CN109486515B - Method and system for efficiently modifying inferior oil - Google Patents
Method and system for efficiently modifying inferior oil Download PDFInfo
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- CN109486515B CN109486515B CN201710812669.4A CN201710812669A CN109486515B CN 109486515 B CN109486515 B CN 109486515B CN 201710812669 A CN201710812669 A CN 201710812669A CN 109486515 B CN109486515 B CN 109486515B
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
The invention relates to a method and a system for efficiently modifying inferior oil, wherein the method comprises the following steps: the modified raw materials are sequentially subjected to heat treatment, conversion reaction, separation treatment and extraction separation to obtain modified oil and tailings, and the obtained tailings are thrown or circularly turned to perform conversion reaction. The method and the system provided by the invention can maintain the long-time operation of the system under the condition that the external throwing tailings are as little as possible, and realize the high-efficiency utilization of low-quality oil and catalytic cracking slurry oil.
Description
Technical Field
The invention relates to a method and a system for efficiently modifying inferior oil.
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.
Chinese patent CN200310104918.2 discloses a method for modifying inferior heavy and residual oil, which comprises subjecting heavy and residual oil to mild hydrocracking in a suspension bed to remove most or all metal impurities 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.
US patent 20130112593a1 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 provide a method and a system for efficiently upgrading poor-quality oil, which can maintain the long-time operation of the system under the condition of reducing the external throwing tailings as little as possible.
In order to achieve the above object, the present invention provides a method for efficiently upgrading inferior oil, comprising:
(1) performing heat treatment on inferior oil serving as a modified raw material to obtain a gas-phase product and a liquid-phase product; wherein the modified raw material comprises at least one asphalt component selected from asphaltene, asphaltene and pre-asphaltene, and the yield of toluene insoluble substances in the liquid-phase product is not more than 0.5 wt%;
(2) carrying out conversion reaction on the liquid-phase product obtained in the step (1) in a conversion reactor under the condition of hydrogen to obtain a conversion product; wherein the total conversion rate of the conversion reaction in the step (2) and the heat treatment in the step (1) is 30 to 70% by weight, which is (weight of components having a distillation range of 524 ℃ or more in the upgraded raw material-weight of components having a distillation range of 524 ℃ or more in the converted product)/weight of components having a distillation range of 524 ℃ or more in the upgraded raw material x 100%;
(3) separating the conversion product obtained in the step (2) to obtain at least a first separated product; wherein, in the first separation product, the content of the components with the distillation range below 350 ℃ is not more than 5 weight percent, and the content of the components with the distillation range between 350 ℃ and 524 ℃ is 20-60 weight percent;
(4) extracting and separating the first separation product obtained in the step (3) in an extraction separation unit to obtain modified oil and tailings;
(5) returning the tailings obtained in the step (4) to the step (2) for the conversion reaction; or, the tailings obtained in the step (4) are thrown outwards; or returning part of tailings obtained in the step (4) to the step (2) for the conversion reaction, and throwing the rest of tailings outwards.
The invention also provides a high-efficiency upgrading system for the inferior oil, which comprises a heat processor, a conversion reactor, a separation processing unit and an extraction separation unit; the heat treatment device is provided with a feed inlet, a gas-phase product outlet and a liquid-phase product outlet, the conversion reactor is provided with a reaction material inlet and a conversion product outlet, the separation treatment unit is provided with a treatment raw material inlet and a first separation product outlet, and the extraction separation unit is provided with an extraction solvent inlet, an extraction raw material inlet, a modified oil outlet and a tailings outlet; the liquid-phase product outlet of the heat treatment device is connected with the reaction material inlet of the conversion reactor, the conversion product outlet of the conversion reactor is connected with the treatment raw material inlet of the separation treatment unit, the first separation product outlet of the separation treatment unit is connected with the extraction raw material inlet of the extraction separation unit, and the tailings outlet of the extraction separation unit is optionally connected with the reaction material inlet of the conversion reactor.
