RU2803809C1 - Method and system for processing fractionated petroleum product with a high content of aromatic compounds - Google Patents

Abstract

FIELD: hydrocarbon oil processing.

SUBSTANCE: invention is related in particular to a method for processing fractionated oil with a high content of aromatic compounds, and it includes: (1) introducing a fractionated high aromatics oil into a fifth reaction unit for hydrogenation and subsequent fractionation to obtain a first light component and a first heavy component; (2) introducing the oil-free asphalt and the aromatics-containing stream containing the first heavy component into a hydrogen dissolution unit for mixing with hydrogen, and introducing the mixed material into a first hydrogenation reaction unit, the first reaction unit being a liquid phase hydrogenation reaction unit; (3) fractionating the liquid phase product from the first reaction unit to obtain a second light component and a second heavy component; (41) introducing the second light component into the second reaction unit for the reaction; and (42) introducing the second heavy component into the delayed coker for the reaction; or using the second heavy component as a low sulphur marine diesel component. The invention is also related to a system for processing fractionated oil with a high content of aromatic compounds.

EFFECT: improved results of hydroprocessing and a long period of stable operation of the device even at low partial pressures of hydrogen, reduced ratios of hydrogen and oil products and increased volumetric velocities.

26 cl, 31 ex, 13 tbl, 2 dwg

Description

Field of the present invention

The present invention relates to the field of hydrocarbon petroleum product processing, in particular to a method and system for processing fractionated petroleum products with a high content of aromatic compounds.

BACKGROUND OF THE INVENTION

Highly efficient processing of oil residues is a major challenge for oil refineries. The main technology for highly efficient processing of petroleum residues is the hydrogenation of petroleum residues in a fixed bed, which ensures the characteristics of high quality products, technological development, etc.

However, the high content of asphaltenes and metals in the petroleum residues is a factor that limits the life of a fixed-bed petroleum residue hydrogenation plant.

To address this problem, the combined hydroprocessing and catalytic cracking (SHF) technology of petroleum residues developed by the Research Institute of Petroleum (RIPP) of SINOPEC, which incorporates solvent deasphalting (demetallization), is an innovative technology for the production of clean fuels. materials for vehicles from low-grade residues of vacuum distillation of oil with maximum yield and long service life. However, due to the high softening point of de-oiled asphaltene (DOA), transportation and disposal are difficult, limiting the spread of SHF technology.

A new process for producing high propylene content products through combined hydrogenation and deep catalytic cracking (DCC) of petroleum residues is also limited by the effects of asphaltenes and metals in the petroleum residues. Hydrogenated petroleum residues have a low hydrogen content, the petroleum residue hydrogenation plant has a short operating life, the propylene yield from DCC is low, and the economic efficiency of the combined technology is limited.

In addition, new standards for low sulfur marine fuel with a sulfur content of no more than 0.5% by weight and new standards for low sulfur petroleum coke with a sulfur content of no more than 3.0% by weight were to be implemented in 2020. . The technology to produce low sulfur marine fuel (low sulfur petroleum coke) at low cost is also a challenge that currently requires an urgent solution.

Thus, processing DOA into a material for the production of low sulfur marine fuel or for the production of low sulfur petroleum coke represents a technical problem for which a solution is required.

Brief Disclosure of the Present Invention

The purpose of the present invention is to provide a new process for processing fractionated petroleum products with high aromatic content, which provides improved hydroprocessing results and extended period of stable operation of the device even at lower partial pressures of hydrogen, reduced hydrogen-to-petroleum ratios and increased space velocities.

To achieve the above object, according to the first aspect of the present invention, there is provided a method for processing fractionated petroleum products with a high content of aromatic compounds, and this method includes:

(1) introducing the fractionated high aromatics oil into a fifth reaction unit for hydrogenation and subsequent fractionation to produce a first light component and a first heavy component, the first light component and the first heavy component having a separation temperature of 100-250° C., and the aromatic content of the first heavy component is greater than or equal to 20 wt. %;

(2) introducing the de-oiled asphalt and the aromatic-containing stream containing the first heavy component into a hydrogen dissolution unit for mixing with the hydrogen and introducing the mixed material into a first reaction unit for the hydrogenation reaction, wherein the first reaction unit contains a feed material high in mineral compounds and /or a hydrogenation catalyst, the first reaction unit is a liquid phase hydrogenation reaction unit, the high mineral content feed material is a material capable of adsorbing at least one metal selected from V, Ni, Fe, Ca and Mg, while being oil-free the asphalt and the aromatic-containing stream are used in such a quantitative ratio that the mixed feed material, which constitutes the oil-free asphalt and the aromatic-containing stream, is in a liquid state at a temperature of not more than 400° C.;

(3) fractionating the liquid phase product from the first reaction unit to obtain a second light component and a second heavy component, the separation temperature for the second light component and the second heavy component being 240-450° C.;

(41) introducing a second light component into a second reaction unit for reacting to produce at least one product selected from a gasoline component, a diesel component, and a BTX (benzene, toluene, xylene) component of the starting material, wherein the second reaction unit is at least one unit selected from the group consisting of a hydrocracking unit, a catalytic cracking unit and a diesel fuel upgrading hydroprocessing unit; And

(42) introducing a second heavy component into a delayed coker to react to produce at least one product selected from the group consisting of coker gasoline, coker diesel, coker paraffinic oil, and low sulfur petroleum coke; or the use of the second heavy component as a component of low sulfur marine diesel fuel.

According to a second aspect of the present invention, there is provided a system for processing fractionated petroleum products with a high aromatic content, the system containing:

a third reaction unit for hydrogenating and fractionating the high aromatic fractionated petroleum product to produce a first light component and a first heavy component;

a unit for dissolving hydrogen in fluid communication with the third reaction unit for mixing the oil-free asphalt contained therein and the aromatics-containing stream containing the first heavy component from the third reaction unit with hydrogen;

a first reaction unit in fluid transfer communication with a hydrogen dissolution unit, which is a liquid phase hydrogenation reaction unit, and is used for carrying out a hydrogenation reaction therein of mixed material from the hydrogen dissolution unit;

a separation unit in communication with the possibility of transferring a fluid with the first reaction unit for fractionating therein a liquid-phase product from the first reaction unit;

a second reaction unit in communication with the possibility of transferring a fluid with a separation unit for carrying out therein the reaction of a second light component obtained in the separation unit, wherein the second reaction unit is at least one unit selected from the group consisting of a hydrocracking unit, a catalytic cracking, and installation of hydroprocessing of diesel fuel with improved quality;

a delayed coking unit in communication with the possibility of transferring a fluid with a separation unit for carrying out in it the reaction of a second heavy component obtained from the separation unit to produce at least one product selected from the group consisting of gasoline from the coker unit, diesel fuel from the unit coker, paraffin oil from the coker, and low sulfur petroleum coke;

release in communication with the possibility of transferring the fluid with the separation unit to remove the second heavy component obtained from the separation unit as a fraction of low sulfur marine diesel fuel from the system.

When the high aromatic fractionated petroleum product processing method of the present invention is applied to the processing of petroleum residues, a relatively improved hydroprocessing effect and a long period of stable operation of the device can be achieved even if the method is carried out at a lower partial pressure of hydrogen, a lower hydrogen-to-oil ratio and increased volumetric speed.

The present invention is particularly suitable for the hydroprocessing of atmospheric distillation residues and vacuum distillation residues, in particular for the hydroprocessing of low-grade petroleum residues having high metal content, high carbon residue content, high condensed cyclic content and high nitrogen content.

The present invention provides a de-oiled asphalt (DOA) hydroprocessing process that efficiently processes heavy petroleum products and produces gasoline and BTX feedstocks, as well as a system and method for the flexible production of low sulfur marine fuel and low sulfur petroleum coke.

Brief description of the figures

In fig. 1 is a flow chart for processing a high aromatic fractionated petroleum product in accordance with a preferred embodiment of the present invention.

In fig. 2 shows a flow diagram for processing fractionated petroleum products with a high content of aromatic compounds in accordance with the first embodiment of the present invention.

Description of symbols

1 - Original heavy oil product

2 - Solvent deasphalting unit

3 - Deasphalted petroleum product

4 - Oil-free asphalt

5 - Aromatic compound

6 - Mixed source material

7 - First reaction plant

8 - Second light component

9 - Second heavy component

10 - Second reaction unit

11 - Delayed coking unit

12 - BTC component of the source material

13 - Gasoline component

14 - Diesel component

15 - Gasoline from coker

16 - Diesel fuel from the coker

17 - Paraffin oil from coker

18 - Low sulfur petroleum coke

19 - Separation unit

20 - Fractionated petroleum product with a high content of aromatic compounds

21 - Third reaction plant

22 - First heavy component

23 - Hydrogen dissolution unit

24- Fourth reaction unit

25 - DCC installation

26 - Propylene

27 - LCO (light recycle gas oil)

28 - HCO (heavy recycle gas oil)

29 - Suspension in petroleum product.

Detailed Disclosure of Embodiments of the Present Invention

The endpoints and any range values that are described herein are not limited to the exact ranges or values, although the stated ranges or values should be understood to cover values in the vicinity of the stated ranges or values. For numerical ranges, all ranges between corresponding endpoints and individual point values, and all individual point values, may be combined with any other values to produce one or more new numerical ranges, and such new numerical ranges should be construed as specifically described herein.

As stated above, according to the first aspect of the present invention there is provided a method for processing a fractionated petroleum product with a high aromatic content, the method comprising:

(1) introducing the fractionated high aromatics oil into a fifth reaction unit for hydrogenation and subsequent fractionation to produce a first light component and a first heavy component, the first light component and the first heavy component having a separation temperature of 100-250° C., and the aromatic content of the first heavy component is greater than or equal to 20 wt. %;

(2) introducing the de-oiled asphalt and the aromatic-containing stream containing the first heavy component into a hydrogen dissolution unit for mixing with the hydrogen and introducing the mixed material into a first reaction unit for the hydrogenation reaction, wherein the first reaction unit contains a feed material high in mineral compounds and /or a hydrogenation catalyst, the first reaction unit is a liquid phase hydrogenation reaction unit, the high mineral content feed material is a material capable of adsorbing at least one metal selected from V, Ni, Fe, Ca and Mg, while being oil-free the asphalt and the aromatic-containing stream are used in such a quantitative ratio that the mixed feed material, which constitutes the oil-free asphalt and the aromatic-containing stream, is in a liquid state at a temperature of not more than 400° C.;

(3) fractionating the liquid phase product from the first reaction unit to obtain a second light component and a second heavy component, the separation temperature for the second light component and the second heavy component being 240-450° C.;

(41) introducing a second light component into a second reaction unit to react to produce at least one product selected from a gasoline component, a diesel component, and a BTX component of the feedstock, wherein the second reaction unit is at least one selected from the group, which consists of a hydrocracking unit, a catalytic cracking unit and a diesel fuel hydroprocessing unit with quality improvement; And

(42) introducing a second heavy component into a delayed coker to react to produce at least one product selected from the group consisting of coker gasoline, coker diesel, coker paraffinic oil, and low sulfur petroleum coke; or the use of the second heavy component as a component of low sulfur marine diesel fuel.

