dissociated from colloid and asphaltene; the obtained hydrogenation product passes through a metal adsorption reactor which can be switched to operate or can replace the added materials on line, and free metal impurities in the suspension bed hydrocracking oil are adsorbed and removed; and (3) sending the demetallized product into a residual oil fixed bed hydrotreater for deep hydrogenation to remove other impurities, and producing high-quality heavy oil catalytic cracking raw materials.
US20130112593a1 discloses a heavy crude oil, distillation residue conversion process that achieves upgrading of heavy oil by combining solvent deasphalting, hydrotreating, distillation, and gasification. But the yield of the modified oil of the heavy residual oil processed by the method is only 75-85%, and the content of metal (Ni + V) in the modified oil is more than 100 microgram/gram.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method and a system for efficiently upgrading inferior oil by hydrogen on the basis of the prior art, and the method and the system provided by the invention can maintain the long-time operation of the system under the condition of throwing away residues as little as possible.
The invention provides a method for efficiently upgrading inferior oil in hydrogen, which comprises the following steps:
(1) mixing inferior oil serving as a modified raw material with a first separation product, and then, introducing the mixture into a solvent extraction unit for extraction separation to obtain modified oil and residue, wherein the inferior oil contains asphaltene;
(2) carrying out conversion reaction on the residue obtained in the step (1); or, throwing the residue obtained in the step (1) outwards; or, carrying out conversion reaction on part of the residue obtained in the step (1), and throwing out the rest of the residue; wherein the residue after the conversion reaction is a circulating residue;
(3) sending the modified oil obtained in the step (1) into a reduced pressure distillation separation unit, and separating to obtain a light fraction, a heavy fraction and specific components, wherein the specific components at least comprise fractions at 450-500 ℃, the aromatic hydrocarbon content of the specific components is more than 70%, and the sum of the tricyclic aromatic hydrocarbon content and the tetracyclic aromatic hydrocarbon content is more than 40%;
(4) carrying out conversion reaction on the specific components obtained in the step (3) and the circulating residue in a conversion reactor under the hydrogen condition to obtain a conversion product; the conversion reaction has an asphaltene conversion of 20 to 70 wt%, the conversion reaction having an asphaltene conversion (weight of asphaltene component in the feed to the conversion unit-weight of asphaltene component in the conversion product)/weight of asphaltene component in the feed to the conversion unit x 100 wt%; the conversion rate of the conversion reaction is 15-60 wt%, the conversion rate of the conversion reaction is (weight of component with distillation range above 524 ℃ in the modified raw material-weight of component with distillation range above 524 ℃ in the converted product)/weight of component with distillation range above 524 ℃ in the modified raw material x 100 wt%; the mass ratio of the specific component to the circulating residue is 0.1-1.0;
(5) separating the conversion product obtained in the step (3) to obtain at least a first separated product; wherein the content of components with distillation range below 350 ℃ is not more than 5 wt%, and the content of components with distillation range between 350 ℃ and 524 ℃ is not less than 20 wt% in the first separated product.
The invention provides an inferior oil upgrading system for high-yield heavy upgraded oil, which comprises an extraction separation unit, a reduced pressure distillation unit, a conversion reactor and a separation treatment unit; the extraction separation unit is provided with an extraction solvent inlet, an extraction raw material inlet, a modified oil outlet and a residue outlet; the vacuum distillation unit is provided with a modified oil inlet, a light fraction outlet, a specific component outlet and a heavy fraction outlet; the conversion reactor is provided with a reaction material inlet and a conversion product outlet, and the separation processing unit is provided with a processing raw material inlet and a first separation product outlet; the conversion product outlet of the conversion reactor is communicated with the processing raw material inlet of the separation processing unit, the first separation product outlet of the separation processing unit and the inferior raw oil are mixed and enter the extraction separation unit, the residue outlet of the extraction separation unit is connected with the reaction material inlet of the conversion reactor, and the inlet of the residue reduction distillation unit is connected with the upgraded oil outlet. The separation processing unit comprises a high-pressure separation unit and a low-pressure separation unit, the high-pressure separation unit is provided with a gas component outlet, a liquid component outlet and a processing raw material inlet, the low-pressure separation unit is provided with a low-pressure raw material inlet and a first separation product outlet, and the liquid component outlet of the high-pressure separation unit is communicated with the raw material inlet of the low-pressure separation unit.
