Modification method and system for producing low-carbon olefin from low-quality oil
阅读说明：本技术 一种由低品质油生产低碳烯烃的改质方法和系统 (Modification method and system for producing low-carbon olefin from low-quality oil ) 是由 侯焕娣 申海平 龙军 梁家林 魏晓丽 张久顺 董明 戴立顺 龚剑洪 侯栓弟 于 2019-03-04 设计创作，主要内容包括：一种由低品质油生产低碳烯烃的方法,该方法包括：低品质油先进行临氢转化反应得到临氢转化产物；将所得临氢转化产物进行分离处理,至少得到第一分离产物,将第一分离产物进行萃取分离,得到改质油和残渣,将残渣返回进行临氢转化反应或者进行外甩；或者,将部分残渣返回进行临氢转化反应,剩余部分残渣进行外甩；将所得改质油进行加氢改质,得到加氢后改质油；将所得加氢后改质油进行催化转化反应生产低碳烯烃。本发明提供的改质方法和系统不仅可实现低品质油高效绿色转化,且可实现由低品质油生产化工原料-低碳烯烃。(A process for producing lower olefins from a low quality oil, the process comprising: carrying out hydro-conversion reaction on low-quality oil to obtain a hydro-conversion product; separating the obtained hydroconversion product to obtain at least a first separation product, extracting and separating the first separation product to obtain modified oil and residue, and returning the residue to the hydroconversion reaction or throwing the residue outwards; or returning part of the residue to carry out the hydroconversion reaction, and throwing the rest of the residue outwards; carrying out hydrogenation modification on the obtained modified oil to obtain hydrogenated modified oil; and carrying out catalytic conversion reaction on the hydrogenated modified oil to produce the low-carbon olefin. The modification method and the modification system provided by the invention can realize efficient green conversion of low-quality oil and can realize production of chemical raw materials, namely low-carbon olefin from the low-quality oil.)
1. An upgrading process for producing lower olefins from a lower quality oil, the process comprising:
(1) carrying out hydro-conversion reaction on low-quality oil serving as a modified raw material to obtain a hydro-conversion product; wherein the conversion rate of the hydroconversion reaction is 30 to 70 wt%, which is (weight of the component having a boiling point of 524 ℃ or higher in the upgraded raw material-weight of the component having a boiling point of 524 ℃ or higher in the hydroconversion product)/weight of the component having a boiling point of 524 ℃ or higher in the upgraded raw material x 100 wt%;
(2) separating the hydroconversion product obtained in the step (1) to obtain at least a first separated product; wherein, in the first separation product, the content of the components with the boiling point below 350 ℃ is not more than 5 weight percent, and the content of the components with the boiling point between 350 ℃ and 524 ℃ is 20-60 weight percent;
(3) extracting and separating the first separation product obtained in the step (2) in an extraction and separation unit by using an extraction solvent to obtain modified oil and residues;
(4) returning the residue obtained in the step (3) to the step (1) for the hydroconversion reaction; or, throwing the residue obtained in the step (3) outwards; or, returning part of the residue obtained in the step (3) to the step (1) for the hydroconversion reaction, and throwing the rest of the residue outwards;
(5) carrying out hydro-upgrading on the upgraded oil obtained in the step (3) to obtain hydro-upgraded oil;
(6) and (4) separating the hydro-upgrading oil obtained in the step (5), and carrying out catalytic conversion reaction on the obtained hydro-upgrading heavy oil to obtain a product containing low-carbon olefins.
2. The upgrading process of claim 1, in step (1), the hydroconversion reaction has a conversion of from 30 to 60 wt%.
3. The upgrading method of claim 1, in step (1), the hydroconversion reaction is carried out in a fluid bed reactor selected from at least one of a slurry bed reactor, a suspended bed reactor, and an ebullating bed reactor.
4. The upgrading process of claim 1, in step (1), the hydroconversion reaction is carried out in the presence or absence of a hydroconversion catalyst comprising at least one selected from the group consisting of a group VB metal compound, a group VIB metal compound, and a group VIII metal compound.