Preferably, the oil-free asphalt and the aromatic stream are used in such a proportion that the mixed feed material that forms the oil-free asphalt and the aromatic stream is in a liquid state at a temperature of no more than 280°C. In addition, it is preferred that the oil-free asphalt and the aromatic-containing stream are used in such a ratio that the mixed feed material that forms the oil-free asphalt and the aromatic-containing stream is in a liquid state at a temperature of no more than 100°C.

Preferably, the hydrogen saturation reaction which is carried out in the third reaction unit is partial hydrogen saturation, and it is particularly preferable that the first light component and the first heavy component have a separation temperature of 180°C.

Preferably, the hydrogen dissolution plant according to the present invention operates under the following conditions: the volume ratio of the incoming amount of hydrogen and the mixed feed material, which is the oil-free asphalt and the aromatics-containing stream (namely, the volume ratio of hydrogen and petroleum product) is 30-200, preferably 50-150 , the operating temperature is 300-450°C, and the pressure is 2-20 MPa.

In the method according to the present invention, the mixed material obtained after mixing with hydrogen in the hydrogen dissolution unit may be supplied to the first reaction unit in an upflow mode or in a downflow mode. Preferably, the mixed material obtained after mixing with hydrogen in the hydrogen dissolution unit enters the first reaction unit in an upward flow mode, so as to substantially prevent the possibility that hydrogen dissolved and dispersed in the petroleum product may collect to form large bubbles and escape during the reaction. As a result, the hydrogenation reaction can be provided with a sufficient source of hydrogen, resulting in an improved processing effect by hydrogenation, further reducing the tendency of the catalyst to coke, maintaining an increased catalytic activity of the catalyst, and further increasing the service life of the catalyst, as well as increasing the period of stable operation of the device.

The first light component preferably enters a catalytic cracker to form lower olefins. The specific process conditions for supplying the first light component to the catalytic cracking unit to form lower olefins are not particularly limited according to the present invention.

Particularly preferably, the second light component and the second heavy component have a separation temperature of 350°C.

Preferably, in step (2), the oil-free asphalt and the aromatic-containing stream are used in such a ratio that the viscosity at a temperature of 100°C of the mixed feed material that the oil-free asphalt and the aromatic-containing stream form is no more than 400 mm ² /s, preferably no more than 200 mm ² /s, even more preferably no more than 100 mm ² /s.

In step (2), the aromatics-containing stream further comprises an aromatic hydrocarbon and/or an aromatic petroleum product, and the aromatic petroleum product is at least one petroleum product selected from the group consisting of LCO, HCO, FGO (fractionated gas oil), ethylene tar, coal tar, diesel fuel from the coker and paraffin oil from the coker.

Preferably, the aromatic hydrocarbon is one or more compounds, such as benzene, toluene, xylene, naphthalene, methyl naphthalene, multi-branched naphthalene, an aromatic hydrocarbon containing more than two rings, and preferably a polycyclic aromatic hydrocarbon containing no more than three rings, or a mixture of them. Particularly preferably, the aromatic hydrocarbon is at least one hydrocarbon selected from the group consisting of benzene, toluene, xylene, naphthalene, substituted naphthalene containing at least one C _1-6 alkyl group, and tricyclic or higher aromatic hydrocarbons.

Preferably, the aromatic hydrocarbon content of the high aromatic fractionated petroleum product is greater than or equal to 20 wt. %, preferably greater than or equal to 25 wt. %, preferably greater than or equal to 40 wt. % and is more preferably greater than or equal to 60 wt. %.

Preferably, in step (2), oil-free asphalt is produced by introducing a heavy oil feedstock into a solvent deasphalting process in a solvent deasphalting unit.

Preferably, in a solvent deasphalting unit, the yield of oil-free asphalt is no more than 50% by weight, more preferably no more than 40% by weight, and even more preferably no more than 30% by weight.

According to a preferred embodiment, in step (2), the aromatics-containing stream is a fractionated petroleum product with a high aromatics content, and the weight ratio of the amount of de-oiled asphalt to the amount of the aromatics-containing stream is from 1:10 to 50:10, preferably from 2: 10 to 30:10 and even preferably from 3:10 to 15:10.

Preferably, the method according to the present invention further provides for the return of the diesel fuel obtained in step (42) from the coker and/or gas oil from the coker to the first reaction unit in step (1) for saturation with hydrogen.

Preferably, in step (1), the third reaction unit is at least one reactor of a fixed bed reactor, a moving bed reactor and a fluidized bed reactor.

Preferably, the third reaction unit operates under the following conditions: the reaction temperature is 200-420°C, the reaction pressure is 2-18 MPa, the hourly liquid flow rate is 0.3-10 h ^-1 , and the volumetric ratio of hydrogen to petroleum product is 50- 5000. More preferably, the third reaction unit is operated under the following conditions: the reaction temperature is 220-400°C, the reaction pressure is 2-15 MPa, the hourly liquid flow rate is 0.3-5 h ^-1 , and the volumetric ratio of hydrogen to petroleum product is 50- 4000.

Preferred embodiments for the third reaction unit according to this fifth embodiment are presented below.

Partial hydrogenation of high aromatic fractionated petroleum product in the presence of hydrogen is generally carried out under the following conditions: Partial hydrogenation technology for high aromatic fractionated petroleum product is a fixed bed/fluidized bed/moving bed hydroprocessing technology. Considered here as an example of industrial technology for the hydrogenation of diesel fuel or paraffinic oil in a fixed bed, the reactor or reaction bed contains at least a hydrotreating catalyst. The hydrotreating catalyst used in partial hydrogenation of high aromatic fractionated petroleum products preferably exhibits high to moderate hydrogenation activity, which prevents further saturation of a tetralin type structure to a decahydronaphthalene or cycloalkane structure with less hydrogen donor capacity. For these catalysts, typically a porous, refractory inorganic oxide such as alumina or a molecular sieve is used as the support and an oxide or sulfide of a Group VIB and/or Group VIII metal such as W, Mo, Co, Ni, etc. .., finds use as an active component, and optionally other various auxiliary components are added, such as elements P, Si, F, B, etc., for example, in the composition of the RS series pre-treatment catalysts developed by the RIPP Institute. The RS series catalyst is a NiMo catalyst.

Particularly preferably, the first reaction unit is a reactor for the liquid phase hydrogenation of petroleum residues.

Preferably, in step (2), the first reaction unit is operated under the following conditions: the reaction temperature is 260-500°C, the reaction pressure is 2.0-20.0 MPa, the volume ratio of return oil product and unrefined oil product at the inlet of the first reaction unit is 0 ,1:1-15:1, and the hourly volumetric fluid flow rate is 0.1-1.5 h ^-1 . The volumetric hourly flow rate of the liquid and the reaction pressure are selected according to the nature of the materials to be processed and the desired degree of processing and purification. The mixed feed material, which is the de-oiled asphalt and the aromatics-containing stream, may enter from above into the reactor of the first reaction unit after being mixed with hydrogen, passing through the catalyst bed from top to bottom; or the catalyst enters the reactor of the first reaction unit from below, passing through the catalyst bed from bottom to top.

Preferably, in step (2), the mineral rich starting material comprises a carrier and an active element component which is supported on the carrier, the carrier being at least one selected from the group consisting of aluminum hydroxide, alumina and silica, and the active element component is at least one metal element selected from the group consisting of Group VIB and Group VIII metals. More preferably, the active component in the mineral rich starting material is an oxide and/or sulfide of a metal element selected from Group VIB and Group VIII metals.

Preferably, in step (2), the starting material with a high content of mineral compounds has a mass loss on ignition of at least 3 wt. %, the specific surface area is not less than 80 m ² /g, and the water absorption is not less than 0.9 g/g. Loss of mass on ignition means the percentage reduction in the mass of the starting material with a high content of mineral compounds as a result of heat treatment at a temperature of 600 ° C for 2 hours compared to the mass before heat treatment; and water absorption means the percentage increase in the weight of the mineral-rich starting material resulting from aging in water for half an hour at room temperature (eg, 25°C) compared to the weight before aging.

According to a preferred embodiment, in step (2), the first reaction unit is sequentially supplied, in accordance with the direction of flow of the reactants, with a first raw material with a high content of mineral compounds and a second starting material with a high content of mineral compounds, wherein the second starting material with a high content of mineral compounds mineral compounds, the weight loss on ignition is the same or greater than that of the first starting material with a high content of mineral compounds.

Moreover, according to the above-described preferred embodiment, it is preferable that the first raw material with a high content of mineral compounds has a weight loss on ignition of 3 to 15 mass. %, and the second source material with a high content of mineral compounds has a weight loss on ignition of at least 15 wt. %.

Further, according to the above-described preferred embodiment, it is preferable that the first mineral-rich raw material and the second mineral-rich raw material are introduced in a volume ratio of 5:95 to 95:5.

The hydrogenation catalyst of the present invention may be a ranged combination of various catalysts, and preferably the hydrogenation catalyst is a catalyst capable of at least catalyzing hydrodemetallization and hydrodesulfurization reactions.

According to the present invention, the specific type of catalyst that is capable of catalyzing the hydrodemetallization reaction, the hydrodesulfurization reaction, the hydrodeasphalting reaction and the hydrodecarbonization reaction is not particularly limited, and a catalyst capable of catalyzing the above reactions and conventionally used in the art can be used for these purposes.

The hydrogenation catalyst of the present invention may, for example, use a porous refractory inorganic oxide as a support, a Group VIB and/or Group VIII metal oxide or sulfide as an active component, and an auxiliary may optionally be added.

Preferably, after the first reaction plant according to the present invention is in operation for a long period of time, the high mineral content raw material is processed into a high vanadium content material, and the vanadium content of the high vanadium content material is not less than 10% by weight; Particularly preferably, the high vanadium content starting material is processed into a high vanadium content material in which the vanadium content is 20 wt. % or more, and from which the high-value V ₂ O ₅ can be isolated by direct purification.

Preferred embodiments for the first reaction plant according to the present invention are presented below.

The feedstock hydroprocessing technology which is carried out in the first reaction unit according to the present invention is a liquid phase hydroprocessing technology, wherein the reactor or reaction catalyst bed contains at least a mineral rich feedstock and/or a hydrogenation catalyst, and a high mineral content feedstock. mineral compounds mainly consist of two components: a carrier having a high adsorption capacity of vanadium-containing organic compounds present in the petroleum product, and an active component that performs the function of active hydrogenation. The carrier is obtained primarily by extruding, molding and drying silica, aluminum hydroxide or a mixture of aluminum hydroxide and alumina. The surface of the carrier has a high content of hydroxyl groups. The carrier has a high ability to adsorb vanadium-containing organic compounds present in the petroleum product. The carrier has a weight loss on ignition of at least 5 wt. % after calcination at a temperature of 600°C for 2 hours. The active component contains mainly oxides or sulfides of metals of group VIB and/or group VIII, such as W, Mo, Co, Ni, etc.