Compared with the prior art, the method and the system for hydro-upgrading the inferior oil have the advantages that:
1. can upgrade the poor-quality oil into the upgraded oil which is rich in saturated structures, basically free of heavy metals and basically free of asphaltenes to the maximum extent with high efficiency, and can produce heavy upgraded oil in a high yield. Under the optimized conditions, the conversion rate of the upgrading raw material is generally more than 90 wt%, preferably more than 95 wt%, the yield of the heavy upgrading oil is more than 350 ℃ under the optimized conditions, the content of heavy metals (based on the total weight of nickel and vanadium) in the obtained heavy upgrading oil is generally less than 10 microgram/g, preferably less than 1 microgram/g, and the content of asphaltene in the upgrading oil is generally less than 2.0 wt%, preferably less than 0.5 wt%, so that the high-efficiency upgrading of poor-quality oil resources is realized.
2. Lower low value gas yields, lower gas product prices, and higher gas yields can reduce process economics. The method provided by the invention firstly leads the inferior oil to enter the extraction separation unit, and the residue with the worst property obtained by separation enters the conversion reaction unit to be modified under the optimal condition, so that the yield of the process gas can be reduced, and the economical efficiency is improved. Meanwhile, the treatment capacity of the conversion reaction unit is reduced, and the investment of the conversion reaction unit is reduced.
3. The method and the system provided by the invention have the advantages of stable operation, high upgrading efficiency, less discharge of three wastes, environmental protection, low coke yield, high heavy upgrading oil yield and the like.
4. On the one hand, the invention can maintain the long-time operation of the conversion reactor on the premise of realizing high conversion rate of the modified raw materials, reduce the external throwing residues and improve the effective utilization rate of resources, on the other hand, the invention can prevent excessive light components less than 350 ℃ in the first separation product from polluting the solvent and further causing the generation of black oil in the extraction separation process by optimizing the composition of the first separation product, and can maintain the components in the distillation range of 350-524 ℃ in the first separation product within a reasonable range to prevent the excessive conversion of the asphaltene.
5. According to the invention, by controlling the composition structure of specific components in the reduced pressure distillation unit and the mixing proportion of the specific components and the circulating tailings, the problems of poor fluidity and difficulty in dissolution when the residues return to the conversion reaction are prevented, and the long-period operation stability of the device is ensured.
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 one embodiment of the method of the present invention and also includes a schematic structural diagram of one embodiment of the system of the present invention.
FIG. 2 is a schematic flow diagram of a process for upgrading poor quality oil as employed in comparative example 5.
Description of the reference numerals
3-extraction separation unit, 9-reduced pressure distillation separation unit, 21-conversion reactor, 29-high pressure separation unit, and the rest are pipelines.
Detailed Description
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.
In the present invention, the boiling point range refers to the boiling point range obtained by distilling an oil product at normal pressure (101325 Pa).
In the present invention, unless otherwise specified, the pressure refers to gauge pressure.
The invention provides a hydro-upgrading method for inferior oil, which comprises the following steps: (1) mixing inferior oil serving as a modified raw material with a first separation product, and then, introducing the mixture into a solvent extraction unit for extraction separation to obtain modified oil and residue, wherein the inferior oil contains asphaltene; (2) carrying out conversion reaction on the residue obtained in the step (1); or, throwing the residue obtained in the step (1) outwards; or, carrying out conversion reaction on part of the residue obtained in the step (1), and throwing out the rest of the residue; wherein, the residue after conversion is the recycling residue; (3) sending the modified oil obtained in the step (1) into a reduced pressure distillation separation unit, and separating to obtain a light fraction, a heavy fraction and specific components, wherein the specific components at least comprise a fraction at 450-500 ℃, and the aromatic hydrocarbon content is more than 70%, and the sum of the tricyclic aromatic hydrocarbon and tetracyclic aromatic hydrocarbon content is more than 40%; the mass ratio of the specific component to the circulating residue is 0.1-1.0; (4) carrying out conversion reaction on the specific components obtained in the step (3) and the circulating residue in a conversion reactor under the hydrogen condition to obtain a conversion product; the conversion reaction has an asphaltene conversion of 20 to 70 wt%, the conversion reaction having an asphaltene conversion (weight of asphaltene component in the feed to the conversion unit-weight of asphaltene component in the conversion product)/weight of asphaltene component in the feed to the conversion unit x 100 wt%; the conversion rate of the conversion reaction is 15-60 wt%, the conversion rate of the conversion reaction is (weight of component with distillation range above 524 ℃ in the modified raw material-weight of component with distillation range above 524 ℃ in the converted product)/weight of component with distillation range above 524 ℃ in the modified raw material x 100 wt%; (5) separating the conversion product obtained in the step (3) to obtain at least a first separated product; wherein the content of components with distillation range below 350 ℃ is not more than 5 wt%, and the content of components with distillation range between 350 ℃ and 524 ℃ is not less than 20 wt% in the first separated product.