5. An upgrading process as claimed in claim 1 wherein in step (1) the hydroconversion reaction conditions include: the temperature is 380-470 ℃, 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 modifying raw material is 500-5000, and the dosage of the converting catalyst is 10-50000 micrograms/g based on the weight of the modifying raw material and calculated by the metal in the hydroconversion catalyst.
6. The upgrading method of claim 1, in step (1), the upgraded feedstock comprising at least one selected from the group consisting of poor crude oil, heavy oil, deoiled bitumen, coal derived oil, shale oil, and petrochemical waste oil.
7. The upgrading process of claim 1, the upgrading feedstock meeting one or more criteria selected from the group consisting of an API degree of less than 27, a boiling point greater than 350 ℃, an asphaltene content greater than 2 wt.%, and a heavy metal content greater than 100 micrograms/gram, based on the total weight of nickel and vanadium.
8. The upgrading method as claimed in claim 1, wherein in step (2), the content of components boiling below 350 ℃ in the first separated product is less than 3 wt%, and the content of components boiling between 350 ℃ and 524 ℃ is 25-55 wt%.
9. The upgrading method according to claim 1, wherein in step (2), the separation process comprises:
(2-1) separating the hydroconversion product obtained in the step (1) at a first pressure and a first temperature to obtain a gas component and a liquid component;
(2-2) separating the liquid component at a second pressure and a second temperature to obtain the first separated product and a second separated product; wherein the first pressure is greater than the second pressure.
10. The upgrading method of claim 9, wherein the first pressure is 10-25 mpa and the first temperature is 380-470 ℃; the second pressure is 0.1-5 MPa, and the second temperature is 150-390 ℃.
11. The upgrading method according to claim 9, wherein the separation process further comprises:
(2-3) cutting the second separation product obtained in the step (2-2) to obtain naphtha and atmospheric gas oil; and/or
(2-4) returning the gas component obtained in the step (2-1) to the step (1) for hydro-conversion reaction and/or the step (5) for hydro-upgrading.
12. The upgrading process of claim 11, wherein the second separation product and/or atmospheric gas oil is hydro-upgraded with the upgraded oil.
13. The upgrading process of claim 1 or 12, wherein the conditions of the hydro-upgrading of step (5) 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.
14. The upgrading process of claim 1 or 12, wherein the catalyst used for the hydro-upgrading of step (5) comprises a hydrofinishing catalyst and a hydrocracking catalyst, the hydrofinishing catalyst comprising a carrier and an active metal component selected from group VIB metals and/or group VIII non-noble metals; the hydrocracking catalyst comprises zeolite, alumina, at least one group VIII metal component and at least one group VIB metal component.
15. The upgrading process of claim 14, wherein 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.
16. The upgrading method of claim 1, wherein the catalytic conversion reaction of step (6) is carried out in a catalytic conversion reactor in the presence of a catalytic conversion catalyst, wherein the catalytic conversion reactor is selected from any one of a riser reactor, a fluidized bed reactor, a down-flow conveyor line reactor, a moving bed reactor, or a composite reactor combining any two reactors.
17. An upgrading method as claimed in claim 1, wherein the conditions of the catalytic conversion reaction in step (6) include: the reaction temperature is 500-750 ℃, the reaction pressure is 0.15-0.50 MPa, the reaction time is 0.2-10 seconds, the agent-oil ratio is 5-40, and the water-oil ratio is 0.05-1.0.
18. An upgrading process according to claim 1 wherein said catalytic conversion catalyst of step (6) comprises zeolite, inorganic oxide and optionally clay in respective amounts: 1-60 wt% of zeolite, 5-99 wt% of inorganic oxide and 0-70 wt% of clay, wherein the zeolite is a mixture of medium-pore zeolite and optional large-pore zeolite, the proportion of the medium-pore zeolite is 50-100 wt%, preferably 70-100 wt%, and the proportion of the large-pore zeolite is 0-50 wt%, preferably 0-30 wt%.
19. The upgrading process of claim 1, in step (3), the extractive separation is carried out in an extraction solvent at a third temperature and a third pressure; wherein the third pressure is 3-12 MPa, the third temperature is 55-300 deg.C, and the extraction solvent is C3-C7A hydrocarbon, the weight ratio of the extraction solvent to the first separation product being (1-7): 1.