The hydrogenation catalyst present according to the above preferred embodiment is generally a heavy residue hydrogenation catalyst, and the heavy residue hydrogenation catalyst is a combination catalyst having the functions of hydrodemetallization, hydrodesulfurization, heavy residue hydrodecarbonization and the like. For these catalysts, typically a porous, refractory inorganic oxide, such as alumina, is used as a support, an oxide or sulfide of a Group VIB and/or Group VIII metal such as W, Mo, Co, Ni, and the like. , is used as an active component, and various other auxiliary components such as elements P, Si, F, B, etc., such as RDM and RCS series heavy metal catalysts, hydrodemetallization catalysts and oil residue desulfurization catalysts developed by the RIPP Institute. Currently, in the technology of liquid-phase hydrogenation of petroleum residues, many catalysts are often used together. According to the present invention, a high mineral content starting material, a hydrodemetallization and desulfurization catalyst, and a hydrodesulfurization catalyst are preferably used, which are generally introduced in such a sequence that the high mineral content starting material, the hydrodemetallization catalyst are sequentially contacted with the starting material and desulfurization and hydrodesulfurization catalyst. Of course, there are technologies for introducing these catalysts into mixtures.

According to a preferred embodiment, in step (41), the second reaction unit is a hydrocracking unit, which operates under the following conditions: the reaction temperature is 360-420°C, the reaction pressure is 10.0-18.0 MPa, the volumetric ratio of hydrogen and petroleum product is 600-2000, and the volumetric hourly flow rate of liquid is 1.0-3.0 h ^-1 .

Preferably, at least one hydroprocessing catalyst and at least one hydrocracking catalyst are introduced into the hydrocracking unit.

Preferably, the hydrocracker is a fixed bed hydrocracker.

When the second reaction unit is a hydrocracker, preferred embodiments in the second reaction unit according to the present invention are presented below.

In step (41), the second light component is introduced into the second reaction unit for reaction, using fixed bed hydrocracking technology. Taking as an example the conventional industrial fixed-bed hydrocracking technology of paraffinic oil, the reactor or reaction catalyst bed contains at least two hydrocracking catalysts, namely, a pre-treatment catalyst and a hydrocracking catalyst. Since the material resulting from liquid phase hydroprocessing followed by fractionation has a high metal, sulfur and nitrogen content and a high carbon residue, the pretreatment catalyst preferably exhibits high activity in demetallization reactions, as well as good activity in desulfurization and denitrification reactions, thus which ensures the activity of the subsequent hydrocracking catalyst. The hydrocracking catalyst preferably exhibits good hydrocracking activity and high vacuum gas oil (VGO) and hydrodesulfurization (HDS) activity. For these catalysts, typically a porous, refractory inorganic oxide, such as alumina or a molecular sieve, is used as a support, an oxide or sulfide of a Group VIB and/or Group VIII metal such as W, Mo, Co, Ni, etc. etc., finds use as an active component, and various other auxiliary components such as elements P, Si, F, B, etc. may optionally be added to catalysts such as RS series pre-treatment catalysts and RHC series hydrocracking catalysts developed by the RIPP Institute. The RS series catalyst is a NiW catalyst, and the RHC series catalyst is a molecular sieve NiMo catalyst.

According to the next preferred embodiment, in step (41), the second reaction unit is a catalytic cracking unit, and the catalytic cracking unit is a fluid catalytic cracking unit (FCC).

In a further preferred embodiment, the technology used to catalytically crack the second light component is a fluid catalytic cracking (FCC) technology, preferably a light recycle gas oil to aromatics and gasoline (LTAG) technology developed by the RIPP Institute, and thereby produces , mainly gasoline fractions and liquefied gas.

Preferably, the fluid catalytic cracking unit operates under the following conditions: the reaction temperature is 500-600° C., the catalyst to oil ratio is 3-12, and the residence time is 0.6-6 seconds.

The ratio of catalyst to petroleum product according to the present invention is the mass ratio of catalyst to petroleum product unless otherwise specified.

According to the next preferred embodiment, in step (41), the second reaction unit is a diesel fuel hydrogenation unit with upgrading, which operates under the following conditions: the reaction temperature is 330-420°C, the reaction pressure is 5.0-18.0 MPa, the volumetric ratio of hydrogen and petroleum product is 500-2000, and the volumetric hourly flow rate of liquid is 0.3-3.0 h ^-1 .

Preferably, at least one diesel fuel hydrogenation catalyst is introduced into the upgrading diesel fuel hydrogenation unit.

The diesel fuel upgrading hydrogenation catalyst may be the RS series pretreatment catalyst and the RHC-100 series diesel hydrocracking catalyst, which are developed by the RIPP Institute.

According to a preferred embodiment, in step (42), the second heavy component is introduced into the delayed coker to react to produce at least one product selected from coker gasoline, coker diesel, coker paraffinic oil, and low sulfur petroleum coke. , and the delayed coking unit operates under the following conditions: the reaction temperature is 440-520°C, and the residence time is 0.1-4 hours.

According to the next preferred embodiment, in step (42), the sulfur content of the second heavy component is not more than 1.8 wt. %, the second heavy component is introduced into the delayed coker to react to produce low sulfur petroleum coke. More preferably, the sulfur content of low-sulfur petroleum coke is not more than 3 wt. %.

Preferably, in step (42), the second heavy component is used as a low sulfur component of the marine diesel fuel, and the conditions are adjusted such that the sulfur content of the low sulfur component of the marine diesel fuel is not more than 0.5 wt. %.

According to the present invention, the specific operation of solvent deasphalting processing is not particularly limited, and a conventional solvent deasphalting process can be used. The process parameters of the solvent deasphalting process are illustrated in examples of the present invention, which should not be construed by those skilled in the art as limiting the present invention.

The method according to the present invention is suitable for the hydroprocessing of atmospheric distillation residues and vacuum distillation residues, in particular for the hydroprocessing of low-grade petroleum residues having a high metal content (Ni+V>150 µg/g, in particular Ni+V>200 µg/g ), high carbon content (mass fraction of carbon residue >17%, in particular mass fraction of carbon residue >20%) and high content of condensed cyclic compounds.

As stated above, according to the second aspect of the present invention there is provided a system for processing fractionated petroleum products with a high aromatic content, the system containing:

a third reaction unit for hydrogenating and fractionating the high aromatic fractionated petroleum product to produce a first light component and a first heavy component;

a unit for dissolving hydrogen in fluid communication with the third reaction unit for mixing the oil-free asphalt contained therein and the aromatics-containing stream containing the first heavy component from the third reaction unit with hydrogen;

a first reaction unit in fluid transfer communication with a hydrogen dissolution unit, which is a liquid phase hydrogenation reaction unit and is used for carrying out a hydrogenation reaction therein of mixed material from the hydrogen dissolution unit;

a separation unit in communication with the possibility of transferring a fluid with the first reaction unit for fractionating therein a liquid-phase product from the first reaction unit;

a second reaction unit in communication with the possibility of transferring a fluid with a separation unit for carrying out therein the reaction of a second light component obtained in the separation unit, wherein the second reaction unit is at least one unit selected from the group consisting of a hydrocracking unit, a catalytic cracking, and installation of hydroprocessing of diesel fuel with improved quality;

a delayed coking unit in communication with the possibility of transferring a fluid with a separation unit for carrying out in it the reaction of a second heavy component obtained from the separation unit to produce at least one product selected from the group consisting of gasoline from the coker unit, diesel fuel from the unit coker, paraffin oil from the coker, and low sulfur petroleum coke;

release in communication with the possibility of transferring the fluid with the separation unit to remove the second heavy component obtained from the separation unit as a fraction of low sulfur marine diesel fuel from the system.

Preferably, the delayed coker is in fluid communication with the hydrogen dissolution unit to return coker gas oil and/or coker gas oil produced in the delayed coker to the first reaction unit.

Preferably, the system further comprises a solvent deasphalting unit in fluid communication with a hydrogen dissolution unit, which is used for solvent deasphalting the heavy oil feedstock contained therein and introducing the deasphalted asphalt obtained after solvent deasphalting into the hydrogen dissolution unit. .

According to a preferred embodiment of the present invention, the second reaction unit in the system is a hydrocracking unit.

According to a further preferred embodiment of the present invention, in the system, the second reaction unit is a catalytic cracking unit, and the catalytic cracking unit is a fluid catalytic cracking unit.

According to another preferred embodiment of the present invention, the second reaction unit in the system is a diesel fuel upgrading hydroprocessing unit.

In addition, according to the present invention, a first embodiment of the method is proposed, wherein this method additionally provides:

(11) introducing the heavy crude oil into a solvent deasphalting unit for solvent deasphalting processing to produce deoiled asphalt and deasphalted petroleum product;

(12) introducing the deasphalted petroleum product into a fourth hydrogenation unit for a hydrogenation reaction, and introducing a liquid phase effluent stream obtained from the fourth hydrogenation unit into a DCC unit for reaction to produce propylene, LCO, HCO and a slurry in the petroleum product, wherein the fourth hydrogenation unit is a unit fixed bed hydrogenation;

(1) using the high aromatics fractionated petroleum product containing LCO and/or HCO from the DCC unit as the high aromatics fractionated petroleum product in step (1).

According to this first embodiment of the present invention, the method preferably further provides for returning the coker diesel fuel and/or gas oil obtained in step (42) from the coker to the third reaction unit for saturation with hydrogen.

Preferably, in step (12), the fourth reaction unit is operated under the following conditions: the reaction temperature is 280-400°C, the reaction pressure is 6.0-14.0 MPa, the volumetric ratio of hydrogen to oil is 600-1200, and the hourly flow rate liquid is 0.3-2.0 h ^-1 .

Preferably, in step (12), at least two hydrogenation catalysts are charged into the fourth reaction unit. More preferably, in step (12), the hydrogenation catalyst is a catalyst capable of catalyzing at least one reaction selected from the group consisting of a hydrodemetallization reaction, a hydrodesulfurization reaction and a hydrodecarbonization reaction. The hydrogenation catalyst is typically supported on a porous, refractory inorganic oxide such as alumina. Particularly preferably, in step (12), the hydrogenation catalyst contains alumina as a support and a metal element from Group VIB and/or Group VIII as an active element component, and optionally at least one auxiliary element selected from P, Si, F and B. In the hydrogenation catalyst, the metal elements of Group VIB and Group VIII may be, for example, W, Mo, Co, Ni, etc. In the hydrogenation catalyst, the active component may be an oxide and/or sulfide of the above-mentioned active element component.

