CN110540877A

CN110540877A - sectional type heavy oil suspension bed hydrogenation thermal cracking reaction separation method

Info

Publication number: CN110540877A
Application number: CN201810567942.6A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Luoyang Ruihua New Energy Technology Development Co ltd
Priority date: 2018-05-29
Filing date: 2018-05-29
Publication date: 2019-12-06

Abstract

A sectional type heavy oil suspension bed hydro-thermal cracking reaction separation method, a reaction product obtained by a heavy oil UR10F mainly composed of hydrocarbons with a conventional boiling point higher than 530 ℃ in a first reaction section of a first reaction separation section is separated into a first separation section discharge heavy oil containing a residual oil component and catalyst solid particles in a first separation section US10, and a reaction product obtained by the first separation section discharge heavy oil in a second reaction section of a second reaction separation section is separated into a second separation section residual oil US20-VR containing a residual oil component and catalyst solid particles in a second separation section US 20; US20-VR may be used partly as export heavy oil from the second separation section and partly as long cycle heavy oil entering the first reaction section; compared with a single-stage process, most of residual oil in the discharged heavy oil of the first separation section can be lightened into distillate oil, the consumption of a fresh catalyst can be obviously reduced, the residual oil with higher metal content or higher carbon residue content can be processed, and various combined processes can be formed.

Description

sectional type heavy oil suspension bed hydrogenation thermal cracking reaction separation method

Technical Field

the invention relates to a sectional type heavy oil suspension bed hydro-thermal cracking reaction separation method, wherein a reaction product obtained by a heavy oil UR10F mainly comprising hydrocarbons with a conventional boiling point higher than 530 ℃ in a first reaction section of a first reaction separation section is separated into a first separation section discharged heavy oil containing a residual oil component and catalyst solid particles in a first separation section US10, and a reaction product obtained by the first separation section discharged heavy oil in a second reaction section of a second reaction separation section is separated into a second separation section residual oil US20-VR containing a residual oil component and catalyst solid particles in a second separation section US 20; US20-VR may be used partly as export heavy oil from the second separation section and partly as long cycle heavy oil entering the first reaction section; compared with a single-stage process, most of residual oil in the discharged heavy oil of the first separation section can be lightened into distillate oil, the consumption of a fresh catalyst can be obviously reduced, the residual oil with higher metal content or higher carbon residue content can be processed, and various combined processes can be formed.

background

The heavy oil UR10F of the present invention is typically a vacuum residue consisting essentially of hydrocarbons with conventional boiling points above 530 ℃.

in the suspension hydrogenation thermal cracking reaction process of the heavy oil UR10F, a suspension hydrogenation reactor is used for carrying out thermal cracking reaction and hydrogenation stabilization reaction of thermal cracking free radicals of at least a part of residual oil components (hydrocarbons with conventional boiling points higher than 530 ℃) in the heavy oil UR10F to generate at least a part of hydrocarbon products (gasifiable and distillable components) with lower boiling points; in the process of the suspension bed hydrocracking reaction of the heavy oil UR10F, a hydrofining reaction of hydrocarbon components (olefin hydrogenation saturation reaction, aromatic hydrocarbon hydrogenation saturation reaction), a heteroatom hydrogenolysis reaction, an organic metal hydrogenolysis reaction, and a thermal condensation reaction of hydrocarbon or hydrocarbon pyrolysis radicals also occur in general; the thermal condensation reaction may produce coke or coke precursors.

the reaction separation section of the present invention refers to a process comprising a raw heavy oil hydrocracking reaction process (or referred to as a reaction section) and a separation process (or referred to as a separation section) of heavy oil hydrocarbon components and lower boiling point hydrocarbon components in a hydrocracking reaction product; the process for separating the heavy oil hydrocarbon component from the lower boiling point hydrocarbon component may be a process for separating the residual oil from the wax oil component (usually including a vacuum fractionation process), a process for separating the heavy wax oil component from the light wax oil component (usually including a vacuum fractionation process), or a process for separating the diesel oil from the wax oil component (which may or may not include a vacuum fractionation process).

the reaction separation process of the present invention comprises a first hydrocracking reaction process of raw heavy oil and a first separation process of heavy oil hydrocarbon components and lower boiling point hydrocarbon components of a first hydrocracking reaction product, and the process can comprise a recycling process of recycling unconverted residual oil or modified oil thereof discharged from the first separation process (generally comprising a vacuum fractionation process) back to the first hydrocracking reaction process for recycling hydrocracking.

The existing suspension bed hydrocracking reaction separation methods of heavy oil or residual oil belong to a reaction separation process, wherein the residual oil suspension bed hydrocracking reaction separation method with industrial operation performance comprises a Canadian CANMET residual oil suspension bed hydrocracking process (which is later integrated into the Uniflex technology of UOP company in the United states) and an EST residual oil suspension bed hydrocracking process of Italy Eny company. Other residual oil suspension bed hydrocracking reaction separation methods include BPVCC technology of British oil company, HDHPLUS technology of Venezuela national oil company (PDVSA), VRSH technology of Chevron in the United states and the like.

If a thermal cracking system of the circulating heavy oil containing solid particles and unconverted residual oil components is arranged, in a first reaction section, in order to prevent the circulating residual oil which is carried by raw oil and is difficult to thermally crack, thermal condensation coke or coke precursors from being excessively accumulated to form high-concentration asphaltene to deteriorate the liquid phase property of the first reaction section (increase the carbon residue value, increase the viscosity value and reduce the average hydrogen content), in order to prevent sulfide solids, other ashes, catalyst solid particles and other solids generated by metals carried by the raw oil from being excessively accumulated to form high-concentration solid-containing circulating residual oil, a certain ratio of vacuum residue discharged by the first separation section is required to be discharged; compared with the fresh residual oil UR10F, the discharged vacuum residual oil of the first separation section has higher solid particle carrying rate, higher asphaltene concentration and more difficult hydrocracking cracking of the asphaltene.

the residual oil suspension bed hydrogenation thermal cracking reaction separation method only provided with one reaction separation process and a solid particle-containing unconverted residual oil circulating thermal cracking system comprises an EST residual oil suspension bed hydrogenation thermal cracking process of Italy Eny company.

in the EST residual oil suspension bed hydrogenation thermal cracking process, the vacuum residual oil is subjected to hydrocracking in a suspension bed reactor under the existence of a molybdenum-based catalyst and mild operating conditions (the temperature is about 400-425 ℃, and the pressure is about 15-17 MPa), and the vacuum residual oil is converted into a light product. The converted oil enters a separation system to recover gas, naphtha, middle distillate oil and wax oil, a hydrogen-containing gas phase product enters an amine washing part after a light product is separated, clean hydrogen-containing gas is recycled to the reaction process after being compressed again and supplemented with hydrogen, and the distillate oil is recovered from a liquid phase. In the EST residual oil suspension bed hydrogenation thermal cracking process, an oil-soluble matrix is used to be converted into unsupported MoS2 in the form of nano-scale thin layers in a reactor. Because the sulfide generated in the reaction process of the metal carried in the raw material residual oil is deposited to form a single phase and does not interfere with the naked MoS2 active center, the catalyst is not changed in the whole operation process, so the catalyst is not aged and can be recycled for a plurality of times. Because the catalyst exists in a nano-scale thin layer form, the catalyst has extremely large external surface area and extremely high dispersity, and the efficiency of activating hydrogen and inducing the side chain of an aromatic ring to break is very high.

In the EST residual oil suspension bed hydrogenation thermal cracking process, for the catalyst, the influence of coke generation is small, the surface area is large, and mass transfer diffusion resistance does not exist, so that the EST catalyst has higher activity than a carrier catalyst. The high specific activity (activity per unit mass) allows the EST catalyst concentration to be maintained only at a level of a few thousand μ g/g to provide good catalytic reaction conditions. Because the catalyst is well dispersed in the feedstock residue, the reaction process, the reaction exotherm, is spatially uniform, and therefore the temperature control is uniform without local overheating. Therefore, the use of unsupported suspended bed catalysts is particularly effective for residual oils with high metal content and high asphaltene content. The residual oil conversion process starts from a thermal reaction to generate free radicals through C-C bond breakage, the free radicals quickly obtain active hydrogen to realize hydrogenation stability, and coking caused by beta fission of the free radicals and continuous combination of the beta fission and the free radicals is avoided. The distance between the MoS2 thin layers in the suspension bed is several orders of magnitude smaller than the distance between the supported catalyst and the oil molecules, thus reducing the free radical generation time and the time required for the free radicals to reach the catalyst surface and complete the hydrogenation stabilization process, which also reduces coking. MoS2 has the ability to catalyze hydrogen to convert into active hydrogen (hydrogen atom), and also has the ability to activate aromatic rings, so that aromatics hydrogenation and carbon residue are reduced, and can remove heteroatom through reactions such as hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, hydrodemetallization and the like by means of C-heteroatom bond hydrogenolysis.

In the EST residual oil suspension bed hydrogenation thermal cracking process, unconverted residual oil is recycled to a reactor together with dispersed catalyst and other solids. Optimizing process severity (reaction time and reaction temperature) according to the quality of raw material residual oil, mixing part of unconverted residual oil (the quality of which is poorer than that of the fresh raw material residual oil in the same boiling range, lower hydrogen content and higher carbon residue value) with the fresh residual oil for circulating hydrogenation thermal cracking reaction, on one hand, enabling the asphaltene capable of being lightened to realize deep conversion lightening through multiple reactions, on the other hand, enabling the asphaltene difficult to lighten to realize multiple thermal reactions to form heat condensation product accumulation, under the condition of maintaining a certain discharged residual oil ratio, discharging part of asphaltenes or coke precursors which are difficult to convert in time, the properties of the circulating residual oil are in a stable state for a long time, the phenomena of coke formation and equipment scaling caused by asphaltene precipitation of the circulating residual oil and the liquid phase of the first reaction section are avoided, cyclic hydrocracker cracking is achieved as such until near complete conversion, where near complete conversion refers to less discharged tail oil than 100% lightening of the residuum feedstock. In order to limit the recycle accumulation of metal (mainly vanadium, nickel, iron) sulfides from the raw resid, a small amount (about 3 wt.% ratio to fresh resid) of unconverted resid, containing resid hydrocarbons, entrained metal sulfide particles, and other solids, must be vented.

taking the EST residual oil suspension bed hydrogenation thermal cracking process of Italy Eny company as an example, the amount of the hydrocarbon oil in the discharged solid residual oil VR-OUTS is usually not more than 5%, and is generally only 2.5-3.3 wt% of the weight of the raw residual oil, and the amount is calculated as 3 wt% below, and the once-through conversion rate of the residual oil is 68 wt%. For 100 ten thousand tons/year residual oil raw material, the quantity is 3 ten thousand tons/year, and because the proportion of the quantity of the molybdenum disulfide solid catalyst in the liquid phase to the quantity of the raw oil in the reaction process is a few thousandths, calculated by two thousandths, the discharged solid residual oil VR-OUTS contains 3 ten thousand tons/year hydrocarbon oil and catalyst molybdenum disulfide solid particles (187.5 tons/year) which are 0.00625 times of the hydrocarbon oil.