20. the upgrading method of claim 1, in step (3), the softening point of the residue is less than 150 ℃.
21. The upgrading method according to claim 1, wherein in the step (4), the proportion of the residue returned to the step (1) to the total amount of the residue is 30 to 95% by weight, preferably 50 to 90% by weight.
22. The upgrading method as claimed in claim 1, wherein in step (6), the hydroupgraded oil is cut and separated into hydroupgraded light oil and hydroupgraded heavy oil, and the cut point between the hydroupgraded light oil and the hydroupgraded heavy oil is 340-360 ℃, preferably 345-355 ℃, and more preferably 350 ℃.
23. The system comprises a hydroconversion reaction unit, an extraction separation unit, a hydrogenation modification unit and a catalytic conversion unit, wherein the hydroconversion reaction unit is connected with the extraction separation unit, the extraction separation unit is connected with the hydrogenation modification unit, and the hydrogenation modification unit is connected with the catalytic conversion unit.
Technical Field
The invention relates to a method and a system for modifying low-carbon olefin produced by low-quality oil.
Background
The low-carbon olefin represented by ethylene and propylene is the most basic raw material in chemical industry, natural gas or naphtha fraction is mostly used as raw material at home and abroad, and the low-carbon olefin is produced by using ethane cracking or naphtha steam cracking process; but the propylene yield of the process is very low, and the requirement of the chemical industry market on propylene cannot be met. Therefore, the production of low-carbon olefins by cracking petroleum resources is a hot point of research of oil refining enterprises.
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 chemical raw materials such as low-carbon olefin to the maximum extent by utilizing unconventional oil or poor-quality oil is the key and key point for broadening the source of the raw materials for producing the low-carbon olefin, adjusting the product structure, improving the quality and enhancing the effect of the low-carbon olefin in petrochemical enterprises.
Chinese patent CN101045884A discloses a method for producing clean diesel oil and low-carbon olefin from residual oil and heavy distillate oil. The method comprises the steps that residual oil and optional catalytic cracking slurry oil enter a solvent deasphalting unit, the obtained deasphalted oil and optional heavy distillate oil enter a hydrogenation unit, hydrocracking reaction is carried out in the presence of hydrogen, and light and heavy naphtha fraction, diesel oil fraction and hydrogenation tail oil are obtained by separating products; the hydrogenated tail oil enters a catalytic cracking unit to carry out catalytic cracking reaction, and products are separated to obtain low-carbon olefin, gasoline fraction, diesel oil fraction and slurry oil; the diesel oil is recycled to the catalytic cracking unit and all or part of the oil slurry is returned to the solvent deasphalting unit. The method processes the mixture of vacuum residuum and catalytic cracking slurry oil to obtain 27.3 wt% propylene and 10.6 wt% ethylene.
WO2015084779a1 discloses a process for producing lower olefins, especially propylene, using a combination of solvent deasphalting and high severity catalytic cracking. The method comprises the following steps: mixing the vacuum residue oil and the solvent, and then performing solvent deasphalting treatment to obtain deasphalted oil and deoiled asphalt rich in the solvent; 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 low-carbon olefin, especially propylene is obtained. The method firstly carries out solvent deasphalting treatment on residual oil, and then realizes the high-efficiency conversion of deasphalted oil and the generation of low-carbon olefin through a combined process, but the deasphalted oil is not used and processed.
Disclosure of Invention
The invention aims to provide a method and a system for modifying low-carbon olefin produced by low-quality oil.