Compared with the prior art, the invention has the following advantages:
1. the upgrading raw material can be upgraded to the upgraded oil which is rich in saturated structure, basically free of heavy metal and basically free of asphaltene with high efficiency and maximum. In preferred aspects, 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 1 microgram/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, environmental protection, low coke yield, high upgrading oil yield, low yield of toluene insoluble substances in 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 tailings 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, thereby preventing the problems of poor fluidity and difficult dissolution when the tailings are returned to carry out the conversion reaction.
4. The invention can reduce the viscosity of the inferior oil by carrying out heat treatment on the inferior oil, reduce the operation severity of equipment (such as a circulating pump) in a subsequent feeding unit and the operation difficulty of a batching unit (such as a batching tank), and prolong the operation period of the device; in addition, toluene insoluble substances generated in situ in the heat treatment process can be used as a 'coke-carrying agent' of a subsequent conversion unit, so that the inactivation of the catalyst in the conversion unit is reduced, the use amount of the catalyst is reduced, and the process economy is improved.
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
1 line 2 thermal processor 3 line
4 line 5 line 6 line
7 line 8 line 9 line
10 conversion reactor 11 line 12 high pressure separation unit
13 line 14 line 15 line
16 low pressure separation unit 17 line 18 line
19 extractive separation unit 20 line 21 line
22 line 23 line
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 high-efficiency upgrading method of inferior oil, which comprises the following steps: (1) performing heat treatment on inferior oil serving as a modified raw material to obtain a gas-phase product and a liquid-phase product; wherein the modified raw material comprises at least one asphalt component selected from asphaltene, asphaltene and pre-asphaltene, and the yield of toluene insoluble substances in the liquid-phase product is not more than 0.5 wt%; (2) carrying out conversion reaction on the liquid-phase product obtained in the step (1) in a conversion reactor under the condition of hydrogen to obtain a conversion product; wherein the total conversion rate of the conversion reaction in the step (2) and the heat treatment in the step (1) is 30 to 70% by weight, which is (weight of components having a distillation range of 524 ℃ or more in the upgraded raw material-weight of components having a distillation range of 524 ℃ or more in the converted product)/weight of components having a distillation range of 524 ℃ or more in the upgraded raw material x 100%; (3) separating the conversion product obtained in the step (2) to obtain at least a first separated product; wherein, in the first separation product, the content of components with the distillation range below 350 ℃ is not more than 5 weight percent, preferably less than 3 weight percent, the content of components with the distillation range between 350 and 524 ℃ (preferably 355 and 500 ℃ or 380 and 524 ℃, and further preferably 400 and 500 ℃) is 20-60 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 ℃; (4) extracting and separating the first separation product obtained in the step (3) in an extraction separation unit to obtain modified oil and tailings; (5) returning the tailings obtained in the step (4) to the step (2) for the conversion reaction; or, the tailings obtained in the step (4) are thrown outwards; or returning part of tailings obtained in the step (4) to the step (2) for the conversion reaction, and throwing the rest of tailings outwards.
The invention can maintain the long-time operation of the system under the conditions of reducing tailings and external throwing as much as possible and improving the resource utilization rate, the poor-quality oil raw material firstly enters a heat treatment device for shallow cracking, and toluene insoluble substances (coke) generated in situ in the heat treatment process can be used as a coke carrying agent, thereby reducing the inactivation of a catalyst in a conversion unit, reducing the using amount of the catalyst, improving the process economy, reducing the viscosity of a liquid phase product in the heat treatment process, reducing the operation difficulty of subsequent equipment and prolonging the operation period, but the stability of the system is reduced due to too deep cracking process of the heat treatment, which is not beneficial to the system stability, so that the yield of the toluene insoluble substances in the liquid phase product obtained after the heat treatment must be strictly controlled, namely the content of the toluene insoluble substances is less than 0.5 percent, wherein the reaction: the temperature is 350-470 ℃, preferably 370-460 ℃;the volume space velocity (the volume of the modified raw material processed by the heat processor in unit volume in unit time) is 0.05-10 hours-1Preferably 0.1 to 8.0 hours-1。
The conversion reactor and the extraction separation unit are the key for determining whether the conversion reactor can be operated for a long time, the conversion rate of the conversion reactor is as high as possible under the condition that the system stability allows, light components below 350 ℃ in the first separation product entering the extraction separation unit are not too much, otherwise, the light components can pollute a solvent, black oil is generated in the extraction separation process, components with the distillation range of 350-524 ℃ are more, otherwise, tailings are easy to flow, and the conversion reaction is not easy to perform in the conversion reactor.