Taking EST residual oil suspension bed hydrogenation thermal cracking process of Italy Eny company as an example, supposing that the discharged residual oil ratio is reduced to 0.3 wt% of the weight of the raw residual oil, for 100 ten thousand tons/year residual oil raw material, the quantity of the circulating residual oil is increased from 42.65 ten thousand tons/year to 46.62 ten thousand tons/year (the weight increase multiplying factor is only 1.09), the quantity of the discharged tail oil is sharply reduced from 3 ten thousand tons/year to 0.3 ten thousand tons/year (the weight reduction multiplying factor is up to 10 times), the ratio of the quantity of the molybdenum disulfide solid catalyst in the liquid phase to the quantity of the raw oil in the reaction process is two thousandths, so that the discharged solid-containing residual oil VR-OUTS contains 0.3 ten thousand tons/year hydrocarbon oil and the molybdenum disulfide solid catalyst particles (18.75 tons/year) which are 0.00625 times of hydrocarbon oil, from the surface of the calculation result, it seems that the improvement of the utilization ratio of the raw residual oil, the, And at the same time, to reduce the fresh catalyst consumption.

However, the above assumptions do not take into account the following 3 factors caused by the change in cycle oil carbon residue values (related to asphaltene species and concentration):

On the basis of 97 weight percent of total conversion rate of residual oil, along with the small increase of the total conversion rate of the residual oil, the quantity of discharged residual oil is sharply reduced, the concentration and the carbon residue value of asphaltene in unconverted residual oil can be rapidly increased, and a concentrated solution of asphaltene which is difficult to convert is formed, so that the circulating residual oil becomes the circulating residual oil with high carbon residue and high concentration and heavy asphaltene which is difficult to hydrocrack; due to the accumulation of the difficult-to-convert asphaltenes, the dissolution balance of the asphaltenes in the residual oil colloidal solution is broken, and the asphaltenes are separated out to quickly coke, so that the overall conversion rate of the raw material residual oil cannot be improved without an upper limit by a single reaction separation section;

the analysis also shows that on the basis of 97 wt% of the total conversion rate of the residual oil, if the attempt is made to further improve the total conversion rate of the residual oil, the stability of a liquid phase in the reaction process is difficult to control, because the asphaltene concentration and the carbon residue value of the circulating residual oil can be rapidly increased and the concentration of the circulating residual oil is difficult to accurately control, for example, the carbon residue content of the circulating residual oil can be improved by 0.50-1.0 times or even higher times when the quantity of the circulating residual oil is improved by only 9%;

thirdly, on the basis of 97 weight percent of total conversion rate of residual oil, along with the small increase of the total conversion rate of the residual oil, the quantity of discharged residual oil is sharply reduced, and the solid concentration in unconverted residual oil is multiplied, so that the circulating residual oil becomes circulating residual oil with high solid concentration, and two influences exist, namely, on one hand, the favorable accumulation effect, namely the concentration effect is favorable for the increase of the concentrations of components such as molybdenum sulfide, nickel sulfide, iron sulfide and the like in a liquid phase of a catalyst in a reaction process, and on the other hand, the harmful accumulation effect, namely the concentration effect causes the increase of the concentration of organic metal product sulfide solid particles (metal sulfides without hydrogenation catalyst effect) carried by fresh raw material residual oil in a liquid phase in the reaction process, thereby causing the increase of the solid concentration carried in distilled oil in a fractionation process, and on the difficult-processing residual oil (the total content of metal Ni + V is, The effect is more obvious when the total amount of metal Ni + V is 200-800 mu g/g, and calculated by the concentration of organic metal (non-molybdenum metal) of 800 mu g/g (the equivalent is about 1200 mu g/g of sulfide), the carrying rate of non-molybdenum metal sulfide in the unconverted residual oil is 0.04g/g when the residual oil conversion rate is 97 wt%, and the carrying rate of non-molybdenum metal sulfide in the unconverted residual oil is 0.40g/g when the residual oil conversion rate is 99.7 wt%.

due to the limitation of the reasons, the total conversion rate of the raw material residual oil of the EST residual oil suspension bed hydrocracking process is constrained to be 95.0-97.5 wt%, that is, the amount of the hydrocarbon oil discharged OUT of the solid residual oil VR-OUT is usually 5%, and is generally only 2.5-3.3 wt% of the weight of the raw material residual oil, and is calculated according to 3 wt%, and the once-through conversion rate of the residual oil is 68 wt%, and for 100 ten thousand tons/year of residual oil raw material, the amount of the residual oil raw material is 3 ten thousand tons/year, and because the ratio of the amount of molybdenum disulfide solid catalyst in the liquid phase to the amount of the raw material oil in the reaction process is several thousandths, the discharged solid residual oil VR-OUTS contains 3 ten thousand tons/year of hydrocarbon oil and molybdenum disulfide solid particles (187.5 tons/year) carrying 0.00625 times of the weight of the hydrocarbon oil. Because the solid content of the discharged residual oil is too high and the solid oxide of the combustion product of partial sulfide belongs to low-melting-point oxide, the utilization mode of the discharged residual oil can only be used as fuel oil admixture, delayed coking admixture, cement fuel, coal blending coking process, asphalt admixture and the like according to the different properties of the hydrocarbon oil containing the discharged solid residual oil VR-OUTS, and the utilization values of the approaches are not high.

therefore, the EST residual oil suspension bed hydrogenation thermal cracking process has the following defects:

Firstly, because the discharged solid residue oil VR-OUT is difficult to realize high-value application, the price difference is about 2000 yuan/ton compared with the hydrocarbon oil which is further converted into low boiling point, and if 90 percent of tail oil can be recovered, namely 2.7 million tons/year of oil product, the price can be increased by 0.54 million yuan RMB/year;

Secondly, the catalyst replenishment amount is difficult to further reduce greatly;

In the process of recycling the metal in the discharged solid residue oil VR-OUT, the problem of utilization of combustible hydrocarbon oil must be solved, so that the metal recycling process is low in economy and complex in working procedure;

If the attempt to pursue the total conversion rate of the extremely difficult-to-process residual oil with high carbon residue content and high metal content reaches an ideal value, such as 97-98 wt%, the stability of a liquid phase in the reaction process is difficult to control, and in fact, the total conversion rate is forced to be reduced, and meanwhile, the consumption of an externally supplied catalyst is rapidly increased.

In fact, the root of the above technical problem lies in the presence of the recycled residue in a single reaction separation section, which has the dual main functions of both recycled residue and recycled catalyst, while reducing the amount of catalyst added requires reducing the rate of discharged residue as much as possible, but reducing the rate of discharged residue inevitably leads to enrichment of unconverted residue with asphaltenes which are difficult to convert. Since engineering technology of the residual oil suspension bed hydrocracking process needs to be optimized and considered by integrating multiple factors, the analysis suggests that the two accumulation effects need to be utilized or responded respectively for the residual oil which is difficult to process and the residual oil which is extremely difficult to process, so that classified processing or classified combined processing to a certain extent is formed. The above analysis suggests that the two main functions of the circulating resid and the circulating catalyst need to be decoupled, one decoupling method is to process the primary hydrocracked product resid separately to form the second reactive separation stage.

the present invention considers that the EST residual oil suspended bed hydro-thermal cracking process of einy italy lacks a high-selectivity secondary oil-solid separation process (avoiding a large amount of asphaltene circulation) which discharges solid residual oil VR-OUT and aims at concentrating metal sulfide (sulfide of metal carried by fresh residual oil and molybdenum disulfide as catalyst) solid particles, and in order to improve the value of hydrocarbon oil in VR-OUT, the oil-solid separation process should be a chemical separation process for realizing the lightening (hydrogenation) of residual oil, and a second heavy oil suspended bed hydro-reaction separation process is required to be arranged for solid residual oil discharged in the conventional heavy oil suspended bed hydro-reaction separation process so as to obtain solid residual oil with a higher proportion of light conversion distillate oil and molybdenum disulfide as catalyst solid particles.

so far, the basic concept of the present invention has been proposed: a sectional type heavy oil suspension bed hydro-thermal cracking reaction separation method, a reaction product obtained by a heavy oil UR10F mainly composed of hydrocarbons with a conventional boiling point higher than 530 ℃ in a first reaction section of a first reaction separation section is separated into a first separation section discharge heavy oil containing a residual oil component and catalyst solid particles in a first separation section US10, and a reaction product obtained by the first separation section discharge heavy oil in a second reaction section of a second reaction separation section is separated into a second separation section residual oil US20-VR containing a residual oil component and catalyst solid particles in a second separation section US 20; US20-VR may be used partly as export heavy oil from the second separation section and partly as long cycle heavy oil entering the first reaction section; compared with a single-stage process, most of residual oil in the discharged heavy oil of the first separation section can be lightened into distillate oil, the consumption of a fresh catalyst can be obviously reduced, the residual oil with higher metal content or higher carbon residue content can be processed, and various combined processes can be formed.

In essence, in the EST resid suspension bed hydrocracking process, the primary hydrocracked product resid (also primary unconverted resid with low catalyst solids concentration) of the resid feedstock and the secondary hydrocracked product resid (which becomes secondary unconverted resid with high catalyst solids concentration when processed separately) of the resid discharged from the first separation section are mixed together, and the process is characterized in that:

firstly, the circulating residual oil and the primary residual oil are mixed to carry out suspension bed hydrogenation thermal cracking reaction and product separation, so the process is simple and the investment is saved;

Secondly, the concentration of solid particles of the catalyst in the liquid phase in the process of hydro-thermal cracking of the primary raw material residual oil (fresh raw material residual oil) in a suspension bed is improved, so that the hydro-thermal cracking reaction of the primary raw material residual oil (fresh raw material residual oil) in the suspension bed is facilitated;

thirdly, one of the disadvantages is that in order to realize the great reduction of the discharged residual oil quantity, the proportion (or concentration) of the solid in the unconverted residual oil flow is necessarily greatly increased, and the proportion (or concentration) of the solid in the liquid phase in the whole circulation flow range flowed by the circulating residual oil is necessarily greatly increased, for example, when the discharge rate of the residual oil is reduced from 3 weight percent to 0.3 weight percent, the carrying proportion of the solid particles of 300 microgram/g generated by the organic metal carried by the raw material in the circulating residual oil is increased from 0.01: 1g/g to 0.10: 1g/g, so that the carrying proportion of the corresponding solid particles in the mixed residual oil of the initial raw material in the reaction process is increased from 0.0032: 1g/g to 0.032: 1 g/g;