According to the invention, the low quality oil may comprise at least one bituminous component selected from the group consisting of asphaltenes, asphaltenes and preasphaltenes, preferably comprising asphaltenes and/or preasphaltenes, more preferably comprising asphaltenes. Asphaltene is a substance which is insoluble in nonpolar small-molecule n-alkanes (such as n-pentane or n-heptane) and soluble in benzene or toluene in the inferior oil, asphaltene is a substance which is soluble in toluene and insoluble in n-hexane in the inferior oil, and preasphaltene is a substance which is soluble in tetrahydrofuran and insoluble in toluene in the inferior oil. 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. Specifically, the low-grade oil may include at least one selected from the group consisting of low-grade crude oil, heavy oil, deoiled asphalt, 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 of crude oil obtained by atmospheric and vacuum distillation, and atmospheric distillation bottoms are generally referred to as atmospheric residuum (generally, the fraction with a boiling point greater than 350 ℃), and vacuum distillation bottoms are generally referred to as vacuum residuum (generally, the fraction with a large boiling point)Fractions at 500 ℃ or 524 ℃), the residual oil may be at least one selected from the group consisting of a topped crude oil, a heavy oil derived 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 inferior oils known to those skilled in the art may also be used alone or in combination as upgrading materials for the conversion reaction, and the present invention is not further described.
The poor oil contains impurities such as asphaltene or asphaltene, metal, sulfur and nitrogen, and the like, which obviously affect the processing process and cause the problems of catalyst deactivation, device blockage, shutdown and the like, so that the impurities such as asphaltene or asphaltene, metal, sulfur and nitrogen and the like in the poor oil are usually removed through pre-modification in the actual processing process so as to reduce the influence on the subsequent processing process. The main purpose of upgrading poor quality oil is to remove impurities (mainly asphaltenes and metals) contained therein, which have a significant impact on subsequent processing, but in the upgrading process, the yield of light products is high due to cracking, which affects the economy of the process.
The invention can maintain the long-time operation of the system under the condition of reducing the external throwing of residues and the gas yield 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 permission, light components less than 350 ℃ in a first separation product entering the extraction separation unit are not too much, otherwise, the solvent is polluted, black oil is generated in the extraction separation process, more components with the distillation range of 350-.
According to the invention, the low-quality oil and the first separation product are mixed to be used as extraction raw materials, extraction separation is used for separating components which are most required to be modified and are rich in asphaltene and metal from the low-quality oil, the components enter a conversion reactor for modification, meanwhile, the easily processed modified oil in the first separation product is separated, and residues are thrown outwards or returned for conversion reaction, specifically, in the step (1), the extraction separation is preferably carried out by carrying out countercurrent contact extraction on an extraction solvent and the first separation product, and can be carried out in any extraction device, such as an extraction tower; wherein the pressure is 3-12 MPa, preferably 3.5-10 MPa, the temperature is 55-300 deg.C, preferably 70-220 deg.C, and the extraction solvent is C3-C7A hydrocarbon, preferably C3-C5Alkane and C3-C 5At least one of olefins, more preferably C3-C4Alkane and C3-C4At least one olefin, the weight ratio of the extraction solvent to the first separation product 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.
According to the invention, the residue is the highest boiling component of the conversion product, the more completely the easily processable component of the conversion product is separated the higher its softening point, but in order to maintain the fluidity of the residue on line transport and solubility on return to the conversion reactor, the softening point of said residue is preferably less than 160 ℃, more preferably less than 150 ℃ in step (1).