According to the invention, the total conversion rate of the heat treatment and the conversion reaction is too high, which is easy to generate coke, thereby reducing the system running time, and the conversion rate is too low, which is easy to cause excessive external tailings and reduce the modification efficiency, and the inventor finds that the content of the liquid phase product toluene insoluble substance obtained by the heat treatment is not more than 0.5 wt% through a large amount of experiments; the total conversion rate of the heat treatment and the conversion reaction may be 30 to 70% by weight, preferably 30 to 60% by weight, and the operation period of the reforming system may be long.
According to the invention, the heat treatment reaction is essentially a thermal conversion reaction, meaning a heat treatment process in the absence of a catalyst; the conversion reaction is essentially a hydro-thermal conversion reaction, which means that the modified raw material is subjected to heat treatment under the condition of hydrogen, and a conversion product at least containing a first separation product is obtained, and the conversion product can also contain a gas component and a liquid product with the distillation range lower than the initial distillation point of the first separation product. The present invention is not particularly limited in terms of the conditions, catalyst and reactor for the conversion reaction, as long as the above-mentioned conversion rate can be achieved.
In one embodiment, the conversion reaction 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 flowing 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 is carried out in the presence or absence of a conversion catalyst, which may contain 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 conditions of the conversion reaction may include: the temperature is 380-470 ℃, preferably 400-440 ℃, the hydrogen partial pressure is 10-25 MPa, preferably 13-20 MPa, and the volume space velocity of fresh feed (referring to liquid phase product obtained by heat treatment) is 0.01-2 hours-1Preferably 0.1 to 1.0 hour-1The volume ratio of hydrogen to fresh feed (liquid phase product obtained by heat treatment) is 500-5000, preferably 800-2000, and the amount of the conversion catalyst is 10-50000 micrograms/g, preferably 30-25000 micrograms/g, based on the metal in the conversion catalyst and the weight of the modified raw material.
According to the present invention, the upgraded feedstock may comprise at least one bituminous component selected from the group consisting of asphaltenes, asphaltenes and preasphatenes, preferably comprising asphaltenes and/or preasphatenes, more preferably comprising asphaltenes. Asphaltene is a substance that is insoluble in nonpolar small-molecule n-alkanes (such as n-pentane or n-heptane) and soluble in benzene or toluene in the upgraded material, asphaltene is a substance that is soluble in toluene and insoluble in n-hexane in the upgraded material, and preasphaltene is a substance that is soluble in tetrahydrofuran and insoluble in toluene in the upgraded material. The upgraded feedstock 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 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 boiling point above 350 ℃, and the distillate oil generally refers to crude oil or secondary processing oil which is subjected to atmospheric distillation and vacuum distillationDistillate products obtained by distillation, such as heavy diesel oil, heavy gas oil, lubricating oil distillate 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; 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.
According to the invention, the first separated product generally consists of the products with the highest distillation range in the converted products, and comprises the tailings in the step (4), wherein the main component of the tailings is asphaltene and also comprises some colloid and aromatic components which are necessary for maintaining fluidity, the first separated product also comprises the upgraded oil besides the tailings, the first separated product can be used as a high-quality raw material for subsequent treatment to obtain other oil products after being separated by extraction, and the rest components with the lower distillation range in the converted products 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 distillation range below 350 ℃.