When the raw material residual oil is difficult-to-process residual oil (the total amount of metal Ni and V is 200-800 mug/g) and extremely difficult-to-process industrial residual oil (the total amount of metal Ni and V is 200-800 mug/g), the metal content is 800 mug/g, the concentration of the metal sulfide is corresponding to the value that the metal carried by the raw material residual oil generates about 1200 mu g/g solid particles, the carrying ratio in the circulating residual oil is increased from 0.04: 1g/g to 0.40: 1g/g, which causes the carrying ratio of corresponding solid particles in the mixed residual oil of the initial raw materials of the reaction process to be increased from 0.0128: 1g/g to 0.128: 1g/g, therefore, the high-particle-concentration liquid phase condition is caused in the circulating process of circulating residual oil, the erosion amplitude of instruments such as a high-pressure-drop valve, a high-flow-rate valve, a flow meter and the like is greatly increased, and the problem of preventing the washing of a large number of particles from depositing is caused to the operation of a liquid level measuring and monitoring instrument;

secondly, in the fractionation process of the suspension bed hydrocracking product, the excessively high weight concentration (up to more than ten percent) of the solid particles of the metal sulfide can increase the probability of carrying the solid particles by the distillate oil, thereby increasing the difficulty of removing the solid particles in the fractionation process, increasing the concentration of the solid particles in the distillate oil product and influencing the product quality;

fifthly, in the fractionation process of the hydrocracking product in the suspension bed for processing the high-carbon residue oil with high asphaltene content, the yield of the unconverted residue oil is too low, so that the asphaltene concentration in the unconverted residue oil is too high, and the cycle residue oil with too high asphaltene concentration can seriously deteriorate the thermocracking property of the suspension bed hydrocracking reaction process of the fresh residue oil;

these recycled residue components are not necessarily present as required for material balance, but are merely the result of the cumulative recycle due to the mode of operation; however, in order to process these extrinsic materials, it is usually necessary to use a certain liquid phase molecular concentration of hydrogen donor solvent oil to inhibit coking or to use a certain amount of aromatic-rich wax oil to dilute the residual oil, and the existence of such poor cycle residual oil in large quantities requires the use of a large amount of hydrogen donor solvent oil or wax oil diluent, thereby greatly increasing the operation cost; the first hydrogenation thermal cracking product residual oil is separately processed to form a second reaction separation section, so that the hydrogen supply solvent oil corresponding to the fresh residual oil can be reduced, the quantity of the hydrogen supply solvent oil is greatly reduced, the thermal cracking loss rate of the hydrogen supply solvent oil can be reduced, and the process economic benefit is improved;

in this case, the first reaction separation stage is used as the first hydrocracking process for very poor residues, with the aim of converting the majority of the hydrocarbon oil (but without excessively pursuing the conversion to prevent excessive deterioration of the properties of the primary unconverted residue) under more optimal reaction conditions (medium or low solids content in the reaction liquid phase, medium or low asphaltene concentration); the second reaction separation section is used as a hydro-thermal cracking process of the primary unconverted residual oil, and aims to convert most of hydrocarbon oil under harsh reaction conditions (high solid content in reaction liquid phase, high asphaltene concentration, large amount of hydrogen supply solvent, low conversion per pass and the like), but does not excessively pursue conversion rate to prevent extreme deterioration of properties of the secondary unconverted residual oil, and then discharge the secondary unconverted residual oil with ultrahigh solid concentration in the separation or fractionation process of the second reaction separation section, so as to finally realize relative separation of the hydrocarbon oil and the solid in the primary unconverted residual oil;

Surprisingly, if the unconverted residual oil of the second separation section is used as the catalyst circulating material, namely the long circulating residual oil, and returns to the first reaction section, the consumption of the fresh catalyst can be greatly reduced, and the absolute quantity of the poor residual oil brought into the first reaction section can be greatly reduced, so that the first reaction separation section short circulating residual oil is responsible for the circulating residual oil with better circulating property, and the second reaction separation section long circulating residual oil is responsible for efficiently circulating the catalyst, thereby achieving the aim of reducing the consumption of the catalyst.

the above analysis also shows that the present invention can convert inferior (higher metals and/or higher asphaltenes) residues compared to the EST residue suspension bed hydrocracking process of Eini, Italy, and thus can expand the residue processing range of the suspension bed hydrocracking process.

therefore, the invention provides a sectional type heavy oil suspension bed hydrogenation thermal cracking reaction separation method.

the two reaction separation processes comprise a first reaction separation section and a second reaction separation section which takes the discharged vacuum residue US10-VR-OUT of the first separation process US10 of the first reaction separation section UT10 as raw oil UR 20F. A second reaction separation process comprising a second hydrocracking reaction process of raw oil UR20F and a second separation process (usually comprising vacuum fractionation) of heavy oil components and lower boiling hydrocarbon components of the second hydrocracking reaction product, which may include a short circulation process for circulating the unconverted residual oil or modified oil thereof discharged from the second separation process (usually comprising vacuum fractionation) back to the second hydrocracking reaction process for cyclic hydrocracking, in order to prevent the accumulation of sulfide solids, ash, solid particles of catalyst, etc. generated by metals carried by raw oil UR20F, during the second hydrocracking reaction, the second separation process (usually including the second vacuum fractionation process) of the second reaction separation section must discharge discharged heavy oil containing solid particles, such as vacuum residue US20-VR-OUT, mainly composed of unconverted residue. In order to simplify the process, the gas phase material flow of the second reaction process can be recovered through the first reaction process or combined with the gas-containing material of the first reaction process, the gas phase material flow of the separation process of the second reaction product can be recovered through the gas-containing material of the separation process of the first reaction product, and the unconverted residual oil of the second reaction process can be recycled to the first reaction process to reduce the consumption of the catalyst, thereby forming the combined process.

The three reaction separation section processes comprise a first reaction separation section and a second reaction separation section, and also comprise a third reaction separation section which takes the discharged vacuum residue US20-VR-OUT of a second section separation process US20 of the second reaction separation section UT20 as raw oil UR 30F. A third reaction separation process, a third hydrocracking reaction process UR30 containing raw oil UR30F and a third separation process (usually including vacuum fractionation) for separating wax oil component and residual oil component of the third hydrocracking reaction product, which can include a short circulation process for circulating the unconverted residual oil or modified oil thereof discharged from the third separation process (usually including vacuum fractionation) back to the third hydrocracking reaction process UR30 for circulating hydrocracking, in order to prevent the accumulation of sulfide solids, ash, solid particles of catalyst, etc. generated by metals carried in raw oil UR30F, and solid particles existing in the third hydrocracking reaction process, the third separation process (usually including the third vacuum fractionation process) of the third reaction separation section must discharge discharged vacuum residue US30-VR-OUT containing solid particles and mainly composed of unconverted residue. In order to simplify the process, the gas phase material flow of the third section of reaction process can be recovered through the upstream reaction section reaction process or jointly with the gas-containing material of the upstream reaction section reaction process, the gas phase material flow of the third section of reaction product separation process can be jointly recovered through the gas-containing material of the upstream reaction section reaction product separation process, and the third section of unconverted residual oil can be recycled to the upstream reaction section reaction process to reduce the consumption of the catalyst, so that the combined process is formed.

the present invention, if necessary, can constitute a process comprising four or more reaction separation stages, and generally, satisfactory results can be obtained by using two reaction separation stages.

When the sectional type heavy oil suspension bed hydrocracking reaction separation method is applied to the heavy oil hydrocracking process, compared with the prior EST process, the method mainly aims to obtain 1 or more of the following target effects:

Setting a secondary suspension bed hydrogenation reaction separation process for discharged residual oil at a first separation section, converting and recovering hydrocarbon oil in tail oil in a chemical reaction mode, and assuming that the total conversion rate of the residual oil at the first reaction section is 97 wt% for 100 ten thousand tons/year of residual oil raw material, if 90% of the recovered tail oil, namely 2.7 ten thousand tons/year of oil product can increase 0.54 million yuan RMB/year value, the benefit is huge;

if 90% of the discharged residual oil of the first separation section is recovered through the hydrogenation conversion of the suspension bed of the second reaction section (namely the hydrogenation thermal cracking conversion rate of the second reaction section is 90 wt%), the weight ratio of the molybdenum disulfide solid particles as the catalyst in the discharged residual oil of the second separation section to the hydrocarbon oil is concentrated by 10 times;

If 95% of the discharged residual oil of the first separation section is recovered through the hydroconversion of the suspension bed of the second reaction section (namely the hydroconversion rate of the second reaction section is 95 wt%), the weight ratio of the molybdenum disulfide solid particles as the catalyst in the discharged residual oil of the second separation section to the hydrocarbon oil is concentrated by 20 times;

the data show that the solid in the discharged residual oil of the second separation section can be concentrated at a high rate, so that the recovery of metal is facilitated, and meanwhile, in the second reaction section, the molybdenum disulfide solid particles which are catalysts with ultrahigh concentration are distributed, so that the processing of the circulating residual oil of the second separation section is facilitated;

the above data also indicate that, in order to achieve high-rate concentration of the molybdenum disulfide solid particles in the discharged residual oil of the second separation section, the second reaction separation section is preferably not diluted by other high-boiling-point hydrocarbon materials with low solid concentration, so as to prevent reduction of the concentration rate of the molybdenum disulfide solid particles in the tail oil of the second reaction separation section and increase of the loss rate of the residual oil;

The data also indicate that the deep processing or recycling process of the material (gas-phase material or liquid-phase material) which does not contain or basically does not contain solid particles of the second reaction separation section is not required or limited, and the deep processing or recycling process of the material (gas-phase material or liquid-phase material) which does not contain or basically does not contain solid particles of the second reaction separation section can be intensively processed with the similar material of the upstream reaction separation section or can be processed by part or all of the flow of the upstream reaction separation section so as to simplify the flow;

the above data also indicate that it is not necessary to require or limit the source and the destination of the hydrogen raw material of the second reaction separation section, therefore, the hydrogen raw material of the second reaction separation section can be jointly heat exchanged or heated with the hydrogen raw material of the first section suspension bed hydrocracking reaction process, or be used in series for the second time to form a combined process;

The data also indicate that the deep processing or recycling process of the solid particle-containing material (gas-phase material or liquid-phase material) discharged from the second reaction separation section is not required or limited; the material (gas phase material or liquid phase material) containing solid particles discharged from the second reaction separation section can be treated with the similar material of the upstream reaction separation section in a centralized way, or a long circulation flow among different flow sections can be formed through partial or all flows of the upstream reaction separation section; that is, the solids-containing material (or ultra-high catalyst solids resid) of the downstream flow section can be mixed back into the upstream solids-containing material; but limiting the solid-containing material with low solid content in the upstream process section to short-circuit and mix the solid-containing material with high solid content in the downstream;

The invention takes the second reaction separation section as a technical approach, and can improve the catalyst circulation efficiency of the circulating oil by times by improving the catalyst concentration in the long circulating residual oil; the concentration of the catalyst in the discharged residual oil of the second separation section can reach 5-20 times of that of the catalyst in the discharged residual oil of the first separation section and can reach tens of to hundreds of times of that of the catalyst carried in the fresh residual oil of the first reaction section, so that the addition amount of the fresh catalyst can be greatly reduced under the condition of realizing the same concentration of the liquid catalyst of the first reaction section, or higher catalyst concentration can be formed in the first reaction section under the condition of the same catalyst consumption, so that the conversion per pass is improved, the quantity of short circulating oil of the first reaction separation section is obviously reduced, the scale, the investment, the energy consumption and the catalyst consumption of the whole process are reduced, and a total flow with higher economy is formed;

The capability of processing inferior fresh residual oil can be improved, and the operating conditions and the conversion rate of the first reaction section and the second reaction section can be flexibly adjusted according to the property of the fresh residual oil;

when processing the residue oil which is difficult to process and the residue oil which is extremely difficult to process, in order to prevent the operation condition of the first reaction separation section from deteriorating, prolong the operation period of the first reaction separation section, improve the distillate oil quality of the first reaction separation section and properly reduce the severity of the first reaction section; in the second reaction separation section, the discharged residual oil of the first separation section can be converted under harsh reaction conditions (high solid content in a reaction liquid phase, high asphaltene concentration, use of a large amount of hydrogen supply solvent, low conversion per pass, and the like), most of the hydrocarbon oil (the conversion rate is not excessively pursued to prevent the extreme deterioration of the properties of the secondary unconverted residual oil) is converted, and then the discharged residual oil of the second separation section with ultrahigh solid concentration is discharged in the separation or fractionation process of the second reaction separation section, so that the relative separation of the hydrocarbon oil and the solid in the discharged residual oil of the first separation section is finally realized;

the operation stability of the process can be greatly improved, and for the discharged residual oil of the first separation section with the flow far lower than that of the fresh residual oil, a small amount of hydrogen supply solvent or diluent oil is used, so that the asphaltene concentration can be obviously reduced, and the carrying proportion of solid particles can be obviously reduced, therefore, the economic process is easy to form;