If the conversion reaction of the present invention is carried out in a fluidized bed reactor, the conversion catalyst therein is subsequently separated along with the conversion product and remains in the residue, and the metal content in the whole system is increased as the amount of the catalyst added increases and as the metal component in the upgrading raw material accumulates. In order to maintain the balance of metals in the system, the residue needs to be discharged intermittently or continuously, and in order to fully use the modified raw material, part of the residue is thrown outwards in the step (2), and the thrown-out residue accounts for less than 10 wt% of the modified raw material; the proportion of residue entering step (3) (based on the total weight of the residue) is preferably greater than 80% by weight, preferably greater than 90% by weight, more preferably greater than 95% by weight. The proportion of the slag thrown outward can be adjusted by those skilled in the art according to the modified raw materials with different asphaltene and metal contents, and the invention is not described in detail.
According to the invention, the specific component is obtained by adopting reduced pressure distillation separation in the step (3), the specific component at least comprises fraction at 450-500 ℃, and the aromatic hydrocarbon content is more than 70%, wherein the sum of the tricyclic aromatic hydrocarbon and the tetracyclic aromatic hydrocarbon is more than 40%; the specific component preferably enters a hydrotreating unit, is subjected to hydrofining and then is mixed with residue to circulate and turn the conversion unit, wherein the active metal component of the catalyst of the hydrotreating unit is selected from VIB group metals and/or VIII group non-noble metals, and the carrier is selected from one or more of alumina, silicon dioxide and amorphous silica-alumina. The hydrotreating unit catalyst active metal component is preferably a nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum, or cobalt-molybdenum combination.
According to the invention, the conversion reaction in step (4) is essentially a thermal conversion reaction, which means that the upgrading raw material is thermally converted in the presence of hydrogen to obtain a conversion product containing at least a first separated product, and the conversion product may further contain a gas component and a liquid product having a distillation range lower than the initial distillation point of the first separated product. The catalyst and the reactor are not particularly limited in the present invention as long as the above-mentioned conversion rate can be achieved.
In one embodiment, the conversion reaction in step (4) is carried out in a fluidized bed reactor using a solid-liquid suspension as a catalyst, so the conversion reactor can be a fluidized bed reactor, and the fluidized bed reactor is a reactor in which the reaction raw material and the catalyst are reacted in a fluidized state, and generally comprises a slurry bed reactor and a fluidized bed reactor, and the slurry bed reactor is preferred in the invention.
In one embodiment, the conversion reaction in step (4) is carried out in the presence or absence of a conversion catalyst, which may contain at least one selected from group VB metal compounds, group VIB metal compounds and group VIII metal compounds, preferably at least one of Mo compounds, W compounds, Ni compounds, Co compounds, Fe compounds, V compounds and Cr compounds; the conditions of the conversion reaction may include: the temperature is 360-440 ℃, preferably 380-430 ℃, the hydrogen partial pressure is 10-25 MPa, preferably 13-20 MPa, and the volume space velocity of the modified raw material is 0.01-2 hours-1Preferably 0.1 to 1.0 hour-1The volume ratio of hydrogen to the upgrading raw material is 500-5000, preferably 800-2000, and the concentration of the conversion catalyst in the conversion reactor is 100-50000 micrograms/g, preferably 200-25000 micrograms/g, calculated on the metal in the conversion catalyst and based on the weight of the feed in the conversion reactor.
According to the present invention, too high a conversion rate of the conversion reaction in the step (4) causes the system to lose stability and coke formation, which is mainly caused by unreasonable conversion of asphaltenes, and the inventors have made extensive studies to show that the conversion reaction has an asphaltene conversion rate of 20 to 70 wt%, which is (weight of asphaltene component in the feed to conversion unit-weight of asphaltene component in the conversion product)/weight of asphaltene component in the feed to conversion unit x 100 wt%; the conversion rate of the conversion reaction is 15-60 wt%, the conversion rate of the conversion reaction is (weight of component with distillation range above 524 ℃ in the modified raw material-weight of component with distillation range above 524 ℃ in the converted product)/weight of component with distillation range above 524 ℃ in the modified raw material x 100 wt%; on the premise of stable system, high conversion rate of asphaltene is ensured, and overhigh gas yield is inhibited, so that higher yield of modified oil can be obtained.
According to the invention, the first separated product in the step (4) is generally composed of the product with the highest distillation range in the converted product, and comprises the residue in the step (1), wherein the main component of the residue is asphaltene and also comprises some colloid and aromatic components which are necessary for maintaining fluidity, the first separated product also comprises upgraded oil besides the residue, the first separated product can be used as a raw material with good quality for subsequent treatment after being separated by extraction to obtain other oil products, and the rest components with the lower distillation range in the converted product can be separated from the first separated product, such as gas products in a standard state (such as dry gas, liquefied gas and the like) and other components with the distillation range below 350 ℃.