According to the present invention, the separation treatment in step (3) 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 (3), the separation process includes step (3-1) and step (3-2):
(3-1) separating the conversion product obtained in the step (2) at a first pressure and a first temperature to obtain a gas component and a liquid component; in the step (3-1), 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;
(3-2) 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 (3-2), 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; 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 (3-3) and/or step (3-4):
(3-3) subjecting the second separated product obtained in the step (3-2) 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
(3-4) returning the gas component obtained in the step (3-1) to the step (2) for conversion reaction, 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 tailings are thrown outwards or returned to carry out the conversion reaction, specifically, in the step (4), 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, the third temperature may be 55-300 deg.C, preferably 70-220 deg.C, and the extraction solvent may 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 tailings are the highest boiling fraction of the conversion product, the more completely the easily processable fraction of the conversion product separates as its softening point increases, but in order to maintain its fluidity during pipeline transport and its solubility on return to the conversion reactor, the softening point of said tailings is preferably less than 150 ℃, more preferably less than 120 ℃ in step (4).
According to the present invention, 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 tailings, and the metal in the whole upgrading system is increased along with the increase of the catalyst addition amount and the accumulation of the metal component in the upgrading raw material. In order to maintain the balance of metals in the upgrading system, the tailings need to be discharged intermittently or continuously, and in order to fully use the upgrading raw materials, in the step (5), part of the tailings are thrown outwards, and the proportion of the thrown tailings in the upgrading raw materials is less than 10 wt%; the proportion of tailings returned to step (1) is preferably greater than 80 wt%, preferably greater than 90 wt%, more preferably greater than 95 wt%. The proportion of the tailings thrown outwards can be adjusted by those skilled in the art according to modified raw materials with different properties, and the invention is not described in detail.
As shown in fig. 1, the present invention also provides a system for efficiently upgrading inferior oil, which comprises a thermal processor 2, a conversion reactor 10, a separation processing unit and an extraction separation unit 19; the heat treatment device 2 is provided with a feed inlet, a gas-phase product outlet and a liquid-phase product outlet, the conversion reactor 10 is provided with a reaction material inlet and a conversion product outlet, the separation treatment unit is provided with a treatment raw material inlet and a first separation product outlet, and the extraction separation unit 19 is provided with an extraction solvent inlet, an extraction raw material inlet, a modified oil outlet and a tailings outlet; the liquid phase product outlet of the heat processor 2 is connected with the reaction material inlet of the conversion reactor 10, the conversion product outlet of the conversion reactor 10 is connected with the processing raw material inlet of the separation processing unit, the first separation product outlet of the separation processing unit is connected with the extraction raw material inlet of the extraction separation unit 19, and the tailings outlet of the extraction separation unit 19 is optionally connected with the reaction material inlet of the conversion reactor 10.
The system provided by the invention is used for carrying out the upgrading reaction provided by the invention, for example, as shown in fig. 1, the separation processing unit comprises a high-pressure separation unit 12 and a low-pressure separation unit 16, the high-pressure separation unit 12 is provided with a gas component outlet, a liquid component outlet and the processing raw material inlet, the low-pressure separation unit 16 is provided with a low-pressure raw material inlet, a second separation product outlet and the first separation product outlet, and the liquid component outlet of the high-pressure separation unit 12 is connected with the raw material inlet of the low-pressure separation unit 16.
The thermal processor according to the invention is well known to the person skilled in the art and may be a column reactor, for example a visbreaker or the like.
According to the present invention, in order to recycle the gaseous components, the gaseous component outlet of the high-pressure separation unit 12 is connected to the reaction mass inlet of the conversion reactor 10, 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 reforming raw material enters a heat treatment device 2 through a pipeline 1 to obtain a gas-phase product and a liquid-phase product, the gas-phase product is led out of the reforming system through a pipeline 3, the liquid-phase product is mixed through a pipeline 4, a reforming catalyst through a pipeline 5, circulating hydrogen through a pipeline 6, fresh hydrogen through a pipeline 7 and tailings through a pipeline 8 and is conveyed into a reforming reactor 10 through a pipeline 9 for reforming reaction. The converted product is conveyed to a high-pressure separation unit 12 through a pipeline 11 for high-pressure distillation, 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 10 through a pipeline 13, a pipeline 6 and a pipeline 9 in sequence, or is led out of the upgrading system through the pipeline 13 and a pipeline 14 in sequence. The liquid component is conveyed via line 15 to a low pressure separation unit 16 for pressure letdown and separation into a second separated product and a first separated product. The second separated product is led out of the upgrading system through a pipeline 18, and the first separated product is conveyed to an extraction separation unit 19 through a pipeline 17 to be in countercurrent contact with an extraction solvent from a pipeline 20 for extraction separation, so that upgraded oil and tailings are obtained. The modified oil is led out of the modifying system through a pipeline 21, one part of the tailings is thrown out through a pipeline 22 and a pipeline 23, and the rest part of the tailings serving as the modified raw material is circulated to the conversion reactor 10 through the pipeline 22, the pipeline 8 and the pipeline 9 to be subjected to conversion reaction with the modified raw material continuously. Alternatively, all the tailings may be thrown out through the line 22 and the line 23 in succession without being circulated.