In order to achieve the above object, the present invention provides an upgrading method for producing lower olefins from low quality oil, the method comprising:
(1) carrying out hydro-conversion reaction on low-quality oil serving as a modified raw material to obtain a hydro-conversion product; wherein the conversion rate of the hydroconversion reaction is 30 to 70 wt%, which is (weight of component having a boiling point of 524 ℃ or higher in the upgraded raw material-weight of component having a boiling point of 524 ℃ or higher in the converted product)/weight of component having a boiling point of 524 ℃ or higher in the upgraded raw material × 100 wt%;
(2) separating the hydroconversion product obtained in the step (1) to obtain at least a first separated product; wherein, in the first separation product, the content of the components with the boiling point below 350 ℃ is not more than 5 weight percent, and the content of the components with the boiling point between 350 ℃ and 524 ℃ is 20-60 weight percent;
(3) extracting and separating the first separation product obtained in the step (2) in an extraction and separation unit by using an extraction solvent to obtain modified oil and residues;
(4) returning the residue obtained in the step (3) to the step (1) for the hydroconversion reaction; or, throwing the residue obtained in the step (3) outwards; or, returning part of the residue obtained in the step (3) to the step (1) for the hydroconversion reaction, and throwing the rest of the residue outwards;
(5) carrying out hydro-upgrading on the upgraded oil obtained in the step (3) to obtain hydro-upgraded oil;
(6) and (4) separating the hydro-upgrading oil obtained in the step (5), and carrying out catalytic conversion reaction on the obtained hydro-upgrading heavy oil to obtain a product containing low-carbon olefins.
The invention also provides an upgrading system for producing low-carbon olefins from low-quality oil, which comprises a hydroconversion reaction unit, an extraction separation unit, a hydroupgrading unit and a catalytic conversion unit, wherein the hydroconversion reaction unit is connected with the extraction separation unit, the extraction separation unit is connected with the hydroupgrading unit, and the hydroupgrading unit is connected with the catalytic conversion unit.
Compared with the prior art, the invention has the following advantages:
1. can upgrade the upgrading raw material into the upgrading oil which is rich in saturated structures and basically free of heavy metals and asphaltene with high efficiency and maximum. In preferred cases, the conversion of upgraded feedstock is generally greater than 90 wt%, preferably greater than 95 wt%, the resulting upgraded oil generally has a heavy metal content (based on the total weight of nickel and vanadium) of less than 10 micrograms/gram, preferably less than 5 micrograms/gram, and the upgraded oil generally has an asphaltene content of less than 2.0 wt%, preferably less than 0.5 wt%.
2. The upgrading method and the upgrading system provided by the invention have the advantages of stable operation, high upgrading efficiency, less three-waste emission, low coke yield, high upgrading oil yield, low yield of toluene insoluble substances in the upgrading oil and the like.
3. 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 material, reduce the external throwing residue 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 prevent the problems of poor fluidity and difficult dissolution when the residue returns to the conversion reaction within a reasonable range when the components with the boiling point of 350-524 ℃ in the first separation product are maintained.
4. The invention can further process the modified oil to produce chemical raw materials, namely low-carbon olefin, and realizes the yield of the low-carbon olefin to be more than 36 percent.
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.
Description of the reference numerals
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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 method for modifying low-carbon olefin produced by low-quality oil, which comprises the following steps: (1) carrying out hydro-conversion reaction on low-quality oil serving as a modified raw material in a hydro-conversion reactor under a hydro-condition to obtain a hydro-conversion product; wherein the conversion rate of the hydroconversion reaction is 30 to 70 wt%, which is (weight of the component having a boiling point of 524 ℃ or higher in the upgraded raw material-weight of the component having a boiling point of 524 ℃ or higher in the hydroconversion product)/weight of the component having a boiling point of 524 ℃ or higher in the upgraded raw material x 100 wt%; (2) separating the hydroconversion product obtained in the step (1) to obtain at least a first separated product; wherein, in the first separation product, the content of components with boiling points below 350 ℃ is not more than 5 weight percent, preferably less than 3 weight percent, the content of components with boiling points between 350 and 524 ℃ (preferably 355 and 500 ℃ or 380 and 524 ℃, and further preferably 400 and 500 ℃) is 20 to 60 weight percent, preferably 25 to 55 weight percent, the initial distillation point of the first separation product is generally not lower than 300 ℃, preferably not lower than 330 ℃, and more preferably not lower than 350 ℃; (3) extracting and separating the first separation product obtained in the step (2) in an extraction and separation unit by using an extraction solvent to obtain modified oil and residues; (4) returning the residue obtained in the step (3) to the step (1) for the hydroconversion reaction; or, throwing the residue obtained in the step (3) outwards; or, returning part of the residue obtained in the step (3) to the step (1) for the hydroconversion reaction, and throwing the rest of the residue outwards; (5) carrying out hydrogenation modification on the modified oil obtained in the step (3) to obtain hydrogenated modified oil; (6) and (4) separating the hydrogenated modified oil obtained in the step (5), and carrying out catalytic conversion reaction on the hydrogenated modified heavy oil to obtain dry gas, low-carbon olefin, aromatic hydrocarbon-rich gasoline, circulating oil and oil slurry. The low-carbon olefin comprises ethylene, propylene and butylene.