Preferred embodiments for the fourth reaction unit according to the present invention are presented below

The conditions of the third unit for hydrogenating deasphalted petroleum oil (DAO) in the presence of hydrogen are generally defined as follows: DAO hydroprocessing technology is a fixed bed hydroprocessing technology. Taking as an example the existing industrial technology for the hydrogenation of heavy petroleum products and petroleum residues in a fixed bed, the reactor or reaction catalyst bed contains at least two hydrogenation catalysts, and the catalyst for the hydrogenation of heavy petroleum products and petroleum residues is a combined catalyst performing the functions of hydrodemetallization, hydrodesulfurization, hydrodenitrification, hydrodecarbonization, etc. in relation to both heavy petroleum products and oil residues. For these catalysts, typically a porous, refractory inorganic oxide such as alumina is used as a support, an oxide or sulfide of a Group VIB and/or Group VIII metal such as W, Mo, Co, Ni, etc. finds use as an active component, and also optionally adds various other auxiliary components, such as elements P, Si, F, B, etc., to the composition of catalysts developed by the RIPP Institute, such as the heavy metal catalysts of the RDM and RCS series , oil residue hydrodemetallization catalysts and desulfurization catalysts. Currently, in the technology of fixed-bed hydrogenation of petroleum residues, a variety of catalysts are often used together. Hydrodemetallization catalyst, hydrodesulfurization catalyst, and hydrodenitrification catalyst are generally used in a loading sequence in which a hydrodemetallization catalyst, a hydrodesulfurization catalyst, and a hydrodenitrification catalyst are contacted sequentially with the crude oil product, and sometimes one or two catalysts are missing depending on the specific situations. For example, only the hydrodemetallization catalyst and the hydrodesulfurization catalyst are loaded, but the hydrodenitrification catalyst is not loaded. Of course, there is a technology for loading these catalysts in the form of a mixture.

The method for processing a fractionated high aromatic petroleum product according to the present invention will now be described in more detail with reference to FIG. 1 and 2.

As illustrated in FIG. 1, the aromatic-rich fractionated petroleum product 20 enters the third reaction unit 21 for hydrogenation and subsequent fractionation to produce a first light component and a first heavy component 22; and the original heavy oil product 1 enters the deasphalting unit using a solvent 2 for deasphalting processing using a solvent to produce oil-free asphalt 4 and deasphalting oil product 3; the oil-free asphalt 4 and the aromatics-containing stream containing the first heavy component 22 are mixed to form a mixed feed material 6, which is mixed with hydrogen in a hydrogen dissolution unit 23, and the resulting mixed material enters the first reaction unit 7 for the hydrogenation reaction, which contains aromatics compound stream preferably also contains aromatic hydrocarbons 5 from an external source, and wherein the first reaction unit contains a feed material with a high content of mineral compounds and a hydrogenation catalyst capable of catalyzing at least one reaction selected from a hydrodemetallization reaction, a hydrodesulfurization reaction, a hydrodeasphalting reaction and a reaction hydrodecarbonization, and the first reaction unit is a liquid phase hydrogenation reaction unit; the liquid phase product from the first reaction unit 7 enters a separation unit 19 for fractionation to obtain a second light component 8 and a second heavy component 9, the second light component and the second heavy component having a separation temperature of 240-450° C.; the second light component 8 enters a second reaction unit 10 to react to produce at least one product selected from a gasoline component 13, a feedstock BTX component 12, and a diesel component 14, wherein the second reaction unit is at least one unit selected from a hydrocracking unit, a catalytic cracking unit and a diesel fuel hydrogenation unit with improved quality; and the second heavy component 9 is supplied to the delayed coker 11 for reaction to produce at least one product selected from the group consisting of gasoline from the coker 15, diesel fuel from the coker 16, paraffinic oil from the coker 17 and low sulfur petroleum coke 18; or the second heavy component 9 finds use as a low-sulfur component of marine diesel fuel.

As illustrated in FIG. 2, the original heavy oil product 1 enters the deasphalting unit using a solvent 2 for deasphalting processing using a solvent to produce oil-free asphalt 4 and deasphalting oil product 3; the deasphalted petroleum product 3 is supplied to the fourth reaction unit 24 for a hydrogenation reaction, and the liquid phase effluent obtained from the fourth reaction unit 24 is supplied to the DCC unit 25 for reaction to produce propylene 26, LCO 27, HCO 28 and a slurry in the petroleum product 29; the fractionated high aromatics petroleum product 20 containing LCO 27 and/or HCO 28 from the DCC unit enters the third reaction unit 21 for hydrogenation, followed by fractionation to produce a first heavy component 22 and a first light component; the mixed feed material 6, which is the de-oiled asphalt 4 and the aromatics-containing stream containing the first heavy component 22, enters the first reaction unit 7 for the hydrogenation reaction, and the aromatics-containing stream preferably also contains aromatic hydrocarbons 5 from an external source, wherein the first reaction unit 7 contains a raw material with a high content of mineral compounds and a hydrogenation catalyst capable of catalyzing at least one reaction selected from a hydrodemetallization reaction, a hydrodesulfurization reaction, a hydrodeasphalting reaction, and a hydrodecarbonization reaction; the liquid phase product from the first reaction unit 7 enters a separation unit 19 for fractionation to obtain a second light component 8 and a second heavy component 9; the second light component 8 enters a second reaction unit 10 to react to produce at least one product selected from the group consisting of a gasoline component 13, a BTX feedstock component 12, a diesel component 14, or a second light component 8 is returned to the DCC unit 25 ; and the second heavy component 9 is supplied to the delayed coker 11 for reaction to produce at least one product selected from the group consisting of gasoline from the coker 15, diesel fuel from the coker 16, paraffinic oil from the coker 17 and low sulfur petroleum coke 18; or the second heavy component 9 finds use as a low-sulfur component of marine diesel fuel.

The technology of the present invention provides efficient processing of heavy petroleum products and is capable of producing gasoline and BTX feedstocks, and provides a system and method for the flexible production of low sulfur marine fuel and low sulfur petroleum coke.

Compared with the prior art, the present invention preferably provides an effective combination of processes such as hydrogenation of petroleum residues, hydrocracking or catalytic cracking, such that low-grade DOA is processed into a low-sulfur marine fuel component and low-sulfur petroleum coke feedstock that satisfy environmental protection requirements. environment, and as a result, high efficiency, environmental protection and complete utilization of heavy oil resources are achieved.

In addition, the technology proposed according to the present invention can provide efficient processing of DOA in a liquid phase residue hydrogenation reactor and can produce gasoline fraction and BTX feedstock, and can also provide feedstock for the production of low sulfur marine fuel and low sulfur coke products.

Hereinafter, the present invention will be described in detail by way of examples. The following examples were implemented using the flow diagram illustrated in FIG. 1 unless otherwise stated. Unless specific conditions are indicated, these examples have the following general characteristics.

The results in Tables I-3 and II-4 in the following examples represent, unless specific conditions are specified, the average values of the results obtained from a study sampling every 25 hours during 100 hours of continuous operation of the equipment.

Saturation experiments by partial hydrogenation of the high aromatic fraction were carried out using a medium sized fixed bed diesel hydroprocessor and the total reactor volume was 200 ml. In the following examples, the hydrogenation catalyst and materials used to partially hydrogenate a high aromatic fractionated petroleum product were RIPP's RS-2100 series hydrogenation catalysts.

The liquid phase stream resulting from saturation by partial hydrogenation was fractionated to obtain a first light component and a first heavy component having a separation temperature of 180° C., the first heavy component and DOA being the mixed feedstock. The mixed feedstock was subjected to a hydrogenation reaction using a medium sized heavy petroleum liquid phase hydroprocessing apparatus with a total reactor volume of 200 ml. In the following examples, the hydrogenation catalyst and material used in the first reaction unit were RIPP RG-30B Shield Catalyst, High Mineral Feed 1, High Mineral Feed 2, Residue Demetallization and Desulfurization Transition Catalyst RDM- 33B and desulfurization catalyst RCS-31, which were developed and researched by the Petrochemical Technology Research Institute. According to the flow direction of the reactants, a protective hydrogenation catalyst, a high mineral content raw material 1, a high mineral content raw material 2, a desulfurization and hydrodemetallization catalyst, and a hydrodesulfurization catalyst were sequentially loaded. In the first reaction unit, the catalyst loading ratio was determined as follows: RG-30B: high mineral feedstock 1: high mineral feedstock 2: RDM-33B: RCS-31=6:30:30:14 :20 by volume.

The second reaction unit was a fixed bed hydrocracking unit, and the catalysts used were RS-2100 refining catalyst and RHC-131 hydrocracking catalyst developed by the RIPP Institute. The fixed bed hydrocracker was operated under the following conditions: the reaction temperature for the cleaning section was 370°C, the reaction temperature for the cracking section was 385°C, the reaction pressure was 10 MPa, the liquid hourly flow rate was 2.0 h ^-1 , and the volumetric ratio of hydrogen and petroleum product was 1200:1.

Example A

To obtain the high mineral content raw material 1, 2000 g of pseudoboehmite RPB110 manufactured by Changling Division of Sinopec Catalyst Co., Ltd. was used, of which 1000 g was treated at 550° C. for 2 hours to obtain approximately 700 g of alumina; approximately 700 g of aluminum oxide and the remaining 1000 g of pseudoboehmite were thoroughly mixed, then 40 g of sesbania powder and 20 g of citric acid were added, 2200 g of deionized water were added, and the mixture was mixed and extruded to form strips, dried at 300°C for 3 hours to obtain approximately 1730 g of carrier, to which 2100 ml of a solution containing Mo and Ni was added to soak until saturation, while the Mo content in the solution was 5.5 wt. % in terms of MoO ₃ , the Ni content was 1.5 wt. % in terms of NiO, and after impregnation for half an hour, it was treated at a temperature of 180°C for 4 hours to obtain a starting material with a high content of mineral compounds 1, and the corresponding properties are presented in Table I-6.

To obtain the high mineral content raw material 2, 2000g of pseudoboehmite RPB220 manufactured by Changling Division of Sinopec Catalyst Co., Ltd. was used, 30g of sesbania powder and 30g of citric acid were added, 2400g of deionized water was added, and the mixture was mixed and extruded , obtaining strips for molding, was dried at a temperature of 120°C for 5 hours to obtain approximately 2040 g of the carrier, to which was added 2200 ml of a solution containing Mo and Ni, for saturation, the Mo content in the solution was 7.5 wt. % in terms of MoO ₃ , the Ni content was 1.7 wt. % in terms of NiO, and after impregnation for half an hour, was processed at a temperature of 200°C for 3 hours to obtain a starting material with a high content of mineral compounds 2, and the corresponding properties are presented in Table I-6.

To obtain the high mineral content starting material 3, 2000 g of commercially available silica was used, 30 g of sesbania powder and 30 g of sodium hydroxide were added, 2400 g of deionized water was added, and the mixture was mixed and extruded to form strips, dried at 120°C for 5 hours to obtain a carrier, to which 2200 ml of a solution containing Mo and Ni was added for impregnation until saturation, while the Mo content in the solution was 4.5 wt. % in terms of MoO ₃ , the Ni content was 1.0 wt. % in terms of NiO, and after impregnation for half an hour, was processed at a temperature of 200°C for 3 hours to obtain a starting material with a high content of mineral compounds 3, and the corresponding properties are presented in Table I-6.

Example I-1

In this example, LCO produced by Shanghai Petrochemical's RLG plant was used as a high aromatic fractionated petroleum product, and LCO hydrogenation was carried out under the following conditions: reaction temperature was 290°C, reaction pressure was 4 MPa, liquid hourly flow rate was 1 h ^-1 , and the volumetric ratio of hydrogen and petroleum product was 800:1.

The properties of LCO and the first heavy component 1 are presented in Table I-1.

DOA from the vacuum distillation residues was mixed with the first heavy component 1 in a mass ratio of 1:10, and the properties of the mixed starting material are shown in Table I-2.