And the process is simplified and the investment and operation cost are reduced by a combined process.

the process similar to the invention is a combined process method for heavy oil modification in Chinese patent ZL200810228415.9 (No. CN101724449B), in which the tail oil unconverted by heavy oil suspension bed hydrocracking is mixed with a hydrogen supply solvent for supercritical treatment, the hydrogen supply solvent comprises tetrahydronaphthalene or decahydronaphthalene, the method does not provide the proposition of using long-circulating residual oil to reduce the consumption of the catalyst and the solution method thereof, the operation mode of the supercritical treatment co-treatment step is different from the operation mode of the second suspension bed hydrocracking process, and the expected effect of the invention can not be realized, therefore, the method is a technical method different from the invention.

from the view point of material flow quantity and component characteristics, the heavy oil suspension bed hydrocracking unconverted residual oil is a residue without macromolecule lightening or a converted substance or a concentrate of macromolecules of a thermal condensate in fresh heavy oil, because the quantity of the heavy oil suspension bed hydrocracking unconverted residual oil is less than that of the fresh residual oil, such as 0.02-0.30 of the weight of the heavy oil, the hydrogen supply solvent is convenient to use under the condition of high solvent-oil ratio, such as reaching 0.5-2.0, to carry out the suspension bed hydrocracking reaction with mild operation condition and carry out more hydrogenation saturation reactions, the high-concentration catalyst condition formed by the solid concentration effect is also beneficial to the hydrocracking reaction process of high-concentration asphaltene, other enriched solid particles have the carrying capacity of possible coke formation, and the synergistic effect among the above elements is beneficial and objective.

The problem and the solution proposed by the invention are a common problem and a commonly used technical scheme in the process of extremely-poor residual oil hydrocracking reaction, and the occurrence of the invention is inevitable due to the great influence of the effect of the invention.

In fact, the heavy oil suspension bed hydrocracking process has roughly 8 key problems:

Preventing coking of a heavy oil raw material heating furnace, which relates to the problem of reducing the outlet temperature of the heavy oil heating furnace and the problem of using a coking inhibitor such as a hydrogen supply solvent;

② suppression of thermal condensation in the initial thermal cracking process of heavy oil feedstocks, which relates to the problem of how to rapidly supply active hydrogen and also to how to use it for use in heavy oil feedstocks

The problem of hydrogen solvents;

thirdly, preventing a solution system at the end of the thermal cracking reaction from generating a super-saturated asphalt phase, namely a second liquid phase, which relates to the problem of reasonably controlling the conversion per pass and also relates to the problem of timely discharging light saturated hydrocarbon to prevent the reduction of the aromaticity of the solution;

Lowering the yield of tail oil and improving the process economy, which relates to the problem of improving the thermal cracking rate of the latter half of the primary thermal cracking process of fresh heavy oil materials and the problem of how to use a hydrogen donor solvent;

Lowering tail oil yield and raising process economy, and this is related to tail oil modification and circular hydrocracking and the use of hydrogen donor solvent;

Sixthly, the cost of the tail oil hydrocracking cycle process is reduced, the process economy is improved, the tail oil modification and cycle hydrocracking reaction process is involved, the combination method of the tail oil modification and cycle hydrocracking reaction process and the fresh heavy oil suspension bed hydrocracking reaction process is involved, and the problem of how to efficiently use a hydrogen supply solvent is also involved;

if hydrogen supply solvent is used, the method is adopted to shorten the circulation path, reduce the pollution degree and improve the use efficiency;

Under the operation targets of improving the conversion rate of heavy oil hydrogenation thermal cracking and prolonging the operation period, how to reduce the concentration of colloid asphaltene in a liquid phase solution and prevent the colloid asphaltene from being separated out to form a second liquid phase relates to the problem of how to form high-performance heavy cycle solvent oil (with coking resistance, abundant hydrogen supply capacity and strong dissolving capacity for the colloid asphaltene).

The present invention has been developed in response to the present teachings, and in particular, in response to the present teachings, a means for alleviating or eliminating some of the problems set forth above is provided.

the invention can be combined with any other suitable residual oil suspension bed hydrocracking process to form a corresponding combined process, and the possible combined technologies are at least:

firstly, in the process of hydrogenation of a suspension bed of fresh heavy oil, a liquid product circulating reactor is used for transferring heat of initial hydrocracking reaction to raw heavy oil, so that the preheating temperature of the raw heavy oil is reduced to 360-400 ℃, coking of a furnace tube of a heavy oil heating furnace is prevented, and a small amount of hydrogen supply solvent (such as 5-10% of the heavy oil) can be used for further preventing coking;

secondly, a high-dispersion high-activity catalyst such as a molybdenum catalyst is used, and a hydrogen donor solvent can be used at the same time, so that active hydrogen is rapidly provided, and thermal condensation in the initial thermal cracking process of the heavy oil raw material is inhibited, which is an essentially active scheme and can obviously improve the property of primary hydro-thermal cracking tail oil;

thirdly, preventing a solution system at the end of the thermal cracking reaction from generating a super-saturated asphalt phase, namely a second liquid phase, reasonably controlling the conversion per pass within the range of 65-80%, using a liquid product circulating reactor to improve the aromaticity of liquid-phase hydrocarbon at the outlet of the reactor, and simultaneously adopting a reaction zone at the tail end of the reactor to spray stripping hydrogen to discharge light hydrocarbon with high saturation in time so as to prevent the light hydrocarbon from reducing the aromaticity of the solution and also prevent the light hydrocarbon from excessively circulating thermal cracking to reduce the liquid yield; the existence of excessive hydrogen donor solvent is reduced, so that the thermal cracking rate can be improved, and the thermal cracking rate of the hydrogen donor solvent can be reduced;

adding high aromatic wax oil into the rear reaction section to safely control the concentration of asphaltene in the liquid phase in the reactor within a safe range and safely carry unconverted asphaltene out of the reactor;

Fifthly, the yield of tail oil is reduced, the process economy is improved, a tail oil hydrogenation modification reaction process CR using hydrogen-supplying solvent oil is set, a hydrogenation modification process taking aromatic hydrogenation saturation reaction as a main target reaction is carried out under the conditions of high catalyst-oil ratio, high catalyst concentration and low reaction temperature, then a product CRP is led into a rear reaction zone ARB in a suspension bed hydrogenation thermal cracking reaction process AR to carry out moderate hydrogenation thermal cracking reaction, excessive thermal condensation reaction caused by too high single-pass thermal cracking rate of the modified tail oil is prevented, the proportion of reaction types (hydrogenation saturation and hydrogenation cracking) in the integral circulating hydrogenation process of the tail oil THC-VR is controlled, the hydrogenation saturation reaction proportion is properly improved, the hydrogenation thermal cracking reaction proportion is reduced, multiple batch conversion is realized by increasing the circulation amount, the stability of the solution is controlled, and the quantity of the discharged tail oil is reduced, the quality of discharged tail oil is improved; the optimal result is that the discharged tail oil is small in amount (for example, less than 3-5%), and the discharged tail oil is only used for discharging solid particles (including catalyst particles, raw material heavy oil metal sulfides and a small amount of coking particles) to prevent the solid particles from being excessively accumulated in a reaction system;

meanwhile, a batch feeding technology can be adopted, so that the coking tendency in the tail oil circulating hydrogenation process is further improved;

The tail oil circulation hydrogenation modification reaction process and the fresh heavy oil suspension bed hydrogenation thermal cracking reaction process are combined, the cost of the tail oil circulation hydrogenation modification reaction process can be reduced, the process economy is improved, and because the hydrogen supply solvent is formed for secondary or even multiple serial circulation use, the hydrogen supply speed of a hydrogenation area and the total hydrogen supply capacity of a circulation path of the hydrogen supply solvent can be obviously improved, and the recycling efficiency is improved;

The high-efficiency circulation path of the hydrogen donor solvent is provided, the length of the circulation path can be shortened, the investment and the energy consumption of the circulation path can be reduced, the pollution degree of the hydrogen donor solvent can be reduced, and the circulation cost can be effectively reduced;

The special reactivation step of the hydrogen donor solvent can be combined with the distillate oil hydrogenation upgrading step, the process integration level is further improved, and the investment and the energy consumption of the overall process are reduced;

Ninthly, a suspension bed hydrogenation reactor is used in the heavy oil hydrogenation process, and a liquid product circulating suspension bed hydrogenation reactor is preferably used;

in the total flow of heavy oil processing, the coke and the heavy oil catalytic cracking process and/or the heavy oil coking process form a combined process, so that the coke yield is reduced, the light oil yield is increased, the hydro-thermal cracking conversion rate of the heavy oil raw material in the hydro-thermal cracking reaction process is improved, and the operation period of the heavy oil hydro-thermal cracking reaction process is prolonged.

The invention can form various combined processes by changing the flow forms of each reaction section or separation section, by jointly processing other hydrocarbon-containing materials suitable for joint processing and by combining the subsequent processing methods of hydrocarbon oil in various thermal high-molecular gases.

in the present invention, diluent oil or hydrogen donor solvent may be used in the downstream reaction section.

the hydrogen donor solvent precursor used in the present invention is diesel oil or heavy cycle oil as heavy oil catalytic cracking product, and thus constitutes the combined process of heavy oil catalytic cracking process and heavy oil hydrocracking process.

In the invention, when the used asphaltene carrier high aromatic hydrocarbon wax oil is heavy oil catalytic cracking product wax oil (heavy cycle oil and clarified oil), a combined process of a heavy oil catalytic cracking process and a heavy oil hydrocracking process is actually formed, the hydro-modification and hydro-thermal cracking of the heavy oil catalytic cracking product wax oil (heavy cycle oil and clarified oil) are realized, on one hand, the processing load of the catalytic cracking reaction process is reduced, the coke yield is reduced, and the liquid yield is increased, on the other hand, the hydrogen supply solvent quantity of the heavy oil hydrocracking process is increased, the yield of thermal condensation products (colloid, asphaltene and coke) in the heavy oil hydrocracking reaction process is reduced, the liquid yield is increased, the quantity of colloid asphaltene carrier solvent oil in the heavy oil hydrocracking product is increased, the heavy oil hydrocracking conversion rate is favorably improved, and on the whole, the distillate oil yield is favorably improved, the coke yield is reduced, and the process economy is obviously improved.

the residual oil hydrogenation thermal cracking product light wax oil can be used in a catalytic cracking reaction process or a catalytic cracking reaction process to produce more catalytic cracking gasoline andor catalytic cracking diesel oil, and the catalytic cracking diesel oil can be used as a precursor of a light hydrogen supply solvent.