According to the present invention, the separation treatment in step (5) is used to obtain the first separated product having the above-mentioned distillation range composition, and the present invention is not particularly limited to the specific embodiment thereof, and specifically, the separation treatment in this step is generally referred to as physical separation, such as extraction, liquid separation, distillation, evaporation, flash evaporation, condensation, and the like.
In one embodiment, in step (5), the separation process comprises step (5-1) high-pressure separation and step (5-2) low-pressure separation:
(5-1) separating the conversion product obtained in the step (1) or the mixture of the conversion product and the catalytic cracking slurry oil under the conditions of the pressure of 10-25 MPa, preferably 13-20 MPa and the temperature of 380-470 ℃, preferably 400-440 ℃, so as to obtain a gas component and a liquid component; in the step (5-1), gas products such as hydrogen and the like are preferably separated, and the gas components are rich in hydrogen, preferably the hydrogen content is more than 85 weight percent; for convenience of measurement, the pressure generally refers to the outlet pressure of the gaseous component as it exits the separation device, and the temperature generally refers to the outlet temperature of the liquid component as it exits the separation device; the way of separation in this step may be distillation, fractionation, flash distillation, etc., preferably distillation, which may be performed in a distillation column, the gas component may be obtained from the top of the distillation column, and the liquid component may be obtained from the bottom of the distillation column;
(5-2) separating the liquid component at a pressure of 0.1 to 5 MPa, preferably 0.1 to 4 MPa, and at a temperature of 150 ℃ and 390 ℃, preferably 200 ℃ and 370 ℃, to obtain the first separated product and the gas separated product; in the step (5-2), the components with the distillation range below 350 ℃ are preferably separated, and the components with the distillation range of 350-524 ℃ are kept as much as possible; wherein the pressure of the high-pressure separation in the step (5-1) is 4-24 MPa greater than that of the low-pressure separation in the step (5-2), and more preferably 7-19 MPa greater; for convenience of measurement, the pressure generally refers to the outlet pressure of the gas separation product as it exits the separation device, and the temperature generally refers to the outlet temperature of the first separation product as it exits the separation device; the separation in this step may be a distillation and/or a fractional distillation, preferably an atmospheric or pressurized fractional distillation, which may be carried out in an atmospheric distillation tank or a pressurized distillation column.
As shown in the attached figure 1, the invention provides a poor oil upgrading system for high-yield heavy upgraded oil, which comprises an extraction separation unit 3, a reduced pressure distillation separation unit 9, a conversion reactor 21 and a separation treatment unit 29; the extraction separation unit 3 is provided with an extraction solvent inlet, an extraction raw material inlet, a modified oil outlet and a residue outlet; the vacuum distillation unit 9 is provided with a modified oil inlet, a light fraction outlet, a specific component outlet and a heavy fraction outlet; the conversion reactor 21 is provided with a reaction material inlet and a conversion product outlet, and the separation processing unit is provided with a processing raw material inlet and a first separation product outlet; the conversion product outlet of the conversion reactor 21 is communicated with the processing raw material inlet of the separation processing unit, the first separation product outlet of the separation processing unit 22 is mixed with the inferior raw oil 1 and enters the extraction separation unit, and the residue outlet of the extraction separation unit 3 is connected with the reaction material inlet of the conversion reactor 21.
The system provided by the invention is used for carrying out the method provided by the invention, for example, as shown in fig. 1, the separation processing unit comprises a high-pressure separation unit 23 and a low-pressure separation unit 29, the high-pressure separation unit 23 is provided with a gas component outlet, a liquid component outlet and the processing raw material inlet, the low-pressure separation unit 29 is provided with a low-pressure raw material inlet and a first separation product outlet, and the liquid component outlet of the high-pressure separation unit 23 is communicated with the raw material inlet of the low-pressure separation unit 29. The high pressure separation unit and the low pressure separation unit may both be distillation units or fractionation units, such as distillation columns and the like, which are distinguished by an operating pressure, the high pressure separation unit being operated at a higher pressure than the low pressure separation unit.