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 nitrogen content in the oil product is carried out according to the SH/T0704-2001 method;
the method for measuring the content of the asphaltene in the oil product is carried out according to SH/T0266-92 (1998);
the conversion rate of the modified raw material is (1-tailing external throwing rate) multiplied by 100 percent, and the tailing external throwing rate is the weight of the external throwing slag/the weight of the modified raw material multiplied by 100 percent;
yield of upgraded oil is upgraded oil weight/upgraded raw material weight × 100%;
the tailing circulation proportion is equal to the weight of the circulating tailing/the weight of the total tailing multiplied by 100 percent;
denitrogenation rate (nitrogen content of modified raw material-nitrogen content of modified oil x yield of modified oil)/nitrogen content of modified raw material x 100%;
yield of toluene insoluble matter in the modified oil is toluene insoluble matter weight/modified raw material weight × 100%;
the softening point of the tailings is measured by a GB/T4507-84 method;
the special component refers to the component with the distillation range between 350 ℃ and 524 ℃ in the first separation product.
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 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 upgraded feedstocks, upgraded feedstock a and upgraded feedstock B were vacuum residuum, upgraded feedstock C was venezuelan heavy oil vacuum residuum, upgraded feedstock D was high temperature coal tar, and upgraded feedstock E was deoiled asphalt, and the properties of these five upgraded feedstocks are shown in table 1.
Examples 1 to 5
On a medium-sized apparatus, first, a heat treatment is performed on the reformed raw material, the resultant liquid-phase product is subjected to a conversion reaction, and then a separation treatment of the converted product is performed in two fractionation columns to obtain a first separated product and a second separated product, and specific conditions and results of the conversion reaction and the separation treatment are shown in tables 2-1 and 2-2.
Examples 6 to 8
On a medium-sized apparatus, the modified raw material was first subjected to heat treatment, the resultant liquid-phase product was subjected to a conversion reaction, and then subjected to a separation treatment in two fractionation columns to obtain a first separated product and a second separated product, and specific conditions and results of the conversion reaction and the separation treatment are shown in table 3.
Examples 9 to 11
The first separated products obtained in example 2, example 4 and example 7 were subjected to extractive separation on a medium-sized apparatus, and specific conditions and results of the extractive separation are shown in Table 4.
Examples 12 to 13
On a medium-sized device, the modified raw material B and the modified raw material C are firstly subjected to heat treatment, the obtained liquid phase product is subjected to conversion reaction, and then separation treatment is carried out, wherein the separation treatment is carried out in two fractionating towers, and a first separation product and a second separation product are obtained. And extracting and separating the first separation product to obtain modified oil and tailings. One part of the tailings circulates, and the other part is thrown outwards. And mixing the obtained tailings with liquid-phase products obtained after heat treatment of the modified raw material B and the modified raw material C respectively, then carrying out conversion reaction, and separating a second separation product to obtain naphtha fraction and normal-pressure gas oil. The specific conditions and results of the respective steps are shown in tables 5-1 and 5-2.
As is clear from comparison of the results in tables 4, 5-1 and 5-2, the recycle of tailings is advantageous in improving the conversion of the upgrading raw material and the yield of the upgrading oil.