According to the invention, when the used asphaltene carrier high aromatic hydrocarbon wax oil is the heavy wax oil which is a coking product, a combined process of a heavy oil coking process and a heavy oil hydrocracking process is actually formed, and the hydrogenation modification and the hydrogenation thermal cracking of the heavy wax oil are realized, so that the processing load in the coking reaction process is reduced, the coke yield is reduced, the liquid yield is increased, the hydrogen supply solvent quantity in the heavy oil hydrocracking process is increased, the yield of thermal condensation products (colloid, asphaltene and coke) in the heavy oil hydrocracking process is reduced, the liquid yield is increased, the quantity of solvent oil carried by colloid asphaltene in the heavy oil hydrocracking product is increased, the heavy oil hydrocracking conversion rate is favorably improved, and in general, the distillate oil yield is favorably improved, the coke yield is reduced, and the process economy is obviously improved.

Particularly, in the heavy oil hydrocracking reaction process using the hydrogen supply solvent, compared with the conventional heavy oil hydrocracking reaction process without the hydrogen supply solvent, under the condition of the same hydrocracking conversion rate, the hydrogen content of the hydrocracking residual oil is obviously increased, the carbon residue value is obviously reduced, the hydrocracking residual oil serving as the circulating hydrocracking residual oil is easier to hydrocrack, the hydrocracking residual oil serving as the discharged oil can be used as a high-quality gasification raw material, and the coke yield is lower when the hydrocracking residual oil serving as the coking process raw material is used, so that the coking distillate oil yield is favorably improved, if a certain proportion of hydrogenation modified oil of high aromatic wax oil is blended in the coking process raw oil such as a delayed coking process serving as the hydrogen supply solvent, a hydrogenation coking reaction process is formed, and the combined process allows the heavy oil hydrocracking reaction process to process worse (higher carbon residue content), Less expensive residua. The combined process of the heavy oil hydrocracking process and the heavy oil coking process is particularly suitable for combining the newly-built heavy oil hydrocracking process with the existing heavy oil coking process.

Heavy oil hydrogenation thermal cracking heavy wax oil or hydrogenation modified oil thereof, heavy oil catalytic cracking product wax oil (heavy cycle oil, clarified oil) hydrogenation modified oil, heavy oil coking product heavy wax oil hydrogenation modified oil, can be used as hydrogen-supplying solvent oil with certain hydrogen-supplying capability in a decoking reaction process such as a delayed coking reaction process or a fluid coking reaction process or a flexible coking reaction process, is combined with heavy oil hydrogenation thermal cracking residual oil to carry out a coking reaction process, the coking reaction process also typically combines processing of straight run vacuum residua to control the carbon residue content of the total coker feedstock and or ash content, metal content in the product coke, and after the hydrogen supply solvent is used in the heavy oil hydrocracking process, the use amount of the heavy oil hydrocracking catalyst solid and the coke carrier solid can be reduced, so that the operation effect of the coking reaction process of the heavy oil hydrocracking residual oil can be optimized.

the method of the present invention has not been reported.

therefore, the first objective of the present invention is to provide a separation method of a segmental heavy oil suspension bed hydrogenation thermal cracking reaction, wherein the heavy oil can be residual oil with extremely high metal concentration or extremely high asphaltene concentration, and the ratio of unconverted residual oil can be effectively reduced.

The second purpose of the invention is to provide a sectional type heavy oil suspension bed hydrogenation thermal cracking reaction separation method, heavy oil can be residual oil with extremely high metal concentration or extremely high asphaltene concentration, part of unconverted residual oil in the second separation section is used as long-circulating residual oil and returned to the first reaction section, the catalyst consumption can be greatly reduced, and the proportion of residual oil carrying metal sulfide particles in discharged residual oil can reach 15-35 wt% or higher, thereby being beneficial to metal recovery.

The third purpose of the invention is to provide a separation method of the segmented heavy oil suspension bed hydrogenation thermal cracking reaction, in the suspension bed hydrogenation thermal cracking reaction process, the active substance of the main catalyst is the sulfide of metal molybdenum, the particle structure of the active substance is preferably nano-scale particles, particularly the particle structure of the active substance is preferably nano-scale flaky particles, thereby reducing the concentration of the catalyst particles, and being particularly beneficial to the deep hydrogenation thermal cracking of the residual oil with extremely high metal concentration or extremely high asphaltene concentration.

The fourth purpose of the invention is to provide a sectional type heavy oil suspension bed hydrogenation thermal cracking reaction separation method, wherein the gas phase material flow in the second section of reaction process can be recovered through the first section of reaction process or combined with the gas phase-containing material in the first section of reaction process, the gas phase material flow in the second section of reaction product separation process can be recovered through the gas phase-containing material in the first section of reaction product separation process, and the second section of unconverted residual oil can be recycled to the first section of reaction process, thereby forming a combined process.

the fifth purpose of the invention is to provide a sectional type heavy oil suspension bed hydrogenation thermal cracking reaction separation method using hydrogen donor solvent oil, which can modify hydrocarbon oil (catalytic cracking diesel oil and/or catalytic cracking heavy cycle oil and/or catalytic cracking clarified oil) rich in aromatic hydrocarbons with 2-4 ring structures, which is generated in a heavy oil catalytic cracking process (or a heavy oil catalytic cracking process), into the hydrogen donor solvent for use, and light wax oil which is a heavy oil hydrogenation thermal cracking product can be removed from the catalytic cracking reaction process to produce more catalytic cracking gasoline and/or catalytic cracking diesel oil, so that a combination of the heavy oil catalytic thermal cracking process and the residual oil suspension bed hydrogenation thermal cracking process is formed.

disclosure of Invention

the invention relates to a sectional type heavy oil suspension bed hydrogenation thermal cracking reaction separation method, which is characterized by comprising the following steps:

heavy oil UR10F, comprising hydrocarbon components having a conventional boiling point above 530 ℃, comprising organometallics and or asphaltenes;

the hydrocracking reaction separation process in the suspension bed of heavy oil UR10F comprises at least 2 reaction separation nodes, namely a first reaction separation node UT10 and a second reaction separation node UT 20;

a first reaction separation section UT10, comprising a first reaction section UR10, a first separation section US 10;

A second reaction separation section UT20, comprising a second reaction section UR20 and a second separation section US 20;

(1) in the first reaction section UR10, heavy oil UR10F undergoes a first suspended bed hydrocracking reaction UR10R to convert into a first hydrogenation reaction product UR10P in the presence of hydrogen, normal liquid hydrocarbons, a first solid particulate catalyst UR10-CAT, and possibly hydrogen-donating hydrocarbons, and possibly other solid particulate miscible materials; the first suspension bed hydrocracking reaction UR10R makes at least a part of the hydrocarbon components with normal boiling point higher than 530 deg.C complete hydrocracking reaction to produce hydrocarbon products with smaller molecular weight;

A stream UR10P-X based on the first hydrogenation reaction product UR10P comprising hydrocarbon components having a conventional boiling point above 530 ℃ and solid particulate catalyst enters the first separation section US 10;

(2) in the first separation section US10, the separation stream UR10P-X yields a first hydrogen-rich gas US10H, a first external light distillate US10-MP, a first heavy oil US10-VR comprising hydrocarbon components having a conventional boiling point above 530 ℃ and a solid particulate catalyst;

at least one part of the first heavy oil US10-VR is used as the first discharged heavy oil US10-VR-OUT and enters the second reaction section UR20 to be used as the raw heavy oil UR 20F;

a part of the first heavy oil US10-VR is returned to the first reaction section UR10 as the short cycle heavy oil US10-VR-TOUR10 of the first reaction separation joint UT10 to be contacted with the hydroconverter of the heavy oil UR10F or the heavy oil UR10F for the first cycle hydro-thermal cracking reaction;

(3) In the second reaction section UR20, heavy oil UR20F containing first discharged heavy oil US10-VR-OUT undergoes a second slurry hydrocracking reaction UR20R to convert into a second hydrogenation reaction product UR20P in the presence of hydrogen, normal liquid hydrocarbons, second solid particle catalyst UR20-CAT, and possibly hydrogen-supplying hydrocarbons, and possibly other solid particles; the second suspension bed hydrocracking reaction UR20R makes at least a part of the hydrocarbon components with normal boiling point higher than 530 deg.C complete hydrocracking reaction to produce hydrocarbon products with smaller molecular weight;

a stream UR20P-X based on the second hydrogenation reaction product UR20P comprising hydrocarbon components having a conventional boiling point above 530 ℃ and solid particulate catalyst enters the second separation section US 20;

(4) in the second separation section US20, the stream UR20P-X is separated to obtain a second hydrogen-rich gas US20H, a second external light distillate US20-MP, a second heavy oil US20-VR comprising hydrocarbon components having a conventional boiling point above 530 ℃ and a solid particulate catalyst;

At least a portion of the second heavy oil US20-VR used as second extra heavy oil US 20-VR-OUT;

It is possible to contact a part of the second heavy oil US20-VR as the short cycle heavy oil US20-VR-TOUR20 of the second reaction separation node UT20 back to the second reaction section UR20 to the heavy oil UR20F or the hydroconverter of the heavy oil UR20F for the second cycle hydrocracking reaction.

in the present invention, at least a portion of the first hydrogen-rich gas, US10H, can be returned to the first reaction stage UR10 for use.

in the present invention, at least a portion of the second hydrogen-rich gas, US20H, can be returned to the second reaction stage UR20 for use.

in the present invention, at least a portion of the first hydrogen-rich gas, US10H, may be introduced into the second reaction stage UR20 for use.

In the present invention, at least a portion of the second hydrogen-rich gas, US20H, may be introduced into the first reaction stage UR10 for use.

In general, heavy oil UR10F is composed mainly of hydrocarbon components having a conventional boiling point of more than 450 ℃.

in general, heavy oil UR10F is composed mainly of hydrocarbon components having a conventional boiling point of above 530 ℃.

according to the invention, in general, in the first reaction stage UR10, a first solid particulate catalyst UR10-CAT is used which contains at least a molybdenum-based catalyst whose operating state is molybdenum disulfide.

in the first reaction stage UR10, the first solid particulate catalyst UR10-CAT used according to the invention generally comprises at least a molybdenum-based catalyst whose operating state is in the form of nanosized plate crystals.

according to the invention, in general, in the first reaction stage UR10, a first solid particulate catalyst UR10-CAT is used which comprises at least a molybdenum-based catalyst whose operating condition is molybdenum disulfide;

the first solid particle catalyst UR10-CAT also contains a compound of one or more metals other than molybdenum in group VIB metal or group VIIB metal or group VIII metal of the periodic table of elements, and the working state of the metal catalysts is sulfide.

The first solid particle catalyst UR10-CAT also contains one or several compounds of Ni, Co, W, Cr and Fe, and these metal catalysts are sulfide.

according to the invention, in general, in the first reaction stage UR10, the first solid particulate catalyst UR10-CAT used comprises at least a molybdenum-based catalyst whose operating state is molybdenum disulfide, at least a portion of which comes from an externally added catalyst;

the first solid particle catalyst UR10-CAT also contains one or several compounds of Ni, Co, W, Cr and Fe, and these metal catalysts are sulfide in working state, and at least part of these catalysts are sulfide products from the hydrodemetallization reaction of heavy oil UR10F in the first reaction stage UR 10.

In the first reaction stage UR10, the total conversion of hydrocarbon components with conventional boiling points higher than 530 ℃ in the heavy oil UR10F is 60 to 98 wt%.