The invention can maintain the long-time operation of the system under the conditions of reducing the outward throwing of the residues as much as possible and improving the resource utilization rate, the hydroconversion reactor and the extraction separation unit are the key for determining whether the hydroconversion reactor and the extraction separation unit can operate for a long time, the conversion rate of the hydroconversion 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 boiling point of 350-.
According to the present invention, the conversion rate of the hydroconversion reaction is too high, which easily leads to coke formation and thus reduces the system operation time, while too low a conversion rate easily leads to too much throwing residue and reduces the upgrading efficiency per unit time, and the inventors have found through a large number of experiments that the conversion rate of the hydroconversion reaction in the present invention may be 30 to 70 wt%, preferably 30 to 60 wt%.
According to the invention, the hydroconversion reaction is essentially a thermal conversion reaction, which means that the upgrading raw material is subjected to thermal conversion under the hydroconversion condition to obtain the hydroconversion product at least containing the first separation product, and the hydroconversion product can also contain a gas component and a liquid product with a boiling point lower than the initial boiling point of the first separation product. The present invention is not particularly limited with respect to the conditions, catalyst and reactor of the hydroconversion reaction, provided that the above-mentioned conversion rates are achieved.
In one embodiment, the hydroconversion reaction is carried out in a fluidized bed reactor using a solid-liquid suspension as a catalyst, so the hydroconversion reactor can be a fluidized bed reactor, the fluidized bed reactor is a reactor in which reaction raw materials and the catalyst are reacted in a fluidized state, and the reactor is at least one selected from a slurry bed reactor, a suspension bed reactor and a fluidized bed reactor, and the slurry bed reactor and the suspension bed reactor are preferred in the invention.
In one embodiment, the hydroconversion reaction is carried out in the presence or absence of a hydroconversion catalyst, which may comprise at least one 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 a Mo compound, a W compound, a Ni compound, a Co compound, a Fe compound, a V compound, and a Cr compound; the hydroconversion reaction conditions 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 modified raw material is 0.01-2 hours-1Preferably 0.1 to 1.0 hour-1The volume ratio of the hydrogen to the modifying raw material is 500-5000, preferably 800-2000, and the dosage of the hydroconversion catalyst is 10-50000 micrograms/g, preferably 30-25000 micrograms/g based on the metal in the hydroconversion catalyst and the weight of the modifying raw material.
According to the invention, the upgraded feedstock is selected from low quality feedstocks containing asphaltenes. Asphaltenes are substances in the upgrading feedstock that are insoluble in non-polar, small-molecule n-alkanes (such as n-pentane or n-heptane) and soluble in benzene or toluene. The modified raw material is preferably selected according to the requirementsOne or more of an API degree of less than 27, a boiling point 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 upgraded feedstock 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; the residue refers to a bottom distillate obtained by atmospheric and vacuum distillation of crude oil, the atmospheric distillation bottom distillate is generally called atmospheric residue (generally a fraction with a boiling point of more than 350 ℃), the vacuum distillation bottom distillate is generally called vacuum residue (generally a fraction with a boiling point of more than 500 ℃ or 524 ℃), the residue can be at least one selected from topped crude oil, heavy oil obtained from oil sand bitumen and heavy oil with a primary boiling point of more than 350 ℃, and the topped crude oil refers to oil discharged from the bottom of a primary distillation 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; 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 combinationAfter the synthesis, the product is used as a modifying raw material to carry out the hydroconversion reaction, and the invention is not repeated.
According to the invention, the first separated product generally consists of the products with the highest boiling point in the hydroconversion product, which comprises the residue in the step (3), wherein the main component of the residue is asphaltene and also comprises some colloid and aromatic components necessary for maintaining fluidity, the first separated product also comprises upgraded oil besides the residue, the first separated product can be used as a high-quality raw material for subsequent treatment to obtain other oil products after extraction and separation, and the rest components with lower boiling point in the hydroconversion product can be separated from the first separated product, such as gas products (such as dry gas, liquefied gas and the like) in a standard state and other components with the boiling point below 350 ℃.