The mixed feedstock containing DOA and the first heavy component 1 was first mixed with hydrogen in the hydrogen dissolution unit (the volume ratio of the input amount of hydrogen and the mixed feedstock, which was deoiled asphalt and the heavy component 1, was 100, the operating temperature of the hydrogen dissolution unit was 320°C, and the pressure was 10 MPa), and the resulting mixed material entered the first reaction unit. The first reaction unit was operated under the following conditions: the reaction temperature was 360°C, the reaction pressure was 10 MPa, the liquid hourly volumetric flow rate was 0.6 h ^-1 , and the volumetric ratio of return oil to unrefined oil at the inlet of the first reaction unit was 0. 5:1. The properties of the mixed starting material after hydrogenation are presented in Table I-3.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table I-4.

The second light component was tested at a temperature of less than 350° C. in the second reaction unit to produce a hydrocracking product, the corresponding properties being presented in Table I-5.

Example I-2

In this example, HCO from the catalytic cracking device of Shanghai Petrochemical was used as a fractionated petroleum product with a high aromatic content, and the hydrogenation of HCO was carried out under the following conditions: the reaction temperature was 330°C, the reaction pressure was 6 MPa, the volumetric hourly flow rate of the liquid was 1 h ^-1 , and the volumetric ratio of hydrogen and petroleum product was 800:1.

The properties of HSO and the first heavy component 2 are presented in Table I-1.

DOA from the vacuum distillation residues was mixed with the first heavy component 2 in a mass ratio of 5:10, and the properties of the mixed starting material are shown in Table I-2.

The mixed feedstock containing DOA and hydrogenated HCO, the first heavy component 2, was first mixed with hydrogen in a hydrogen dissolution unit (the volume ratio of the incoming amount of hydrogen and the mixed feedstock, which was oil-free asphalt and the first heavy component 2, was 100, temperature The operating temperature of the hydrogen dissolution unit was 320°C and the pressure was 10 MPa), and the resulting mixed material entered the first reaction unit. The first reaction unit was operated under the following conditions: the reaction temperature was 380°C, the reaction pressure was 10 MPa, the liquid hourly volumetric flow rate was 0.6 h ^-1 , and the volumetric ratio of return oil to unrefined oil at the inlet of the first reaction unit was 0. 5:1. The properties of the mixed starting material after hydrogenation are presented in Table I-3.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table I-4.

The second light component was tested at a temperature of less than 350° C. in a second reaction unit to produce a hydrocracking product, the corresponding properties being presented in Table I-5.

Example I-3

In this example, the same LCO as in Example I-1 was used as a fractionated petroleum product with a high aromatic content, and the hydrogenation of LCO was carried out under the following conditions: reaction temperature was 320°C, reaction pressure was 6 MPa, space hourly rate the liquid supply was 1 h ^-1 , and the volumetric ratio of hydrogen and petroleum product was 800:1.

The properties of LCO and the first heavy component 3 are presented in Tables I-1.

DOA was obtained from the vacuum distillation residues and mixed with the first heavy component 3 in a mass ratio of 10:10, and the properties of the mixed starting material are shown in Table I-2.

The mixed feedstock containing DOA and the first heavy component 3 was first mixed with hydrogen in a hydrogen dissolution unit (the volume ratio of the input amount of hydrogen and the mixed feedstock, which was deoiled asphalt and the first heavy component 3, was 100, the operating temperature of the dissolution unit hydrogen was 320°C, and the pressure was 8 MPa), and the resulting mixed material entered the first reaction unit. The first reaction unit was operated under the following conditions: the reaction temperature was 370°C, the reaction pressure was 8 MPa, the liquid hourly volumetric flow rate was 0.6 h ^-1 , and the volumetric ratio of return oil to unrefined oil at the inlet of the first reaction unit was 0. 5:1. The properties of the mixed starting material after hydrogenation are presented in Table I-3.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table I-4.

The second heavy component was introduced into the coking reaction at a reaction temperature of 500°C for half an hour to obtain petroleum coke (with a yield of 32 wt.%), in which the sulfur content was 2.7 wt. %.

The second light component was tested at a temperature of less than 350° C. in a second reaction unit to produce a hydrocracking product, the corresponding properties being presented in Table I-5.

Example I-4

The high aromatic fractionated petroleum product used in Example I-4 was coal tar produced by a coal tar production plant in the People's Republic of China. Hydrogenation of coal tar was carried out under the following conditions: the reaction temperature was 300°C, the reaction pressure was 10 MPa, the volume hourly liquid flow rate was 0.8 h ^-1 , and the volumetric ratio of hydrogen to petroleum product was 800:1.

The properties of coal tar and the first heavy component 4 are shown in Table I-1.

DOA from the vacuum distillation residues was mixed with the first heavy component 4 in a mass ratio of 15:10, and the properties of the mixed starting material are shown in Table I-2.

The mixed feedstock containing DOA and the first heavy component 4 was first mixed with hydrogen in a hydrogen dissolution unit (the volume ratio of the input amount of hydrogen and the mixed feedstock, which was deoiled asphalt and the first heavy component 4, was 100, the operating temperature of the dissolution unit hydrogen was 320°C, and the pressure was 12 MPa), and the resulting mixed material entered the first reaction unit. The first reaction unit was operated under the following conditions: the reaction temperature was 350° C., the reaction pressure was 12 MPa, the liquid hourly volumetric flow rate was 0.6 h ^-1 , and the volumetric ratio of return oil to crude oil at the inlet of the first reaction unit was 2: 1. The properties of the mixed starting material after hydrogenation are presented in Table I-3.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table I-4.

The second light component was tested at a temperature of less than 350° C. in a second reaction unit to produce a hydrocracking product, the corresponding properties being presented in Table I-5.

Example I-5

A method similar to that in Example I-3 was used, except for the following conditions.

In this example, hydroprocessing in the first reaction unit was carried out at a temperature of 395°C.

Other conditions were the same as in Example I-3.

The properties of the mixed starting material after hydrogenation are presented in Table I-3.

The main physicochemical properties of the obtained second heavy component at a temperature of more than 350°C are presented in Table I-3.

Example I-6

The starting materials, catalyst contents and process conditions of the heavy petroleum liquid hydroprocessing unit in Examples I-6 were the same as in Example I-1, except for the following conditions.

After the same mixed starting material as in Example I-1 was subjected to liquid phase hydrogenation of heavy petroleum products, the reaction temperature was increased by 3° C. every 30 days, and operation was stopped after 360 days of hydrogenation research.

The high-mineral content raw material 1 and the high-mineral content raw material 2, which were initially charged into the reactor, after reaction were converted into a high-V content material 1 and a high-V content material 2, in which the V content was respectively , 76 wt. % and 71 wt. % after calcination analysis, which represented a V content more than 10 times that of natural ore, and which thus represented high-quality materials for producing high-value V ₂ O ₅ .

Example I-7

A catalytic cracking study of the second light component was carried out at a temperature of less than 350° C. from Example I-3 in a small-sized fixed-bed catalytic cracking test apparatus, the catalyst being an MLC-500 catalytic cracking catalyst manufactured by Changling Division of the company. Sinopec Catalyst Co., Ltd.; and the fluid catalytic cracking unit was operated under the following conditions: the reaction temperature was 540° C., the catalyst to oil ratio was 6, and the residence time was 2 seconds.

As a result, the gasoline product was obtained in a yield of 42 wt. %, and the research octane number (RON) of gasoline was 92.

Example I-8

The procedures were similar to those in Example I-1, except that in the present example, the resulting second heavy component was supplied to a delayed coker for reaction to produce gasoline from the coker, diesel fuel from the coker, and paraffinic oil from the coker.

The delayed coker was operated under the following conditions: the reaction temperature was 510°C and the residence time was 0.6 hours.

The diesel fuel from the coker had a sulfur content of 0.26 wt. %, a dew point of -11°C and a cetane number of 48.

The paraffin oil from the coker had a sulfur content of 1.12 wt. %, and a condensation temperature of 32°C.

Gasoline from the coker was obtained with a yield of 14.7%, the sulfur content was 0.10 wt. %, and the motor octane number (MON) was 61.8.

Diesel fuel from the coker and paraffinic oil from the coker were returned to the third reaction unit and mixed with LCO 1 for hydroprocessing, for which the reaction conditions were the same as in Example I-1.

The properties of the blended petroleum product containing coker diesel, coker paraffinic oil and LCO, and the properties of the first heavy component 8 are shown in Table I-1.

DOA from the vacuum distillation residues was mixed with the first heavy component 8 in a mass ratio of 1:10, and the properties of the mixed starting material are shown in Table I-2.

The mixed feedstock containing DOA and the first heavy component 8 was first mixed with hydrogen in a hydrogen dissolution unit (the volume ratio of the incoming amount of hydrogen and the mixed feedstock, which was deoiled asphalt and the first heavy component 8, was 100, the operating temperature of the dissolution unit hydrogen was 320°C, and the pressure was 8 MPa), and the resulting mixed material entered the first reaction unit. The first reaction unit was operated under the following conditions: the reaction temperature was 360°C, the reaction pressure was 8 MPa, the liquid hourly volumetric flow rate was 0.3 h ^-1 , and the volumetric ratio of return oil to unrefined oil at the inlet of the first reaction unit was 0. 5:1. The properties of the mixed starting material after hydrogenation are presented in Table I-3.

The liquid phase product obtained from the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table I-4.

The second light component was tested at a temperature of less than 350° C. in a second reaction unit to produce a hydrocracking product, the corresponding properties being presented in Table I-5.

Example I-9

The study was carried out on the second light component obtained from Example I-1 using a diesel fuel hydrocracking apparatus at a temperature of less than 350° C. to obtain a diesel component.

Process conditions were used in which the reaction temperature was 360° C., the reaction pressure was 10 MPa, the volumetric ratio of hydrogen to petroleum product was 1000, and the volume hourly liquid flow rate was 1.0 h ^-1 .

The resulting diesel component had a sulfur content of 5 ppm, a dew point of -32°C and a cetane number of 53.

Example I-10

The procedures were similar to those in Example I-1, except that in the present example, loading of catalysts in the first reaction unit was carried out as follows.

According to the flow direction of the reactants, a protective hydrogenation catalyst, high mineral content raw material 1, a desulfurization and hydrodemetallization catalyst, and a hydrodesulfurization catalyst were sequentially loaded. In the first reaction unit, the catalyst loading ratio was determined as follows: RG-30B: high mineral feedstock 1: RDM-33B: RCS-31=6:60:14:20 by volume.

The properties of the mixed starting material after hydrogenation are presented in Table I-3.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table I-4.

The second light component was tested at a temperature of less than 350° C. in a second reaction unit to produce a hydrocracking product, the corresponding properties being presented in Table I-5.

Example I-11

The procedures were similar to those in Example I-1, except that in the present example, loading of catalysts in the first reaction unit was carried out as follows.

According to the flow direction of the reactants, a protective hydrogenation catalyst, a high mineral content raw material 2, a high mineral content raw material 1, a desulfurization and hydrodemetallization catalyst, and a hydrodesulfurization catalyst were sequentially loaded. In the first reaction unit, the catalyst loading ratio was determined as follows: RG-30B: high mineral feedstock 2: high mineral feedstock 1: RDM-33B: RCS-31=6:30:30:14 :20 by volume.