In the first reaction stage UR10, the total conversion of hydrocarbon components having a normal boiling point of more than 530 ℃ is 50 to 80 wt%, based on the total flow of heavy oil UR10F and short-cycle heavy oil US10-VR-TOUR10, if any.

in the second reaction stage UR20, the total conversion rate of hydrocarbon components with conventional boiling point higher than 530 ℃ in heavy oil UR20F is 60 to 90 wt%.

in the second reaction stage UR20, the total conversion of hydrocarbon components having a normal boiling point of more than 530 ℃ is 30 to 60 wt%, based on the total flow of heavy oil UR20F and short cycle heavy oil US20-VR-TOUR20, if any.

the operating conditions for the two-stage process of the present invention are typically:

oil UR10F consists essentially of hydrocarbon components having a conventional boiling point above 500 ℃;

in the first reaction section UR10, the total conversion rate of hydrocarbon components with the conventional boiling point higher than 530 ℃ in the heavy oil UR10F is 60-98 wt%;

in the first reaction stage UR10, the total conversion rate of hydrocarbon components with conventional boiling points higher than 530 ℃ is 50-80 wt% based on the total flow of heavy oil UR10F and short cycle heavy oil, if any, US10-VR-TOUR 10;

In the second reaction section UR20, the total conversion rate of hydrocarbon components with the conventional boiling point higher than 530 ℃ in the heavy oil UR20F is 60-90 wt%;

in the second reaction stage UR20, the total conversion rate of hydrocarbon components with conventional boiling point higher than 530 ℃ is 30-60 wt% based on the total flow of heavy oil UR20F and short cycle heavy oil US20-VR-TOUR 20;

in the first reaction stage UR10, the first solid particulate catalyst UR10-CAT used contains at least molybdenum-based catalysts whose operating state is molybdenum disulfide, at least a portion of these molybdenum-based catalysts coming from externally added catalysts;

the invention defines the ratio of the weight US20-VR-OUT-WT of the second external heavy oil US20-VR-OUT to the weight UR10F-WT of the heavy oil UR10F as K500;

k500 is (US20-VR-OUT-WT)/(UR10F-WT), and K500 is usually 0.001 to 0.02, usually 0.003 to 0.01.

according to the invention, in general, (4) in the second separation section US20, the separated stream UR20P-X yields a second heavy oil US20-VR containing hydrocarbon components having a conventional boiling point above 530 ℃ and solid particulate catalyst;

at least a part of the second heavy oil US20-VR is returned to the first reaction section UR10 as long-circulating heavy oil US20-VR-TOUR10 to contact with heavy oil UR10F or the hydrogenation converted matter of heavy oil UR10F to carry out the first suspension bed hydrogenation thermal cracking reaction UR 10R.

the invention defines the ratio of the weight of US20-VR-TOUR10-WT of the long circulating heavy oil US20-VR-TOUR10 to the weight of US20-VR-OUT-WT of the second external row heavy oil US20-VR-OUT as K700;

K700 is (US20-VR-TOUR10-WT)/(US20-VR-OUT), and K700 is usually 0.01 to 100, usually 0.1 to 70, preferably 20 to 50.

according to the invention, in the first reaction stage UR10, a first solid particle catalyst UR10-CAT is used, which contains a molybdenum-based catalyst, and the working state of the molybdenum-based catalyst is molybdenum disulfide;

Defining the adding ratio of the externally added molybdenum-based catalyst IN the first reaction section UR10, and the ratio of the weight of the metal molybdenum of the externally added molybdenum-based catalyst, namely, US10-IN-MO-WT, to the weight of heavy oil UR10F, namely, UR10F-WT, as K900;

k900 (US10-IN-MO-WT) 1000000/(UR10F-WT), K900 is usually 5-300, usually 10-150, preferably 20-50.

in the present invention, generally, the heavy oil UR10F is mainly composed of hydrocarbon components having a normal boiling point higher than 450 ℃, and has a metal content of 10 to 1200 μ g/g and a carbon residue content of 10 to 30 wt%.

In the present invention, generally, the heavy oil UR10F is mainly composed of hydrocarbon components having a normal boiling point higher than 530 ℃, and has a metal content of 10 to 1200 μ g/g and a carbon residue content of 20 to 40 wt%.

according to the invention, generally, the carbon residue value of the first discharged heavy oil US10-VR-OUT is lower than 1.5 times of the carbon residue value of the heavy oil UR 10F;

the carbon residue value of the second externally discharged heavy oil US20-VR-OUT is 2 times lower than that of the first externally discharged heavy oil US 10-VR-OUT.

According to the invention, generally, the carbon residue value of the first discharged heavy oil US10-VR-OUT is 1.3 times lower than that of the heavy oil UR 10F;

The carbon residue value of the second externally discharged heavy oil US20-VR-OUT is 1.5 times lower than that of the first externally discharged heavy oil US 10-VR-OUT.

In the present invention, the operating conditions of the suspension bed hydrocracking reaction section are as follows: the reaction temperature is 390-445 ℃, the reactor pressure is 6-25 MPa, the volume concentration of gas-phase hydrogen is 50-95%, the volume ratio of gas to liquid is 100-2000 standard cubic meters per ton, and the reaction residence time is 5-150 minutes.

in the present invention, the first reaction stage UR10 may use a hydrogen donating hydrocarbon.

in the present invention, the second reaction stage UR20 may use a hydrogen donating hydrocarbon.

in the invention, the recovery system of the hydrogen-containing gas UR20-VPX obtained by separating the intermediate product or the final product of the second reaction stage UR20 can be partially or completely combined with the recovery system of the hydrogen-containing gas UR10-VPX obtained by separating the intermediate product or the final product of the first reaction stage UR 10.

In the invention, the hydrogen-containing gas UR20-VPX obtained by separating the intermediate product or the final product of the second reaction stage UR20 can be used in series through part or all of the flow of the first reaction stage UR 10.

According to the invention, hydrocarbon-containing oil gas obtained in the second separation section US20, US20-VPX, can be jointly recovered in the first separation section US 10.

According to the invention, hydrocarbon-containing oil gas obtained in the second separation section US20, US20-VPX, can be fed into the first separation section US10 to be jointly recovered with materials with similar gas phase compositions.

According to the invention, the feed containing solid particles and containing hydrocarbon components having a conventional boiling point above 530 ℃ obtained in the second separation stage U.S. Pat. No. 4, 20 is generally not fed into the flow scheme of the first separation stage U.S. Pat. No. 3, 10.

in general, the first efflux heavy oil, US10-VR-OUT, consists essentially of hydrocarbon components with conventional boiling points above 450 ℃;

the second external heavy oil US20-VR-OUT is mainly composed of hydrocarbon components with conventional boiling points above 450 ℃.

in general, the first externally discharged heavy oil, US10-VR-OUT, consists essentially of hydrocarbon components having a conventional boiling point above 530 ℃;

the second external heavy oil US20-VR-OUT is mainly composed of hydrocarbon components with conventional boiling points above 530 ℃.

in the present invention, generally, the operation mode of the suspension bed hydrogenation reactor used in the suspension bed hydrogenation reaction process is selected from 1 or more of the following:

option 1, an empty-tube bubbling bed suspended bed reactor system;

Option 2, in the reactor, the collected liquid of which the top is provided with a liquid collecting cup is pressurized by a circulating pump and then forcibly circulated and returned to the suspended bed reactor of the raw material inlet of the reactor;

Option 3, in the reactor, the collecting liquid of which the top is provided with a liquid collecting cup is pressurized by a circulating pump and then forcibly circulated and returned to the suspended bed reactor at the raw material inlet of the reactor, and the circulating pump conveys the circulating liquid and simultaneously conveys liquid material products to the downstream;

option 4, in the reactor, the collected liquid of which the top is provided with a liquid collecting cup is pressurized by a circulating pump and then forcibly circulated and returned to the suspended bed reactor at the raw material inlet of the reactor, and meanwhile, other collected liquids discharged by the collecting cup are conveyed to the downstream by other special feeding pumps to obtain liquid material products;

option 5, in the reactor, a liquid collecting cup is arranged at the top of the reactor to discharge liquid products, the liquid products are conveyed to the downstream by a special feeding pump, and a suspension bed reactor system for forced circulation of the liquid products is not arranged;

option 6, arranging a suspended bed reactor system of a central upstream and peripheral downstream type of an internal guide flow cylinder in the reactor;

Option 7, arranging a suspended bed reactor system with a central downward flow and peripheral upward flow pattern of an internal guide cylinder in the reactor;

Option 8, a suspended bed reactor system with an external reactor circulation pipe is formed, wherein the external reactor circulation pipe is used for the liquid phase downflow of the upper reaction zone of the reactor and the external reactor circulation flow returning to the lower reaction zone of the reactor;

Option 9, a gas stripping step of a tail end gas-liquid product entering a top liquid collecting cup and a gas-liquid separation step of the top liquid collecting cup are arranged in the reactor, the average molecular weight of an equilibrium liquid phase formed after the hydrogen-rich gas stripping gas and the tail end gas-liquid product are mixed is larger than that of the equilibrium liquid phase of the tail end gas-liquid product, and the concentration of hydrocarbon components with the conventional boiling point higher than 350 ℃ of the equilibrium liquid phase formed after the hydrogen-rich gas stripping gas and the tail end gas-liquid product are mixed is larger than that of the hydrocarbon components with the conventional boiling point higher than 350 ℃ of the equilibrium liquid phase of the tail end gas-liquid product; the slurry discharged from the liquid collecting cup in the final reactor of the reaction section through the flow guide pipe is used as a slurry product of the reaction section or a circulating reaction liquid phase.

The invention, heavy oil UR10F, comprising and consisting essentially of hydrocarbon components having a normal boiling point above 530 ℃; comprising an organometallic and or an asphaltene;

the hydrocracking reaction separation process in the suspension bed of heavy oil UR10F may include at least 3 reaction separation nodes, i.e. first reaction separation node UT10, second reaction separation node UT20, third reaction separation node UT 30;

a third reaction separation section UT30, which comprises a third reaction section UR30 and a third separation section US 30;

It is possible to contact a part of the second heavy oil US20-VR as the short cycle heavy oil US20-VR-TOUR20 of the second reaction separation node UT20 back to the second reaction section UR20 to be contacted with the heavy oil UR20F or the hydroconverter of the heavy oil UR20F for the second cycle hydrocracking reaction;

it is possible to return a part of the second heavy oil US20-VR as long-circulating heavy oil US20-VR-TOUR10 to the first reaction section UR10 to contact with the heavy oil UR10F or the hydroconverter of the heavy oil UR10F to carry out the first suspended bed hydrocracking reaction UR 10R;

(5) In the third reaction stage UR30, heavy oil UR30F containing second external row heavy oil US20-VR-OUT is subjected to a third suspension bed hydrocracking reaction UR30R to convert into a third hydrogenation reaction product UR30P in the presence of hydrogen, normal liquid hydrocarbons, third solid particle catalyst UR30-CAT, and possibly hydrogen-supplying hydrocarbons, and possibly other solid particles; the third suspension bed hydrocracking reaction UR30R makes at least a part of the hydrocarbon components with normal boiling point higher than 530 deg.C complete hydrocracking reaction to produce hydrocarbon products with smaller molecular weight;

A stream UR30P-X based on the third hydrogenation reaction product UR30P comprising hydrocarbon components having a conventional boiling point above 530 ℃ and solid particulate catalyst enters the third separation section US 30;

(6) In the third separation section US30, the stream UR30P-X is separated to yield a third hydrogen-rich gas US30H, a third external light distillate US30-MP, a third heavy oil US30-VR comprising hydrocarbon components having a conventional boiling point above 530 ℃ and a solid particulate catalyst;

at least a portion of the third heavy oil, US30-VR, is used as the third efflux heavy oil, US 30-VR-OUT;