According to the present invention, the separation treatment in step (2) 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 step (2) 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 (2), the separation process includes step (2-1) and step (2-2):
(2-1) separating the hydroconversion product obtained in the step (1) at a first pressure and a first temperature to obtain a gas component and a liquid component; in the step (2-1), 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 example, the first pressure may be in the range of from 10 to 25 MPa, preferably in the range of from 13 to 20 MPa, for convenience of measurement, the first pressure generally referring to the outlet pressure of the gaseous component as it leaves the separation device, the first temperature may be in the range of from 380 ℃ to 470 ℃, preferably in the range of from 400 ℃ to 440 ℃, for convenience of measurement, the first temperature generally referring to the outlet temperature of the liquid component as it leaves 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;
(2-2) separating the liquid component at a second pressure and a second temperature to obtain the first separated product and a second separated product; in the step (2-2), it is preferable to separate out the components having boiling points below 350 ℃ while retaining the components having boiling points at 350-524 ℃; said first pressure is preferably greater than said second pressure, said first pressure further preferably being 4 to 24 MPa greater than the second pressure, more preferably 7 to 19 MPa greater; in particular, the second pressure may be in the range of from 0.1 to 5 MPa, preferably in the range of from 0.1 to 4 MPa, for convenience of measurement, the second pressure generally referring to the outlet pressure of the second separated product as it leaves the separation device, the second temperature may be in the range of from 150 ℃ to 390 ℃, preferably 200 ℃ to 370 ℃, for convenience of measurement, the second temperature generally referring to the outlet temperature of the first separated product as it leaves 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.
In an alternative embodiment, the separation process further comprises step (2-3) and/or step (2-4):
(2-3) subjecting the second separated product obtained in the step (2-2) to a cleavage to obtain naphtha and atmospheric gas oil, the cleavage being carried out by fractionation or distillation, preferably fractionation, for example, in a fractionating column, which may be operated at a pressure of 0.05 to 2.0 MPa, preferably 0.1 to 1.0 MPa, and at a temperature of 50 to 350 ℃, preferably 150 to 330 ℃; and/or
(2-4) returning the gas component obtained in the step (2-1) to the step (1) for hydro-conversion reaction and/or the step (5) for hydrotreatment, wherein the gas component can be directly used or separated to be used as recycle hydrogen.
According to the invention, the extraction separation is used for separating the easily processed modified oil in the first separation product, and the residue is thrown outwards or returned to the hydro-conversion reaction, specifically, in the step (3), the extraction separation can be carried out in the extraction solvent at the third temperature and the third pressure, preferably, the extraction solvent is in countercurrent contact with the first separation product for extraction, and can be carried out in any extraction device, such as an extraction tower; wherein the third pressure may be 3-12 MPa, preferably 3.5-10 MPa, and the third temperature may be 55-300 MPaThe temperature is preferably 70-220 ℃, and the extraction solvent can be 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 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 hydroconversion product and the more completely the readily processable components of the hydroconversion product are separated the higher the softening point, but in order to maintain the fluidity of the residue on-line and solubility of the residue on return to the hydroconversion reactor, the softening point of the residue in step (3) is preferably less than 150 ℃, more preferably less than 120 ℃.
According to the present invention, if the hydroconversion reaction of the present invention is carried out in a fluidized bed reactor, the hydroconversion catalyst therein is subsequently separated along with the hydroconversion product and remains in the residue, and the metal in the whole upgrading system is continuously increased along with the increase of the catalyst addition and the accumulation of the metal components in the upgrading raw material. In order to maintain the balance of metals in the upgrading system, the residue needs to be discharged intermittently or continuously, and in order to fully use the upgrading raw material, in the step (4), part of the residue is thrown outward, and the proportion of the thrown-outward residue in the total amount of the residue is preferably 5 to 70 wt%, more preferably 10 to 50 wt%; the proportion of the residue returned to step (1) is preferably 30 to 95% by weight, more preferably 50 to 90% by weight. The proportion of the slag thrown out can be adjusted by those skilled in the art according to the modified raw materials with different metal contents, and the invention is not described in detail.