According to the present invention, in order to recycle the gaseous components, the gaseous component outlet of the high-pressure separation unit 23 is connected to the reaction material inlet of the conversion reactor 21, as shown in fig. 1.
The invention will be further illustrated by the following specific embodiments, but the invention is not limited thereto.
As shown in fig. 1, the modified raw material is mixed and conveyed into the extraction separation unit 3 through a pipeline 1 and the first separation product through a pipeline 31, and the mixture is contacted with the extraction solvent from a pipeline 5 in a countercurrent manner for extraction and separation, so that modified oil and residue are obtained. The modified oil enters a reduced pressure distillation separation unit 9 through a pipeline 4, light fraction 10, heavy fraction 11 and specific components 12 are obtained through separation, a part of specific components 14 are mixed with circulating residues, a part of residues are thrown out through a pipeline 6 and a pipeline 7 in sequence, the rest parts are mixed with the specific components to serve as modified raw materials, and the modified raw materials are mixed with a conversion catalyst in a pipeline 16, circulating hydrogen in a pipeline 17 and a vulcanizing agent in a pipeline 19 in sequence and are conveyed to a conversion reactor 21 through a pipeline 15, a pipeline 18 and a pipeline 20 to perform conversion reaction. The converted product is sent to a high-pressure separation unit 23 through a pipeline 22 to be subjected to pressure distillation, separated into a gas component and a liquid component, and then the gas component is sent to a conversion reactor 21 as circulating hydrogen through a pipeline 25, a pipeline 27 and a pipeline 17 in sequence or is led out of the system through a pipeline 25 and a pipeline 26 in sequence. The liquid component is conveyed via line 24 to a low pressure separation unit 29 to separate a first separated product. The upper product is taken off to the outside of the system via line 30 and the first separated product is passed via line 31 to the extractive separation unit 3, the invention being illustrated in further detail below using examples, to which the invention is not restricted.
In the context of the present invention and included in the following examples and comparative examples:
the determination of the heavy metal content (based on the total weight of nickel and vanadium) in the oil is carried out according to ASTM D5708;
the method for measuring the content of the asphaltene in the oil product is carried out according to SH/T0266-92 (1998);
the conversion of the modified raw material is (1-removal rate of the residue) x 100 wt%, and the removal rate of the residue is (weight of the removed residue/weight of the modified raw material x 100 wt%;
the yield of heavy modified oil is that the distillation range in the product is more than 350 ℃ weight/weight of the modified raw material multiplied by 100 weight percent;
the residue recycle ratio is the recycle residue amount/total residue amount multiplied by 100 weight percent;
yield of toluene insolubles was represented by toluene insolubles weight/modified oil weight × 100%;
the softening point of the residue was measured by the GB/T4507-84 method.
The operation stability of the upgrading process was evaluated by the number of days of steady operation of the system. Specifically, the system is determined to be unable to operate stably if any of the following conditions occurs:
(1) the maximum temperature difference delta T (absolute value) of different temperature measuring points in the conversion reactor is more than 5 ℃;
(2) the upgraded oil appears black, which normally appears yellow or yellowish green.
The following examples and comparative examples were modified according to the embodiment shown in FIG. 1.
In the following examples and comparative examples, as the upgrading raw materials, upgrading raw material a and upgrading raw material B are vacuum residue, upgrading raw material C is venezuelan heavy oil vacuum residue, and upgrading raw material D is high temperature coal tar, and properties of these four raw materials are shown in table 1.
Examples 1 to 5
On a medium-sized device, firstly, performing extraction separation on a modified raw material, feeding the obtained modified oil into a reduced pressure distillation unit for distillation and cutting to obtain a specific component, mixing the obtained residue and the specific component for conversion reaction, performing separation treatment on a conversion product, performing separation treatment in two fractionating towers to obtain a first separation product and a gas separation product, mixing the first separation product and the modified raw material, feeding the first separation product and the modified raw material into an extraction separation unit, partially throwing the obtained residue, mixing part of the residue with the specific component for continuous conversion, and listing specific conditions and results of the conversion reaction and the separation treatment in tables 2-1, 2-2 and 2-3.
As can be seen from tables 2-2 and 2-3, with the process and system of the present invention, the conversion of upgraded feedstock is typically greater than 90 wt.%, the yield of heavy upgraded oil is greater than 350 ℃, the heavy metals (based on the total weight of nickel and vanadium) content of the resulting heavy upgraded oil is less than 5 microgram/gram, and the asphaltene content of the upgraded oil is typically less than 2.0 wt.%, preferably less than 0.5 wt.%, and the gas yield is < 10%. The device runs stably, and no phenomenon that the device cannot run stably due to black oil or delta T in the reactor is more than 5 ℃ or the like occurs.