It is possible to contact a part of the third heavy oil US30-VR as short cycle heavy oil US30-VR-TOUR30 of the third reaction separation node UT30 back to the third reaction section UR30 to be contacted with the hydroconversion of the heavy oil UR30F or the heavy oil UR30F for the third cycle hydrocracking reaction;

A part of the third heavy oil US30-VR is returned to the second reaction section UR20 as the long-circulating heavy oil US30-VR-TOUR20 of the third reaction separation joint UT30 to be contacted with the hydroconversion of the heavy oil UR20F or the heavy oil UR20F for the second hydrocracking reaction;

it is possible to return a part of the third heavy oil US30-VR as the long-circulating heavy oil US30-VR-TOUR10 of the third reaction separation node UT30 to the first reaction section UR10 to contact with the hydroconverter of the heavy oil UR10F or the heavy oil UR10F for the first hydrocracking reaction.

the hydrocracking reaction separation process in the suspension bed of heavy oil UR10F may include at least 4 reaction separation nodes, i.e. first reaction separation node UT10, second reaction separation node UT20, third reaction separation node UT30, fourth reaction separation node UT 40;

a fourth reaction separation section UT40, comprising a fourth reaction section UR40 and a fourth separation section US 40;

(7) In the fourth reaction section UR40, heavy oil UR40F containing third discharged heavy oil US30-VR-OUT is subjected to a fourth suspended bed hydrocracking reaction UR40R to convert to a fourth hydrogenation reaction product UR40P in the presence of hydrogen, normal liquid hydrocarbons, fourth solid particle catalyst UR40-CAT, and possibly hydrogen-supplying hydrocarbons, and possibly other solid particles of miscible materials; the fourth suspension bed hydrocracking reaction UR40R makes at least a part of the hydrocarbon components with normal boiling point higher than 530 deg.C complete hydrocracking reaction to produce hydrocarbon products with smaller molecular weight;

a stream UR40P-X based on the fourth hydrogenation reaction product UR40P comprising hydrocarbon components having a conventional boiling point above 530 ℃ and solid particulate catalyst enters the fourth separation stage US 40;

(8) In a fourth separation section US40, the separation stream UR40P-X yields a fourth hydrogen-rich gas US40H, a fourth external light distillate US40-MP, a fourth heavy oil US40-VR containing hydrocarbon components having a conventional boiling point above 530 ℃ and solid particulate catalyst;

at least a portion of the fourth heavy oil, US40-VR, is used as the fourth extra heavy oil, US 40-VR-OUT;

it is possible to return a part of the fourth heavy oil US40-VR as short cycle heavy oil US40-VR-TOUR40 of the fourth reaction separation node UT40 to the fourth reaction section UR40 to contact with the heavy oil UR40F or the hydroconverter of the heavy oil UR40F for the fourth cycle hydrocracking reaction;

A part of the fourth heavy oil US40-VR is returned to the third reaction section UR30 as the long-circulating heavy oil US40-VR-TOUR30 of the fourth reaction separation joint UT40 to be contacted with the hydroconversion of the heavy oil UR30F or the heavy oil UR30F for the third hydrocracking reaction;

a part of the fourth heavy oil US40-VR is returned to the second reaction section UR20 as the long-circulating heavy oil US40-VR-TOUR20 of the fourth reaction separation joint UT40 to be contacted with the hydroconversion of the heavy oil UR20F or the heavy oil UR20F for the second hydrocracking reaction;

it is possible to return a part of the fourth heavy oil US40-VR as the long-circulating heavy oil US40-VR-TOUR10 of the fourth reaction separation section UT40 to the first reaction section UR10 to contact with the hydroconversion of the heavy oil UR10F or the heavy oil UR10F for the first hydrocracking reaction.

in the invention, the operating conditions of any suspension bed hydrogenation thermal cracking reaction section can be as follows: the reaction temperature is 390-445 ℃, the reactor pressure is 6-25 MPa, the volume concentration of gas-phase hydrogen is 50-95%, the volume ratio of gas to liquid is 100-2000 standard cubic meters per ton, and the reaction residence time is 5-150 minutes.

In the present invention, 1 or more suspension bed hydrocracking reaction stages may use a hydrogen-donating hydrocarbon.

in the present invention, the recovery system of the hydrogen-containing gas obtained by separating the intermediate product or the final product in the downstream reaction section may be partially or entirely combined with the recovery system of the hydrogen-containing gas obtained by separating the intermediate product or the final product in the upstream reaction section.

according to the invention, the hydrogen-containing gas obtained by separating the intermediate product or the final product of the downstream reaction section can be used in series through part or all of the flow of the upstream reaction section.

according to the invention, hydrocarbon-containing oil gas obtained in the downstream separation section can be jointly recovered in the upstream separation section.

According to the invention, hydrocarbon-containing oil gas obtained in the downstream separation section can enter the upstream separation section to be jointly recovered with materials with the composition close to that of a gas phase.

According to the invention, the material containing solid particles and containing hydrocarbon components with a normal boiling point higher than 530 ℃ obtained in the downstream separation section is not fed into the flow path of the upstream separation section.

According to the invention, the carbon residue value of the discharged heavy oil of the downstream separation section is 1.5 times lower than that of the discharged heavy oil of the upstream separation section.

in the invention, generally, the carbon residue value of the discharged heavy oil of the downstream separation section is 1.3 times lower than that of the discharged heavy oil of the upstream separation section.

in the present invention, generally, the effluent heavy oil of any downstream separation stage consists essentially of hydrocarbon components having conventional boiling points above 450 ℃.

in the present invention, in general, the discharged heavy oil of any downstream separation section consists essentially of hydrocarbon components having a conventional boiling point above 530 ℃.

In the present invention, generally, the total conversion rate of hydrocarbon components having a normal boiling point higher than 530 ℃ in the heavy oil feed without the circulating oil in any of the downstream reaction stages is 60 to 90% by weight.

In the present invention, generally, any downstream reaction zone has an overall conversion of hydrocarbon components having a normal boiling point of greater than 530 ℃ of from 30 to 60 wt.%, based on the total heavy oil feed.

option 1, an empty-tube bubbling bed suspended bed reactor system;

according to the invention, normally, the discharged heavy oil USEND-VR-OUT discharged from the last separation section enters a deep vaporization process ENDKS to be separated into deep vaporization gas ENDKS-V and deep vaporization liquid ENDKS-L, and at least part of hydrocarbons in the discharged heavy oil USEND-VR-OUT are vaporized and enter the deep vaporization gas ENDKS-V; the total weight of the hydrocarbons in the deep vaporization liquid ENDKS-L is lower than that in the discharged heavy oil USEND-VR-OUT;

At least a part of the deep boil-off gas ENDKS-V may enter a separation section of a suspension bed hydrogenation thermal cracking reaction separation process of the heavy oil UR10F for combined recovery.

the present invention, generally, the deep vaporisation process ENDKS, operates in a mode selected from 1 or more of the following:

Option 1, a deep reduced pressure vaporization mode is adopted;

Option 2, a film evaporation reduced pressure deep vaporization mode is adopted;

Option 3, a gas stripping vaporization mode of mixing and heating high-temperature gas heat carriers and then carrying out flash evaporation vaporization is adopted;

option 4, a gas stripping vaporization mode of mixing and heating high-temperature gas heat carriers and then carrying out flash vaporization is adopted; the process medium of the high-temperature gas heat carrier is hydrocarbon gas in a separation section in a suspension bed hydrogenation thermal cracking reaction separation process of heavy oil UR 10F;

Option 5, adopting a gas stripping vaporization mode of mixing and heating high-temperature gas heat carriers and then carrying out flash evaporation vaporization; the process medium of the high-temperature gas heat carrier is heated by using a heater of hydrocarbon gas in a separation section of a suspension bed hydrogenation thermal cracking reaction separation process of heavy oil UR 10F.

Drawings

FIG. 1 is a schematic flow chart of a two-stage basic flow of the separation method of the present invention.

FIG. 1 shows a schematic flow chart of a two-stage basic flow of the fractional suspended bed hydrocracking reaction-separation method of the present invention, which comprises a first reaction-separation section UT10 and a second reaction-separation section UT 20. Wherein the first reaction separation section UT10 comprises a first reaction section UR10 and a first separation section US10, and the second reaction separation section UT20 comprises a second reaction section UR20 and a second separation section US 20.

as shown in FIG. 1, fresh raw material residue UR10F enters first reaction stage UR10 through pipe 101, first reaction stage hydrogen UR10H enters first reaction stage UR10 through pipe 102, suspension bed hydrocracking reaction UR10R of the first reaction stage is carried out in the presence of hydrogen, high dispersity hydrocracking catalyst, hydrogen supply solvent possibly used and coke carrying agent possibly used to generate first reaction stage suspension bed hydrocracking reaction product UR10P, reaction product UR10P enters first separation stage US10 through pipe 111 to separate out hydrogen-rich gas, distillate US10MP discharged through pipe 129 and first separation stage residue US10-VR, the first separation stage residue US10-VR contains unconverted residue component, thermally cracked residue product, catalyst solid, raw material converted substance (metal organic metal sulfide) and other solid particles.

as shown in FIG. 1, in the first separation section US10, the carrying amounts of catalyst solid, raw organometallic conversion (metal sulfide) and other solid particles in the reaction product UR10P are all concentrated in the discharged residue of the first separation section US10-VR-OUT, since the weight flow rate of the discharged residue from the first separation section US10-VR-OUT (e.g. 3% unconverted residue) is much less than the weight flow rate of the fresh feed residue UR10F, therefore, the carrying amount of the catalyst solid, the raw material organic metal converted matter (metal sulfide) and other solid particles of the first separation section discharged residual oil US10-VR-OUT is many times of the carrying amount of the catalyst solid carried by the fresh residual oil, for example, the carrying amount of the catalyst solid, the raw material organic metal converted matter (metal sulfide) and other solid particles in the first separation section discharged residual oil US10-VR-OUT is generally increased to 33 times for the working condition of 3% of unconverted residual oil.

As shown in FIG. 1, in the first reaction separation section UT10, in order to form the condition that the liquid phase of the first reaction section UR10 carries a sufficient amount of catalyst solid particles to meet the concentration requirement of the liquid phase space catalyst of the hydrocracking reaction and to reduce the addition amount of fresh catalyst to reduce the catalyst cost, a part (usually most of the first separation section residuum US10-VR) is used as short cycle residuum US10-VR-TOUR10 and returned to the first reaction section UR10 through the pipe 122 to be mixed and contacted with the fresh raw material residuum UR 10F; for example, for the working condition of 3% unconverted residual oil, the reaction condition of 68 wt% per pass conversion, the amount of short cycle residual oil US10-VR-TOUR10 is 42.65 wt% of the fresh residual oil of the raw material, and the weight carrying rate of the molybdenum disulfide solid particles in the catalyst in the total residual oil of the first reaction section is controlled to be 0.002: 1, so that the weight carrying rate of the molybdenum disulfide solid particles in the catalyst in the fresh raw material is required to be 0.0001875: 1 (about 188 μ g/g); on the other hand, the properties of the asphaltenes in the first reaction section product residual oil are much worse than those of the asphaltenes in the fresh residual oil UR10F, for example, the relative value of the carbon residue of the first reaction section product residual oil is usually 20-30% higher or even more.