According to the invention, in order to facilitate the production of chemical raw materials, namely low-carbon olefins, the obtained cycle oil can be subjected to hydro-upgrading independently or together with the upgraded oil, the obtained hydro-upgraded oil is cut and separated into hydro-upgraded light oil and hydro-upgraded heavy oil, and the cut point between the hydro-upgraded light oil and the hydro-upgraded heavy oil is 340-360 ℃, preferably 345-355 ℃, and more preferably 350 ℃; carrying out catalytic conversion reaction on the obtained hydrogenation modified heavy oil to obtain dry gas, low-carbon olefin, gasoline, circulating oil and slurry oil; and/or returning the obtained oil slurry to the step (1) for hydro-conversion reaction; and/or separating the obtained C3 and C4 hydrocarbons to send C3 and C4 alkanes to the step (3) to be used as extraction solvents. Meanwhile, in the step (6), the second separated product and/or the atmospheric gas oil may be catalytically converted together with the hydro-upgraded heavy oil. The step (6) and the steps can produce chemical raw materials to the maximum extent, and the utilization rate of the modified oil and the second separation product is improved. The cycle oil generally comprises light cycle oil and heavy cycle oil, the light cycle oil can also be called diesel oil and refers to fraction with a boiling point between 205 ℃ and 350 ℃ obtained by catalytic cracking reaction, the heavy cycle oil refers to fraction with a boiling point between 343 ℃ and 500 ℃, the slurry oil generally refers to bottom oil obtained by a fractionation step of the catalytic cracking reaction, the bottom oil is separated by a settler and is discharged from the bottom of the settler, and the product discharged from the upper part of the settler is generally called clarified oil. The method can return the oil slurry to carry out conversion reaction, on one hand, the utilization rate of raw materials can be improved, and the oil slurry with low added value is converted into the gasoline product rich in aromatic hydrocarbon with high added value; on the other hand, the oil slurry is rich in aromatic hydrocarbon components, so that the stability of the conversion unit can be improved, and the operation period of the device can be prolonged.
The hydro-upgrading and catalytic conversion reactions according to the present invention are well known to those skilled in the art, and the hydro-upgrading can be carried out in any manner known in the art, without particular limitation, in any hydrotreater known in the art (e.g., fixed bed reactor, fluidized bed reactor), and those skilled in the art can make a reasonable choice for this. For example, the conditions for the hydro-upgrading 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 hydro-upgrading unit comprises hydrofining catalyst andthe hydrocracking catalyst, the hydrorefining catalyst and the hydrocracking catalyst may be any catalyst conventionally used for this purpose in the art or may be produced by any production method conventionally known in the art, and the amounts of the hydrorefining catalyst and the hydrocracking catalyst used in the above step are not particularly limited, as long as they are conventionally known in the art. For a specific example, the hydrofining catalyst comprises a carrier and an active metal component, wherein 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; preferably, the hydrocracking catalyst may comprise 3 to 60 wt% of zeolite, 10 to 80 wt% of alumina, 1 to 15 wt% of nickel oxide and 5 to 40 wt% of tungsten oxide, based on the dry weight of the hydrocracking catalyst, wherein the zeolite is a Y-type zeolite. Other compositions of hydrocracking catalysts may also be employed by those skilled in the art. The filling volume ratio of the hydrofining catalyst to the hydrocracking catalyst is 1-5:1, and the hydrofining catalyst is filled at the upstream of the hydrocracking catalyst according to the flow direction of reaction materials.