Comparative examples 1 to 4
The same basic procedure as in example 1, comparative examples 1 to 4 were carried out with the operating conditions changed as shown in Table 3-1, comparative example 2 was free from specific components, and the results of the experiments are shown in tables 3-2 and 3-3.
Comparative example 5
By the flow shown in fig. 2, the poor oil is transferred to the shift reactor 7 for shift reaction through the line 1, the shift catalyst through the line 2, the recycle hydrogen through the line 3, the fresh hydrogen through the line 4, and the residue through the line 5. The mixture formed by mixing the converted product with a pipeline 9 from catalytic cracking slurry oil feeding through a pipeline 8 is conveyed to a high-pressure separation unit 11 through a pipeline 10 for pressure distillation, and is separated into a gas component and a liquid component, and then the gas component is taken as circulating hydrogen and conveyed to a conversion reactor 7 through a pipeline 12, a pipeline 3 and a pipeline 6 in sequence, or is led out of the system through the pipeline 12 and a pipeline 13 in sequence. The liquid component is conveyed via line 14 to a low pressure separation unit 15 for pressure letdown to separate a gas separation product and a first separation product. The gas separation product is led out of the system through a pipeline 16, and the first separation product is conveyed to an extraction separation unit 18 through a pipeline 17 to be in countercurrent contact with an extraction solvent from a pipeline 19 for extraction separation, so that the modified oil and the residue are obtained. The modified oil is led out of the system through a pipeline 20, one part of the residue is thrown out through a pipeline 21 and a pipeline 22, and the rest part of the residue is used as a modified raw material and is circulated to the conversion reactor 7 through the pipeline 21, the pipeline 5 and the pipeline 6 to be subjected to conversion reaction with the modified raw material continuously. Alternatively, all the residues may be thrown out through the line 21 and the line 22 one after another without being circulated. The main conditions are shown in Table 4-1, and the results are shown in tables 4-2 and 4-3.
The results in tables 3-1 to 3-3 show that when one of the conversion rate of the conversion reaction, the asphaltene conversion rate, the first separated product content less than 350 ℃ and the specific component content does not meet the corresponding requirements of the invention, the conversion rate of the modified raw material is reduced by about 7.7 to 13.4 percentage points, the yield of the heavy modified oil is reduced by 7 to 17.6 percentage points, and the stable operation days of the system are greatly reduced because the delta T is more than 5 ℃ or the modified oil is black.
Tables 4-1 to 4-3, the gas yield decreased by 29.9 percentage points and the heavy modified oil yield increased by 8% compared to the comparative ratio using the method and system of this patent.
TABLE 1
Name (R)
Modified raw material A
Modified raw material B
Modified raw material C
Modified raw Material D
Density (20 ℃ C.)/(kg/m)3)
1064.4
1060.3
1064
1083.0
Degree of API
1.44
1.95
1.49
/
Solids content/weight%
/
/
/
/
Carbon residue value/weight%
26.3
23.2
33.0
5.5
Element content/weight%
Carbon (C)
84.20
83.87
85.84
84.73
Hydrogen
9.77
9.98
9.38
10.52
Sulfur
5.50
4.90
3.20
0.14
Nitrogen is present in
0.38
0.34
0.69
0.47
Oxygen gas
/
/
/
3.47
Four components composition/weight%
Saturation fraction
8.6
9.0
10.1
36.6
Aromatic component
51.9
53.6
38.3
21.2
Glue
25.3
24.4
26.5
37.6
Asphaltenes
14.2
12.7
25.1
4.6
Metal content/(microgram/gram)
Ca
1.6
2.4
33.0
6.8
Fe
9.4
23.0
15.0
78.3
Ni
69.7
42.0
147.0
0.5
V
230.0
96.0
621.0
<0.1
Al
/
/
/
/
Content/weight% of components > 524%
100
100
100
15
TABLE 2-1
Tables 2 to 2
Tables 2 to 3
TABLE 3-1
TABLE 3-2
Tables 3 to 3
TABLE 4-1
TABLE 4-2
Tables 4 to 3
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