The properties of the mixed starting material after hydrogenation are presented in Table I-3.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table I-4.

The second light component was tested at a temperature of less than 350° C. in a second reaction unit to produce a hydrocracking product, the corresponding properties being presented in Table I-5.

Example I-12

The procedures were similar to those in Example I-1, except that in the present example, loading of catalysts in the first reaction unit was carried out as follows.

According to the flow direction of the reactants, a protective hydrogenation catalyst, a desulfurization and hydrodemetallization catalyst, and a hydrodesulfurization catalyst were sequentially loaded. In the first reaction unit, the catalyst loading ratio was determined as follows: RG-30B:RDM-33B: RCS-31=15:35:50 by volume.

The properties of the mixed starting material after hydrogenation are presented in Table I-3.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table I-4.

The second light component was tested at a temperature of less than 350° C. in a second reaction unit to produce a hydrocracking product, the corresponding properties being presented in Table I-5.

Example I-13

The procedures were similar to those in Example I-1, except that in the present example, loading of catalysts in the first reaction unit was carried out as follows.

According to the flow direction of the reactants, a protective hydrogenation catalyst, a high mineral content raw material 3, a desulfurization and hydrodemetallization catalyst, and a hydrodesulfurization catalyst were sequentially loaded. In the first reaction unit, the catalyst loading ratio was determined as follows: RG-30B: high mineral feedstock 3: RDM-33B: RCS-31=10:40:20:30 by volume.

The properties of the mixed starting material after hydrogenation are presented in Table I-3.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table I-4.

The second light component was tested at a temperature of less than 350° C. in a second reaction unit to produce a hydrocracking product, the corresponding properties being presented in Table I-5.

Comparative Example I-1

The catalyst and apparatus were similar to Example I-1, except for the following conditions.

In this comparative example, high aromatic fractionated petroleum product QY (20 wt.% aromatic content) was directly mixed with DOA without passing through a partial hydrogen saturation unit. DOA and QY were mixed in a mass ratio of 1:10, and the properties of the mixed starting material are shown in Table I-2.

In the same manner as in Example I-1, the mixed raw material in this comparative example was first mixed with hydrogen in a hydrogen dissolution unit, and the resulting mixture entered the first reaction unit in which it was subjected to hydroprocessing, and the product properties are shown in the table I-3.

The liquid phase product obtained from hydroprocessing using the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table I-4.

The second light component was tested at a temperature of less than 350° C. in a fixed bed hydrocracker to produce a hydrocracker product, the corresponding properties being presented in Table I-5.

Comparative Example I-2

The catalyst and apparatus were similar to Example I-1, except for the following conditions.

In this comparative example, high aromatic fractionated petroleum product QY was directly mixed with DOA without passing through a partial hydrogen saturation unit. DOA and QY were mixed in a mass ratio of 2:10, and the properties of the mixed starting material are shown in Table I-2.

In the same manner as in Example I-1, the mixed raw material in this comparative example was first mixed with hydrogen in a hydrogen dissolution unit, and the resulting mixture entered the first reaction unit in which it was subjected to hydroprocessing, and the product properties are shown in the table I-3.

The liquid phase product obtained from hydroprocessing using the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table I-4.

The second light component was tested at a temperature of less than 350° C. in a fixed bed hydrocracker to produce a hydrocracker product, the corresponding properties being presented in Table I-5.

Comparative Example I-3

The catalyst and apparatus were similar to Example I-1, except for the following conditions.

In this comparative example, high aromatic fractionated petroleum product QY was directly mixed with DOA without passing through a partial hydrogen saturation unit. DOA and QY were mixed in a mass ratio of 3:10. Since the mixed starting material contained a large amount of solid particles (at a temperature of 100°C), it was impossible to carry out the subsequent experiment.

Example B

Solvent deasphalting was carried out using vacuum distillation residues as the starting material, the solvent was a mixture of hydrocarbons containing butane (butane content was 70 wt.%), and solvent deasphalting was carried out at a temperature of 120 ° C, while the mass the ratio of solvent to vacuum distillation residue was 3:1, resulting in DAO in a yield of 70 wt. %, and DOA with a yield of 30 wt. %.

The properties of the resulting DAO and DOA are presented in Table II-1.

Example II-1

The DAO and DOA used in this example were obtained in Example II-B.

The properties of the liquid phase product obtained from DAO introduced into the hydrogenation reaction in the fourth reaction unit are presented in Table II-1. The liquid product entered the DCC unit for reaction to produce LCOl and HCOl.

LCOl was subjected to hydrogenation in the third reaction unit, and then fractionated to obtain the first light component 1 and the first heavy component 1. Hydrogenation in the third reaction unit was carried out under the following conditions: reaction temperature was 290°C, reaction pressure was 4 MPa, space hourly rate the liquid supply was 1 h ^-1 , and the volumetric ratio of hydrogen and petroleum product was 800:1. The properties of LCOl and the first heavy component 1 are presented in Table II-2.

DOA and the first heavy component 1 were mixed in a mass ratio of 1:10, and the properties of the mixed starting material are shown in Table II-3.

DOA and the first heavy component 1 were mixed with hydrogen in a hydrogen dissolution unit to obtain a mixed material (the corresponding hydrogen content is shown in Table II-3). The first reaction unit was operated for the mixed material under the following conditions: the reaction temperature was 360° C., the reaction pressure was 10 MPa, the volumetric hourly liquid feed rate was 0.3 h ^-1 , and the volumetric ratio of return oil to crude oil at the inlet of the first reaction unit was 0.5:1. The properties of the mixed starting material after hydrogenation are presented in Table II-4.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table II-5.

The second light fraction was tested at a temperature of less than 350° C. in a second reaction unit to obtain a hydrocracking product, the corresponding properties being presented in Table II-6.

Example II-2

The DAO and DOA used in this example were obtained in Example II-B.

The properties of the liquid phase product obtained from DAO introduced into the hydrogenation reaction in the fourth reaction unit are presented in Table II-1. The liquid product entered the DCC unit for reaction to produce LCO2 and HCO2.

HCO2 was subjected to hydrogenation in the third reaction unit, and then fractionated to obtain the first light component 2 and the first heavy component 2. Hydrogenation in the third reaction unit was carried out under the following conditions: reaction temperature was 330°C, reaction pressure was 6 MPa, space hourly rate the liquid supply was 1 h ^-1 , and the volumetric ratio of hydrogen and petroleum product was 800:1. The properties of HCO2 and the first heavy component 2 are presented in Table II-2.

DOA and the first heavy component 2 were mixed in a mass ratio of 5:10, and the properties of the mixed starting material are shown in Table II-3.

DOA and the first heavy component 2 were mixed with hydrogen in a hydrogen dissolution unit to obtain a mixed material (the corresponding hydrogen content is shown in Table II-3). The first reaction unit was operated for the mixed material under the following conditions: the reaction temperature was 380° C., the reaction pressure was 8 MPa, the volumetric hourly liquid feed rate was 0.3 h ^-1 , and the volumetric ratio of return oil to crude oil at the inlet of the first reaction unit was 0.5:1. The properties of the mixed starting material after hydrogenation are presented in Table II-4.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table II-5.

The second light fraction was tested at a temperature of less than 350° C. in a second reaction unit to obtain a hydrocracking product, the corresponding properties being presented in Table II-6.

Example II-3

The DAO and DOA used in this example were obtained in Example II-B.

The properties of the liquid phase product obtained from DAO introduced into the hydrogenation reaction in the fourth reaction unit are presented in Table II-1. The liquid phase product entered the DCC unit (process conditions were the same as in Example II-1) for reaction to produce LCOl and HCOl.

LCOl was subjected to hydrogen saturation in the third reaction unit, and then fractionated to obtain the first light component 3 and the first heavy component 3. Hydrogenation in the third reaction unit was carried out under the following conditions: reaction temperature was 320°C, reaction pressure was 6 MPa, space hourly rate the liquid supply was 1 h ^-1 , and the volumetric ratio of hydrogen and petroleum product was 800:1. The properties of LCOl and the first heavy component 3 are presented in Table II-2.

DOA and the first heavy component 3 were mixed in a mass ratio of 10:10, and the properties of the mixed starting material are shown in Table II-3.

DOA and the first heavy component 3 were mixed with hydrogen in a hydrogen dissolution unit to obtain a mixed material (the corresponding hydrogen content is shown in Table II-3). The first reaction unit was operated for the mixed material under the following conditions: the reaction temperature was 370°C, the reaction pressure was 8 MPa, the volume hourly liquid feed rate was 0.3 h ^-1 , and the volumetric ratio of return oil to crude oil at the inlet of the first reaction unit was 0.5:1. The properties of the mixed starting material after hydrogenation are presented in Table II-4.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table II-5.

The second heavy component was introduced into the coking reaction at a reaction temperature of 500°C for half an hour to obtain petroleum coke (with a yield of 31 wt.%), in which the sulfur content was 2.7 wt. %.

The second light fraction was tested at a temperature of less than 350° C. in a second reaction unit to obtain a hydrocracking product, the corresponding properties being presented in Table II-6.

Example II-4

The DAO and DOA used in this example were obtained in Example II-B.

The properties of the liquid phase product obtained from DAO introduced into the hydrogenation reaction in the fourth reaction unit are presented in Table II-1. The liquid phase product entered the DCC unit (process conditions were the same as in Example II-1) for reaction to produce LCOl and HCOl.

The high aromatic fractionated petroleum product used in the example was coal tar (properties shown in Table II-1) from China coal tar production and LCOl. LCOl and coal tar were used in a mass ratio of 1:1. The fractionated petroleum product with a high content of aromatic compounds was subjected to saturation with hydrogen in the third reaction unit, and then fractionated to obtain the first light component 4 and the first heavy component 4. Hydrogenation in the third reaction unit was carried out under the following conditions: the reaction temperature was 300°C, the reaction pressure was 10 MPa, the liquid hourly flow rate was 0.8 h ^-1 , and the hydrogen to oil volumetric ratio was 800:1. The properties of the fractionated high aromatic petroleum product and the first heavy component 4 are presented in Table II-2.

DOA and the first heavy component 4 were mixed in a mass ratio of 15:10, and the properties of the mixed starting material are shown in Table II-3.

DOA and the first heavy component 4 were mixed with hydrogen in a hydrogen dissolution unit to obtain a mixed material (the corresponding hydrogen content is shown in Table II-3). The first reaction unit was operated for the mixed material under the following conditions: the reaction temperature was 350° C., the reaction pressure was 12 MPa, the volume hourly liquid feed rate was 0.3 h ^-1 , and the volumetric ratio of return oil to crude oil at the inlet of the first reaction unit was 0.5:1. The properties of the mixed starting material after hydrogenation are presented in Table II-4.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table II-5.

The second light fraction was tested at a temperature of less than 350° C. in a second reaction unit to obtain a hydrocracking product, the corresponding properties being presented in Table II-6.

Example II-5

A method similar to that in Example II-3 was used, except for the following conditions.

In this example, hydroprocessing in the first reaction unit was carried out at a temperature of 395°C.

Other conditions were the same as in Example II-3.