The catalytic conversion reaction is carried out in the presence of a catalytic conversion catalyst, which conditions may include: the reaction temperature is 500-750 ℃, preferably 510-680 ℃, the reaction pressure is 0.15-0.50 MPa, the reaction time is 0.2-10 seconds, preferably 2-4 seconds, the catalyst-oil ratio (the weight ratio between the catalytic conversion catalyst and the catalytic conversion raw oil) is 5-40, preferably 5-30, and the water-oil ratio (the weight ratio between the water vapor and the catalytic conversion raw oil) is 0.05-1.0, preferably 0.05-0.5. The catalytic conversion may be carried out in any catalytic conversion device known in the art, such as a riser and fluidized bed combined reactor, and is typically carried out in the presence of a catalytic conversion catalyst. Here, the catalytic conversion catalyst is not particularly limited, and may be any catalytic conversion catalyst conventionally used in the art for this purpose, or may be produced by any production method conventionally known in the art. By way of specific example, the catalytic conversion catalyst comprises zeolite, inorganic oxide and optionally clay, and the contents of the components are respectively as follows: 1-60 wt% of zeolite, 5-99 wt% of inorganic oxide and 0-70 wt% of clay, wherein the zeolite is a mixture of medium-pore zeolite and optional large-pore zeolite, the proportion of the medium-pore zeolite is 50-100 wt%, preferably 70-100 wt%, and the proportion of the large-pore sub-sieve is 0-50 wt%, preferably 0-30 wt%. In the invention, the average pore diameter of the medium pore zeolite is 0.5-0.6 nm, and the average pore diameter of the large pore zeolite is 0.7-1.0 nm. The intermediate pore size zeolite can be selected from zeolites having MFI structure, such as ZSM series zeolites and/or ZRP zeolites, which can also be modified with nonmetallic elements such as phosphorus and/or metallic elements such as rare earth, aluminum, magnesium, calcium, iron, cobalt, nickel, etc., as described in more detail in U.S. Pat. No. 5,232,675, the ZSM series zeolites are selected from one or more mixtures of ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other zeolites of similar structure, and the ZSM-5 is described in more detail in U.S. Pat. No. 3,702,886. The large-pore zeolite is preferably at least one of Y-type zeolite, rare earth element-containing HY-type zeolite, and rare earth element-containing ultrastable Y-type zeolite. Further, as the carrier, at least one selected from the group consisting of refractory inorganic oxides, natural clays, alumina, silica and amorphous silica-alumina is exemplified. The present invention is not particularly limited with respect to the respective contents of the cleavage active component and the carrier, and reference can be made to conventional knowledge in the art. The product of catalytic conversion can be isolated by any method and in any manner known in the art, and specific examples thereof include distillation and fractional distillation, particularly fractional distillation. The above-mentioned conditions, catalysts and apparatuses for the hydro-upgrading and catalytic conversion reactions are applicable to different hydro-upgrading raw materials and catalytic conversion raw materials, and the optimum conditions, catalysts and apparatuses for the different hydro-upgrading raw materials and catalytic conversion raw materials can be selected for the reactions.
The invention will be further illustrated by the following specific embodiments, but the invention is not limited thereto.
As shown in the figure1, the modified raw material is conveyed to a hydroconversion reactor 7 for hydroconversion reaction through a
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
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%;
yield of upgraded oil is upgraded oil weight/upgraded raw material weight × 100%;
the yield of the hydrogen high added value product/%, namely the yield of liquefied gas, the yield of distillate oil and the yield of modified oil;
the yield of toluene insolubles was determined as toluene insolubles weight/modified feedstock weight × 100%;
the softening point of the residue is measured by a GB/T4507-84 method;
the special component refers to the component with the boiling point between 350 ℃ and 524 ℃ in the first separation product;
ethylene yield ═ ethylene weight/catalytically converted feed oil weight × 100 weight%;
the yield of propylene is equal to the weight of propylene/the weight of catalytic conversion raw oil multiplied by 100 weight percent;
the yield of the butene is the weight of the butene/the weight of the catalytic conversion raw oil multiplied by 100 weight percent;
the yield of the low-carbon olefin is the yield of ethylene, the yield of propylene and the yield of butylene.
The operation stability of the reforming process was evaluated by the number of days of stable operation of the reforming system. Specifically, the upgrading system is determined to be unable to operate stably if any one of the following conditions occurs:
(1) the maximum temperature difference delta T (absolute value) of different temperature measuring points in the hydroconversion 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 processed in accordance with the embodiment of FIG. 1 described above.
In the following examples and comparative examples, both of upgraded feedstock a and upgraded feedstock B were vacuum residuum, and their properties are shown in table 1.
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