Example 14
On a medium-sized device, the modified raw material B is firstly subjected to heat treatment, the obtained liquid-phase product is subjected to conversion reaction, and then separation treatment is carried out, wherein the separation treatment is carried out in two fractionating towers to obtain a first separated product and a second separated product. The first separated product is extracted and separated again (the extraction and separation conditions are the same as those in example 12), and modified oil and tailings are obtained. And mixing one part of tailings with the liquid-phase product obtained after the heat treatment of the modified raw material B, carrying out conversion reaction, and throwing the rest part of tailings outwards. And (3) separating the conversion products of the mixed raw materials in two fractionating towers in sequence, and performing extraction separation to obtain the modified oil and the tailings. And simultaneously separating the obtained second separation product to obtain naphtha fraction and normal-pressure gas oil. The specific conditions and results of the respective steps are shown in tables 6-1 and 6-2.
Comparative examples 1 to 6
The basic procedure was the same as in example 14 except for changing the conditions shown in Table 7-1, comparative example 6 was conducted without heat treatment, and the conditions for extraction and separation were the same as in example 12.
The results in Table 7-2 show that when one of the conversion rate of the conversion reaction, the component content of the first separated product 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 6-12 percent, the yield of the modified oil is reduced by 5-16 percent, the yield of the toluene insoluble substance is improved by 1-4.6 percent, and the stable operation days of the modified system are greatly reduced because the delta T is more than 5 ℃ or the modified oil is black. Comparing comparative examples 1 and 5 with example 14, the number of days for stable operation of the apparatus was also greatly reduced when the heat treatment conditions were inappropriate to result in a yield of toluene insolubles of > 0.5%. Comparing example 14 with comparative example 6, it can be seen that the amount of catalyst used can be reduced after the upgrading oil is heat-treated.
TABLE 1
TABLE 2-1
Tables 2 to 2
TABLE 3
TABLE 4
TABLE 5-1
TABLE 5-2
TABLE 6-1
TABLE 6-2
| Item | Example 14 |
| Yield of toluene insoluble matter in heat-treated liquid-phase product,% by weight | 0.4 |
| Total conversion of heat treatment and conversion reaction% | 56.4 |
| Product distribution/weight% | |
| First separated product | 67.9 |
| Distillation range/. degree.C.of particular components in the first separation product | 350-524 |
| Content/weight% of particular component in first separated product | 34 |
| The distillation range of the first separated product is less than 350 ℃ component content/ |
3 |
| End point of the second separation product/. degree.C. | 324 |
| Modified result | |
| Conversion of modified feedstock/% | 94.8 |
| Yield of upgraded oil/% | 86.7 |
| Heavy metal content/weight (microgram/gram) of modified oil | <1 |
| Modified oil asphaltene content/weight% | <0.1 |
| Yield of toluene insolubles/weight% | 0.8 |
| Number of days of Stable operation | >30 days |
TABLE 7-1
TABLE 7-2
Claims (15)
1. A method for efficiently upgrading poor-quality oil comprises the following steps:
(1) performing heat treatment on inferior oil serving as a modified raw material to obtain a gas-phase product and a liquid-phase product; wherein the modified raw material comprises at least one asphalt component selected from asphaltene, asphaltene and pre-asphaltene, and the yield of toluene insoluble substances in the liquid-phase product is not more than 0.5 wt%;
(2) carrying out conversion reaction on the liquid-phase product obtained in the step (1) in a conversion reactor under the condition of hydrogen to obtain a conversion product; wherein the total conversion rate of the conversion reaction in the step (2) and the heat treatment in the step (1) is 30-70 wt%, and the total conversion rate = (the weight of the component with the distillation range above 524 ℃ in the modified raw material-the weight of the component with the distillation range above 524 ℃ in the converted product)/the weight of the component with the distillation range above 524 ℃ in the modified raw material x 100%;
(3) separating the conversion product obtained in the step (2) to obtain at least a first separated product; wherein, in the first separation product, the content of the components with the distillation range below 350 ℃ is not more than 5 weight percent, and the content of the components with the distillation range between 350 ℃ and 524 ℃ is 20-60 weight percent;
(4) extracting and separating the first separation product obtained in the step (3) in an extraction separation unit to obtain modified oil and tailings;
(5) returning the tailings obtained in the step (4) to the step (2) for the conversion reaction; or, the tailings obtained in the step (4) are thrown outwards; or returning part of the tailings obtained in the step (4) to the step (2) for the conversion reaction, and throwing the rest of the tailings outwards;
in the step (1), the heat treatment conditions include: the temperature is 350-470 ℃, and the volume space velocity is 0.05-10 hours-1；
In the step (2), the conversion reaction conditions include: the temperature is 380-470 ℃, the hydrogen partial pressure is 10-25 MPa, and the fresh feeding volume space velocity is 0.01-2 hours-1The volume ratio of the hydrogen to the fresh feed is 500-5000, and the amount of the conversion catalyst is 10-50000 micrograms/g based on the weight of the modified raw material and calculated by the metal in the conversion catalyst;
in step (4), the extraction 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-C7Hydrocarbons, said extraction solvent and saidThe weight ratio of the first separation product is (1-7): 1.