The properties of the mixed starting material after hydrogenation are presented in Table II-4.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table II-5.

Example II-6

The catalyst loading and hydroprocessing conditions were the same as in Example II-4.

After the same mixed starting material as in Example II-4 was subjected to hydroprocessing in the first reaction unit, the reaction temperature was increased by 3° C. every 30 days, and operation was stopped after 360 days of hydrogenation research.

The high-mineral content raw material 1 and the high-mineral content raw material 2, which were initially charged into the reactor, after reaction were converted into a high-V content material 1 and a high-V content material 2, in which the V content was respectively , 69 wt. % and 60 wt. % after analysis by calcination, and which thus represented high-quality materials for the production of high-value V ₂ O ₅ .

Example II-7

A catalytic cracking test of the second light component at a temperature of less than 350° C. from Example II-3 was carried out in a small-sized fixed-bed catalytic cracking test apparatus, the catalyst being an MLC-500 catalytic cracking catalyst manufactured by Changling Department. Sinopec Catalyst Co., Ltd.; and the fluid catalytic cracking unit was operated under the following conditions: the reaction temperature was 540° C., the catalyst to oil ratio was 6, and the residence time was 3 seconds.

As a result, the gasoline product was obtained in a yield of 40 wt. %, and the research octane number (RON) of the gasoline was 93. Example II-8

The procedures were similar to those in Example II-1, except that in the present example, the resulting second heavy component was supplied to a delayed coker for reaction to produce gasoline from the coker, diesel fuel from the coker, and paraffinic oil from the coker.

The delayed coker was operated under the following conditions: the reaction temperature was 510°C and the residence time was 0.6 hours.

The diesel fuel from the coker had a sulfur content of 0.26 wt. %, a dew point of -11°C and a cetane number of 48.

The paraffin oil from the coker had a sulfur content of 1.12 wt. %, and a condensation temperature of 32°C.

Gasoline from the coker was obtained in a yield of 14.7%, with a sulfur content of 0.10 wt. %, and the motor octane number (MON) was 61.8.

Diesel fuel from the coker and paraffinic oil from the coker were returned to the third reaction unit and mixed with LCO 1 for hydrogenation, and then fractionated to obtain the first light component 8 and the first heavy component 8 with a separation temperature of 180° C. and at In this case, the reaction conditions were the same as in example II-1. The properties of the mixed petroleum product containing coker diesel, coker paraffinic oil and LCOl, and the properties of the first heavy component 8 are shown in Table II-2.

The DOA of Example II-B and the first heavy component 8 were mixed in a mass ratio of 1:10, and the properties of the mixed starting material are shown in Table II-3.

DOA and the first heavy component 8 were mixed with hydrogen in a hydrogen dissolution unit to obtain a mixed material (the corresponding hydrogen content is shown in Table II-3). The first reaction unit was operated under the following conditions: the reaction temperature was 360° C., the reaction pressure was 8 MPa, the liquid hourly flow rate was 0.3 h ^-1 , and the hydrogen to oil volume ratio was 800:1. The properties of the mixed starting material after hydrogenation are presented in Table II-4.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table II-5.

The second light fraction was tested at a temperature of less than 350° C. in a second reaction unit to obtain a hydrocracking product, the corresponding properties being presented in Table II-6.

Example II-9

The study was carried out on the second light component obtained in Example II1 at a temperature of less than 350°C using a diesel fuel hydroprocessing device to improve the quality and obtain a diesel component.

The diesel fuel upgrading hydroprocessing apparatus was operated under the following conditions: the reaction temperature was 360° C., the reaction pressure was 12 MPa, the volumetric ratio of hydrogen to petroleum product was 1000, and the volume hourly liquid flow rate was 1.0 h ^-1 .

The resulting diesel component had a sulfur content of 5 ppm, a dew point of -33°C and a cetane number of 53.

Example II-10

The procedures were similar to those in Example II-1, except that in the present example, loading of catalysts in the first reaction unit was carried out as follows.

According to the flow direction of the reactants, a protective hydrogenation catalyst, high mineral content raw material 1, a desulfurization and hydrodemetallization catalyst, and a hydrodesulfurization catalyst were sequentially loaded. In the first reaction unit, the catalyst loading ratio was determined as follows: RG-30B: high mineral feedstock 1: RDM-33B: RCS-31=6:60:14:20 by volume.

The properties of the mixed starting material after hydrogenation are presented in Table II-4.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table II-5.

The second light fraction was tested at a temperature of less than 350° C. in a second reaction unit to obtain a hydrocracking product, the corresponding properties being presented in Table II-6.

Example II-11

The procedures were similar to those in Example II-1, except that in the present example, loading of catalysts in the first reaction unit was carried out as follows.

According to the flow direction of the reactants, a protective hydrogenation catalyst, a high mineral content raw material 2, a high mineral content raw material 1, a desulfurization and hydrodemetallization catalyst, and a hydrodesulfurization catalyst were sequentially loaded. In the first reaction unit, the catalyst loading ratio was determined as follows: RG-30B: high mineral feedstock 2: high mineral feedstock 1: RDM-33B: RCS-31=6:30:30:14 :20 by volume.

The properties of the mixed starting material after hydrogenation are presented in Table II-4.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table II-5.

The second light fraction was tested at a temperature of less than 350° C. in a second reaction unit to obtain a hydrocracking product, the corresponding properties being presented in Table II-6.

Example II-12

The procedures were similar to those in Example II-1, except that in the present example, loading of catalysts in the first reaction unit was carried out as follows.

According to the flow direction of the reactants, a protective hydrogenation catalyst, a desulfurization and hydrodemetallization catalyst, and a hydrodesulfurization catalyst were sequentially loaded. The catalyst loading ratio was determined as follows: RG-30B: RDM-33B: RCS-31=15:40:45 by volume.

The properties of the mixed starting material after hydrogenation are presented in Table II-4.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table II-5.

The second light fraction was tested at a temperature of less than 350° C. in a second reaction unit to obtain a hydrocracking product, the corresponding properties being presented in Table II-6.

Example II-13

The procedures were similar to those in Example II-1, except that in the present example, loading of catalysts in the first reaction unit was carried out as follows.

According to the flow direction of the reactants, a protective hydrogenation catalyst, a high mineral content raw material 3, a desulfurization and hydrodemetallization catalyst, and a hydrodesulfurization catalyst were sequentially loaded. The catalyst loading ratio was determined as follows: RG-30B: high mineral feedstock 3: RDM-33B: RCS-31=10:40:25:35 by volume.

The properties of the mixed starting material after hydrogenation are presented in Table II-4.

The liquid phase product resulting from processing in the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table II-5.

The second light fraction was tested at a temperature of less than 350° C. in a second reaction unit to obtain a hydrocracking product, the corresponding properties being presented in Table II-6.

Comparative Example II-1

The catalyst and device were similar to example II-1, except for the following conditions.

In a comparative example, high aromatic fractionated petroleum product QY (20 wt.% aromatic content) was directly mixed with DOA without passing through a partial hydrogen saturation unit. DOA and QY were mixed in a mass ratio of 1:10, and the properties of the mixed starting material are shown in Table II-3.

The mixed material was mixed with hydrogen in a hydrogen dissolution unit, and the resulting mixed material (the corresponding hydrogen content is shown in Table II-3) was hydroprocessed using the first reaction unit, and the properties of the corresponding product are shown in Table II-4.

The liquid phase product obtained by hydroprocessing using the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table II-5.

The second light fraction was tested at a temperature of less than 350° C. in a second reaction unit to obtain a hydrocracking product, the corresponding properties being presented in Table II-6.

Comparative Example II-2

The catalyst and device were similar to example II-1, except for the following conditions.

In a comparative example, high aromatic fractionated petroleum product QY was directly mixed with DOA without passing through a partial hydrogen saturation unit. DOA and QY were mixed in a mass ratio of 2:10, and the properties of the mixed starting material are shown in Table II-3.

The mixed material was mixed with hydrogen in a hydrogen dissolution unit, and the resulting mixed material (the corresponding hydrogen content is shown in Table II-3) was hydroprocessed using the first reaction unit, and the properties of the corresponding product are shown in Table II-4.

The liquid phase product obtained by hydroprocessing using the first reaction unit was fractionated, and the properties of the second heavy component at a temperature greater than or equal to 350° C. are presented in Table II-5.

The second light fraction was tested at a temperature of less than 350° C. in a second reaction unit to obtain a hydrocracking product, the corresponding properties being presented in Table II-6.

Comparative Example II-3

The catalyst and device were similar to example II-1, except for the following conditions.

In Comparative Example II-3, high aromatic fractionated petroleum product QY was directly mixed with DOA without passing through a partial hydrogen saturation unit. DOA and QY were mixed in a mass ratio of 3:10. Since the mixed starting material contained a large amount of solid particles (at a temperature of 100°C), it was impossible to carry out the subsequent experiment.

Based on the results presented above, it can be seen that the technology according to the present invention provides high quality starting materials for the production of low sulfur marine fuel or low sulfur coke products from DOA.

In addition, the technology according to the present invention can provide high quality gasoline products that meet government V standards.

Preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to them. Within the scope of the technical idea of the present invention, numerous simple modifications of the technical solution of the present invention can be made, including various technical features can be combined in any other suitable ways, and these simple modifications and combinations should also be considered as the disclosure of the present invention, all of them are within the scope of the present invention.

Claims (58)

1. A method for processing fractionated petroleum products with a high content of aromatic compounds, characterized in that it contains: (1) introducing the aromatic-rich fractionated petroleum product into a third reaction unit for hydrogenation and subsequent fractionation to produce a first light component and a first heavy component, the first heavy component being used as the first heavy component that is present in the aromatics-containing stream at stages (2); (2) introducing the oil-free asphalt and the aromatic-containing stream containing the first heavy component into a hydrogen dissolution unit for mixing with hydrogen and introducing the mixed material into a first reaction unit for the hydrogenation reaction, wherein the oil-free asphalt and the aromatic-containing stream are used in such quantitative the relationship that the mixed feed material, which constitutes the oil-free asphalt and the aromatic-containing stream, is in a liquid state at a temperature of not more than 400°C; (3) fractionating the liquid phase product from the first reaction unit to obtain a second light component and a second heavy component, the separation temperature for the second light component and the second heavy component being 240-450° C.; (41) introducing a second light component into a second reaction unit for reacting to produce at least one product selected from a gasoline component, a diesel component, and a BTX (benzene, toluene, xylene) component of the feedstock, wherein the second reaction unit is at least one unit selected from the group consisting of a hydrocracking unit, a catalytic cracking unit and a diesel fuel upgrading hydroprocessing unit; And (42) introducing a second heavy component into a delayed coker to react to produce at least one product selected from the group consisting of coker gasoline, coker diesel, coker paraffinic oil, and low sulfur petroleum coke; or the use of the second heavy component as a component of low sulfur marine diesel fuel. 2. The method according to claim 1, wherein in step (1), the first light component and the first heavy component have a separation temperature of 100-250°C, and the aromatic content of the first heavy component is more than or equal to 20 wt.% . 3. The method according to claim 1, wherein in step (2) the first reaction unit contains a starting material with a high content of mineral compounds and/or a hydrogenation catalyst, the first reaction unit is a liquid phase hydrogenation reaction unit, a starting material with a high content of mineral compounds is a material capable of adsorbing at least one metal selected from V, Ni, Fe, Ca and Mg. 4. The method according to claim 1, wherein in step (2), the oil-free asphalt and the aromatic-containing stream are used in such a ratio that the viscosity at a temperature of 100°C of the mixed feed material that forms the oil-free asphalt and the aromatic-containing stream is no more than 400 mm ² /s, more preferably no more than 200 mm ² /s and even more preferably no more than 100 mm ² /s. 5. The method according to claim 1, wherein in step (2) the aromatics-containing stream further contains an aromatic hydrocarbon and/or an aromatic petroleum product, and the aromatic petroleum product is at least one petroleum product selected from the group consisting of LCO (light recycle gas oil), HCO (heavy recycle gas oil), FGO (fractionated gas oil), ethylene tar, coal tar, coker diesel and coker paraffinic oil; preferably the aromatic hydrocarbon is at least one hydrocarbon selected from the group consisting of benzene, toluene, xylene, naphthalene, substituted naphthalene containing at least one C _1-6 alkyl group, and tricyclic or higher aromatic hydrocarbons. 6. The method of claim 1, wherein the aromatic hydrocarbon content of the high aromatic fractionated petroleum product is greater than or equal to 20% by weight, preferably is greater than or equal to 25% by weight, and more preferably is greater than or equal to 40% by weight .%. 7. The method according to claim 1, wherein in step (2), oil-free asphalt is obtained by introducing a heavy oil product into a solvent deasphalting process in a solvent deasphalting unit; preferably, in a solvent deasphalting unit, the yield of oil-free asphalt is no more than 50% by weight, more preferably no more than 40% by weight, and even more preferably no more than 30% by weight. 8. The method according to claim 1, wherein in step (2) the aromatics-containing stream is a fractionated petroleum product with a high content of aromatics, and the mass ratio of the amount of de-oiled asphalt to the amount of the aromatics-containing stream is from 1:10 to 50:10 , preferably from 2:10 to 30:10 and even more preferably from 3:10 to 15:10. 9. The method according to claim 1, which additionally includes: returning diesel fuel from the coker and/or gas oil from the coker obtained in step (42) to the first reaction unit in step (1) for saturation with hydrogen. 10. The method according to claim 1, wherein in step (1), the third reaction unit is at least one reactor of a fixed bed reactor, a moving bed reactor and a fluidized bed reactor; preferably, the third reaction unit is operated under the following conditions: the reaction temperature is 200-420°C, the reaction pressure is 2-18 MPa, the hourly liquid flow rate is 0.3-10 h ^-1 , and the volumetric ratio of hydrogen to petroleum product is 50- 5000; preferably, the third reaction unit is operated under the following conditions: the reaction temperature is 220-400°C, the reaction pressure is 2-15 MPa, the hourly liquid flow rate is 0.3-5 h ^-1 , and the volumetric ratio of hydrogen to petroleum product is 50- 40000. 11. The method according to claim 1, in which at stage (2) the first reaction unit operates under the following conditions: the reaction temperature is 260-500°C, the reaction pressure is 2.0-20.0 MPa, the volume ratio of the returned oil product and unprocessed the oil product at the inlet of the first reaction unit is 0.1:1-15:1, and the hourly liquid flow rate is 0.1-1.5 h ^-1 . 12. The method according to claim 3, in which at stage (2) the starting material with a high content of mineral compounds has a mass loss on ignition of not less than 3 wt.%, a specific surface area of not less than 80 m ² /g, and water absorption is not less than 0.9 g/g. 13. The method according to claim 12, wherein in step (2) the high mineral content starting material comprises a carrier and an active element component which is supported on the carrier, wherein the carrier is at least one material selected from the group consisting of aluminum hydroxide, aluminum oxide and silicon dioxide, and wherein the active element component is at least one metal element selected from the group consisting of Group VIB and Group VIII metals. 14. The method according to claim 13, in which in step (2), according to the direction of flow of the reactants, a first starting material with a high content of mineral compounds and a second starting material with a high content of mineral compounds are sequentially introduced into the first reaction unit, and at the same time, the second starting material of a material with a high content of mineral compounds, the weight loss on ignition is the same or more than that of the first starting material with a high content of mineral compounds; preferably the first high mineral content starting material has a loss on ignition of 3-15% by weight, and the second high mineral content starting material has a loss on ignition of at least 15% by weight; preferably, the first mineral-rich starting material and the second mineral-rich starting material are added in a volume ratio of 5:95 to 95:5. 15. The method according to claim 1, in which at stage (41), the second reaction unit is a hydrocracking unit, which operates under the following conditions: the reaction temperature is 360-420°C, the reaction pressure is 10.0-18.0 MPa , the volumetric ratio of hydrogen and petroleum product is 600-2000, and the volumetric hourly flow rate of liquid is 1.0-3.0 h ^-1 ; Preferably, at least one hydroprocessing catalyst and at least one hydrocracking catalyst are introduced into the hydrocracking unit. 16. The method according to claim 1, wherein in step (41), the second reaction unit is a catalytic cracking unit, and the catalytic cracking unit is a fluid catalytic cracking unit; Preferably, the fluid catalytic cracking unit is operated under the following conditions: reaction temperature is 500-600°C, catalyst to oil ratio is 3-12, and residence time is 0.6-6 seconds. 17. The method according to claim 1, in which at stage (41) the second reaction unit is a diesel fuel hydrogenation unit with upgrading, which operates under the following conditions: the reaction temperature is 330-420°C, the reaction pressure is 5.0- 18.0 MPa, the volumetric ratio of hydrogen and petroleum product is 500-2000, and the volumetric hourly flow rate of liquid is 0.3-3.0 h ^-1 ; Preferably, at least one diesel fuel hydrogenation catalyst is introduced into the upgrading diesel fuel hydrogenation unit. 18. The method according to claim 1, wherein in step (42) the second heavy component is introduced into the delayed coker to react to produce at least one product selected from gasoline from the coker, diesel fuel from the coker, paraffin oil from the coker coking and low-sulfur petroleum coke, and the delayed coking unit operates under the following conditions: the reaction temperature is 440-520°C, and the residence time is 0.1-4 hours; preferably, in step (42), the sulfur content of the second heavy component is not more than 1.8 mass%, the second heavy component is introduced into a delayed coker to react to produce low sulfur petroleum coke; More preferably, the sulfur content of the low sulfur petroleum coke is no more than 3 wt%. 19. The method according to claim 1, wherein in step (42) the second heavy component is used as a low sulfur component of marine diesel fuel, and the conditions are adjusted so that the sulfur content of the low sulfur component of marine diesel fuel is not more than 0.5 wt. .%. 20. The method according to claim 2, which additionally provides: (11) introducing the heavy crude oil into a solvent deasphalting unit for solvent deasphalting processing to produce deoiled asphalt and deasphalted petroleum product; (12) introducing the deasphalted petroleum product into a fourth reaction unit for a hydrogenation reaction and introducing the liquid phase effluent stream obtained from the fourth reaction unit into a deep catalytic cracking (DCC) unit for reacting to produce propylene, LCO, HCO and a slurry in the petroleum product, the fourth reaction unit The plant is a fixed bed reaction plant; And using the high aromatics fractionated petroleum product containing LCO and/or HCO from the DCC unit as the high aromatics fractionated petroleum product in step (1). 21. The method according to claim 20, which further comprises: returning diesel fuel from the coker and/or gas oil from the coker obtained in step (42) to the third reaction unit for saturation with hydrogen. 22. The method according to claim 20, in which at stage (12), the fourth reaction unit operates under the following conditions: the reaction temperature is 280-400°C, the reaction pressure is 6.0-14.0 MPa, the volume ratio of hydrogen and oil product is 600-1200, and the hourly volumetric fluid flow rate is 0.3-2.0 h ^-1 ; preferably, in step (12), at least two hydrogenation catalysts are introduced into the fourth reaction unit; preferably, in step (12), the hydrogenation catalyst is a catalyst capable of catalyzing at least one reaction selected from the group consisting of a hydrodemetallization reaction, a hydrodesulfurization reaction and a hydrodecarbonization reaction; And preferably in step (12) the hydrogenation catalyst contains alumina as a support and a metal element from Group VIB and/or Group VIII as an active element component, and optionally at least one auxiliary element selected from P, Si, F and B . 23. A system for processing fractionated petroleum products with a high content of aromatic compounds, which contains: a third reaction unit for hydrogenating and fractionating the high aromatic fractionated petroleum product to produce a first light component and a first heavy component; a unit for dissolving hydrogen in fluid communication with the third reaction unit for mixing the oil-free asphalt contained therein and the aromatics-containing stream containing the first heavy component from the third reaction unit with hydrogen; a first reaction unit in fluid transfer communication with a hydrogen dissolution unit, which is a liquid phase hydrogenation reaction unit and is used for carrying out a hydrogenation reaction therein of mixed material from the hydrogen dissolution unit; a separation unit in communication with the possibility of transferring a fluid with the first reaction unit for fractionating therein a liquid-phase product from the first reaction unit; a second reaction unit in fluid communication with the separation unit for reacting therein a second light fraction obtained in the separation unit, wherein the second reaction unit is at least one unit selected from the group consisting of a hydrocracking unit, a catalytic cracking unit and a diesel fuel hydroprocessing plant with improved quality; a delayed coker in communication with the possibility of transferring a fluid with a separation unit for reacting therein a second heavy component obtained from the separation unit to produce at least one product selected from the group consisting of gasoline from a coker, diesel fuel from a coker , paraffin oil from the coker, and low sulfur petroleum coke; And release in communication with the possibility of transferring the fluid with the separation unit to remove the second heavy fraction obtained from the separation unit as a fraction of low sulfur marine diesel fuel from the system. 24. The system of claim 23, wherein the delayed coker is in fluid communication with a hydrogen dissolution unit to return coker gas oil and/or coker gas oil produced in the delayed coker to the first reaction unit. 25. The system according to claim 23, additionally containing a deasphalting unit using a solvent in communication with the possibility of transferring a fluid with a hydrogen dissolution unit, which is used for deasphalting using a solvent of the original heavy oil product contained in it and introducing deasphalting asphalt obtained after deasphalting with using a solvent in a hydrogen dissolution unit. 26. The system according to clause 23, which additionally provides: a solvent deasphalting unit used to carry out deasphalting processing of heavy crude oil using a solvent to produce oil-free asphalt and deasphalting petroleum product; a fourth reaction unit in fluid communication with a solvent deasphalting unit, the fourth reaction unit being a fixed bed reaction unit for carrying out a hydrogenation reaction of deasphalted petroleum product from the solvent deasphalting unit; installing a DCC in fluid communication with a fourth reaction unit to react therein a liquid-phase effluent stream obtained from the fourth reaction unit to produce propylene, LCO, HCO and a slurry in a petroleum product; wherein the DCC unit is in fluid communication with a third reaction unit for moving the high aromatics fractionated petroleum product containing LCO and/or HCO from the DCC unit to the third reaction unit for use as the high aromatics fractionated petroleum product connections.