2. the upgrading process of claim 1, in step (2), the total conversion is 30-60 wt%.
3. The upgrading process of claim 1, in step (2), the conversion reactor is a fluidized bed reactor;
the conversion reaction is carried out in the presence or absence of a conversion catalyst comprising at least one selected from the group consisting of group VB metal compounds, group VIB metal compounds and group VIII metal compounds.
4. 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.
5. 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 distillation range of greater than 350 ℃, a bitumen component content of greater than 2 wt.%, and a heavy metal content of greater than 100 micrograms/gram, based on the total weight of nickel and vanadium.
6. The upgrading method as claimed in claim 1, wherein in step (3), the content of components with distillation range below 350 ℃ in the first separated product is less than 3 wt%, and the content of components with distillation range between 350 ℃ and 524 ℃ is 25-55 wt%.
7. The upgrading method according to claim 1, wherein in step (3), the separation process comprises:
(3-1) separating the conversion product obtained in the step (2) at a first pressure and a first temperature to obtain a gas component and a liquid component;
(3-2) 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.
8. The upgrading process of claim 7, wherein the first pressure is 4-24 megapascals greater than the second pressure.
9. The upgrading method of claim 7, 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 ℃.
10. The upgrading method according to claim 7, wherein the separation process further comprises:
(3-3) cutting the second separation product obtained in the step (3-2) to obtain naphtha and atmospheric gas oil; and/or
(3-4) returning the gas component obtained in the step (3-1) to the step (2) for conversion reaction.
11. The upgrading method of claim 1, in step (4), the tailings having a softening point of less than 150 ℃.
12. The upgrading method of claim 1, wherein in step (5), the proportion of tailings returned to step (2) is greater than 80% by weight.
13. The upgrading method of claim 1, wherein in step (5), a portion of tailings is thrown outward, the thrown-outward tailings comprising less than 10 wt.% of the upgrading feedstock.
14. An efficient upgrading system of inferior oil, which comprises a heat processor (2), a conversion reactor (10), a separation processing unit and an extraction separation unit (19);
the heat treatment device (2) is provided with a feed inlet, a gas-phase product outlet and a liquid-phase product outlet, the conversion reactor (10) is provided with a reaction material inlet and a conversion product outlet, the separation treatment unit is provided with a treatment raw material inlet and a first separation product outlet, and the extraction separation unit (19) is provided with an extraction solvent inlet, an extraction raw material inlet, a modified oil outlet and a tailings outlet;
the liquid-phase product outlet of the heat processor (2) is connected with the reaction material inlet of the conversion reactor (10), the conversion product outlet of the conversion reactor (10) is connected with the processing raw material inlet of the separation processing unit, the first separation product outlet of the separation processing unit is connected with the extraction raw material inlet of the extraction separation unit (19), and the tailings outlet of the extraction separation unit (19) is connected with or not connected with the reaction material inlet of the conversion reactor (10).
15. The system according to claim 14, wherein the separation process unit comprises a high pressure separation unit (12) and a low pressure separation unit (16), the high pressure separation unit (12) being provided with a gaseous component outlet, a liquid component outlet and the process feed inlet, the low pressure separation unit (16) being provided with a low pressure feed inlet, a second separation product outlet and the first separation product outlet, the liquid component outlet of the high pressure separation unit (12) being connected to the feed inlet of the low pressure separation unit (16).
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