Table 1 is a summary table of the operating conditions of the first reaction separation section UT 10.

TABLE 1 summary of operating conditions of the first reaction separation section UT10

For a 100 million ton/year resid slurry bed hydrocracking unit operating under the conditions listed in Table 1, the first separation stage discharges a 3 million ton/year resid US10-VR-OUT containing 178.5 ton/year catalyst molybdenum disulfide solid particles.

in order to recover most of the hydrocarbons in the oil residue US10-VR-OUT discharged from the first separation section, a second reaction separation section is set up according to the present invention, as shown in fig. 1, the oil residue US10-VR-OUT discharged from the first separation section enters the second reaction section UR20 through a pipe 121 (or 201), the hydrogen gas UR20H of the second reaction section enters the second reaction section UR20 through a pipe 202, the suspension bed hydrocracking reaction UR20R of the second reaction section is performed under the conditions of hydrogen gas, high dispersity hydrocracking catalyst (usually the catalyst carried in the oil residue US10-VR-OUT discharged from the first separation section is satisfied), possibly used hydrogen solvent and possibly used coke carrying agent, the suspension bed hydrocracking reaction UR20P of the second reaction section is generated, the reaction product UR20P enters the second separation section US20 through a pipe 211 to separate hydrogen-rich distillate oil US20MP discharged through a pipe 229 and the oil residue US 20-VR-20, the second separation stage resid US20-VR contains unconverted resid components, thermally cracked resid products, catalyst solids, organometallic starting material transformations (metal sulfides), and other solid particles.

As shown in FIG. 1, in the second separation stage US20, the carrying amount of catalyst solids, raw organometallic conversions (metal sulfides), and other solid particles in the reaction product UR20P is totally concentrated in the second separation stage discharge residuum US20-VR-OUT, and since the weight flow rate (e.g., 10% unconverted residuum) of the second separation stage discharge residuum US20-VR-OUT is much less than the weight flow rate of the second reaction stage feed UR20F (i.e., US10-VR-OUT), the carrying amount of catalyst solids, raw organometallic conversions (metal sulfides), and other solid particles in the second separation stage discharge residuum US20-VR-OUT is many times that of the second reaction stage feed UR20F (i.e., US10-VR-OUT), e.g., 10% unconverted residuum conditions, the second separation stage discharge residuum US20, VR-OUT carries catalyst solids, The carrying capacity of the raw material organometallic conversion substances (metal sulfides) and other solid particles is improved by 10 times in general.

as shown in fig. 1, at the second reaction separation node UT20, in order to form the condition that the liquid phase of the second reaction section UR20 carries a sufficient amount of catalyst solid particles (it is usually desirable that the liquid phase catalyst carrying rate of the second reaction section UR20 is 3-4 times higher than that of the first reaction section UR10) to meet the concentration requirement of the liquid phase space catalyst of the second reaction section UR20 hydrocracking reaction, or in order to control the single-pass conversion rate of the second reaction section UR20 to be appropriately low to reduce the operation temperature and inhibit coking, it is necessary to mix and contact a part (usually most of the second separation section residual oil US20-VR) as short-cycle residual oil US20-VR-TOUR20, which is returned to the second reaction section UR20 through the pipe 222, with the second reaction section feed UR20F (i.e. US 10-VR-OUT); for example, for 10% unconverted residue condition, reaction conditions of 50 wt% per pass conversion, the amount of oil recycled is 80% of the feed UR20F (i.e. US10-VR-OUT) of the second reaction zone.

Table 2 is a summary table of the operating conditions of the second reaction separation section UT 20.

TABLE 2 summary of operating conditions of the second reaction separation section UT20

As can be seen from Table 2, the process shown in FIG. 1 achieves the task of recovering most of the hydrocarbons in the residue US10-VR-OUT discharged from the first separation stage, with a recovery rate of 90%, and for a 100-ten-thousand-ton/year residue suspension bed hydrocracking unit, operating under the above conditions, the amount of the recovered residue is 2.7-ten-thousand-ton/year, and the income is increased by 0.54-hundred-million RMB, calculated according to the increased benefit of about 2000 RMB/ton.

As can be seen from Table 2, the weight carrying rate of the molybdenum disulfide solid particles carried by the second reaction section total residual oil is 31250 μ g/g, which is 15.6 times of the weight carrying rate of the molybdenum disulfide solid particles carried by the first reaction section total residual oil 2000 μ g/g, which is much greater than the desired value by 3-4 times.

It can also be seen from table 2 that the weight carrying rate of the disulfide carrying non-catalyst metal carried by the second reaction stage total residue is 50000 μ g/g, the weight carrying rate of the total solids carried by the second reaction stage total residue is 81250 μ g/g, and the weight concentration of the liquid-solid total material is as high as 7.5 wt%, which high concentration brings the following effects:

Some metal sulfides in the non-special catalyst solid of the organic metal product carried by the residual oil have the function of activating hydrogen, so that the catalyst can be regarded as a self-produced hydrogenation catalyst, and the catalytic hydrogenation effect is enhanced;

Secondly, the abrasion speed of high-concentration metal solids on equipment, pipelines and throttling parts (regulating valves and flow measuring instruments) in the system is increased;

High concentrations of metal solids tend to result in increased distillate solids concentration in the second separation stage.

On the other hand, the property of the asphaltene in the product residual oil of the second reaction section is much worse than that of the asphaltene in the product residual oil of the first reaction section, for example, the relative value of carbon residue is usually higher by 30-50% or even more.

On the basis of retaining the advantages of the flow scheme shown in figure 1 (recovering hydrocarbons in the residue and concentrating solids in the discharged residue), the function of reducing the amount of fresh catalyst is arranged, and a part of second separation section residue US20-VR is recycled to the first reaction section UR10 as long-circulating residue US20-VR-TOUR10 through a pipeline 223, and the specific flow scheme is shown in figure 2.

FIG. 2 is a schematic flow chart of a two-stage process for setting a long circulating residual oil flow in the sectional type heavy oil suspension bed hydro-thermal cracking reaction separation method of the present invention.

The principle flow chart of the two-stage flow of the long circulating residual oil flow in the sectional type heavy oil suspension bed hydrocracking reaction separation method of the invention shown in fig. 2 is different from the two-stage basic flow of the sectional type heavy oil suspension bed hydrocracking reaction separation method of the invention shown in fig. 1 only in that: a long cycle residual oil US20-VR-TOUR10 flow path is set up.

because the carrying proportion of the catalyst molybdenum disulfide solid particles in the second separation section residual oil is 333 times of the carrying proportion of the catalyst molybdenum disulfide solid particles in the fresh residual oil, a small amount of second separation section long circulation residual oil US20-VR-TOUR10 is circulated to the first reaction section, so that the carrying proportion of the catalyst molybdenum disulfide solid particles carried by the total residual oil raw material (short circulation residual oil without the first reaction separation section is considered only by the sum of the fresh residual oil UR10F and the long circulation residual oil US20-VR-TOUR10) outside the first reaction separation section can be greatly increased, and the consumption of the fresh catalyst can be greatly reduced.

as shown in the flow chart of fig. 2, the first reaction section receives 2 circulating residues, and the process targets or process advantages are as follows:

first reaction separation section UT10 and second reaction section UT20 form the overall conversion pathway for fresh resid UR10, while the ratio of catalyst carryover in the overall resid of first reaction section UR10, the ratio of the discharged resid US10-VR-OUT weight flow rate of first fractionation section US10 to the short circulating resid US10-VR-TOUR10 weight flow rate, and the ratio of the discharged resid US20-VR-OUT weight flow rate of second fractionation section US20 to the long circulating resid US20-VR-TOUR10 weight flow rate, collectively determine the amount of fresh catalyst added (or the amount of catalyst carryover in the final discharged resid), since the "ratio of catalyst carryover the entire resid of first reaction section, the ratio of the discharged resid US10-VR-OUT weight flow rate of first fractionation section to the short circulating resid US10-VR-TOUR10 weight flow rate" generally varies only within a small range, "the ratio of the discharged residue US20-VR-OUT weight flow rate of the second fractionation section to the long cycle residue US20-VR-TOUR10 weight flow rate" is generally a sensitive indicator for determining the amount of fresh catalyst added (or the amount of catalyst carried in the final discharged residue);

in other words, the ratio of the weight flow rate of discharged residue US20-VR-OUT in the second fractionation section to the weight flow rate of long circulating residue US20-VR-TOUR10 generally determines the amount of fresh catalyst added (or the amount of catalyst carried in the final discharged residue);

compared with the EST process, the flow shown in the figure 2 of the invention can improve the catalyst carrying ratio of the first reaction section total residual oil by times under the condition of the same fresh catalyst consumption, therefore, the invention can process the fresh residual oil with poorer quality;

Compared with the EST process, the flow shown in the figure 2 of the invention can reduce the consumption of fresh catalyst by times under the condition that the ratio of the catalyst carried by the total residual oil in the first reaction section is the same, therefore, the invention can obviously reduce the consumption of the catalyst;

secondly, short cycle residual oil US10-VR-TOUR10 of a first reaction separation joint UT10 is used for circulation accumulation balance of unconverted residual oil hydrocarbon components and circulation accumulation balance of solid particles of a catalyst in a first reaction section under the condition that the carrying proportion of solid particles of the catalyst in total residual oil raw materials (the cycle residual oil US10-VR-TOUR10 without the first reaction separation joint is considered, and only the sum of fresh residual oil UR10F and long cycle residual oil US20-VR-TOUR10 is considered) is unchanged outside the first reaction separation joint, and the single-pass conversion rate of the first reaction section is usually low (for example, 55-80 wt%), so the flow rate of short cycle residual oil US10-VR-TOUR10 is large;

fresh residuum UR10F and short cycle residuum US10-VR-TOUR10 together determine the basic properties of the total residuum of the first reaction zone;

compared with the EST process, the flow scheme shown in the figure 2 of the invention has the advantages that under the condition that the ratio of the catalyst carried by the total residue in the first reaction section is the same, the consumption of the fresh catalyst can be reduced by times, and the residue property of the first reaction section is only slightly deteriorated or not deteriorated, so that the first reaction section has basically identical optimized reaction conditions;

thirdly, the weight ratio of the catalyst to the hydrocarbon oil of the long circulating residual oil US20-VR-TOUR10 is far higher than that of the catalyst to the hydrocarbon oil of the short circulating residual oil US10-VR-TOUR10, so that the catalyst has high selectivity of a circulating accumulated catalyst, and the circulating amount of the poor residual oil entering the first reaction section is greatly reduced;

different from the EST process, the flow shown in the figure 2 can realize the decoupling of the circulation of asphaltene and the circulation of catalyst in the circulating residual oil in the first reaction section, and the quantity of the poor residual oil from the second separation section, namely the long circulating residual oil brought into the first reaction section is less while reducing the consumption of fresh catalyst, namely long circulating residual oil US20-VR-TOUR10 is used for accumulating solid particles of equilibrium catalyst, so that the dual aims of optimizing the operation condition of the first reaction section and reducing the consumption of fresh catalyst can be realized;

therefore, the method is more suitable for processing the extremely poor residual oil (with extremely high metal content and extremely high carbon residue);

fourthly, since the long circulating residual oil US20-VR-TOUR10 also passes through the second reaction section UR20, the long circulating residual oil US20-VR-TOUR10 is also the circulating oil of the second reaction section UR20, so that the number of the special short circulating residual oil US20-VR-TOUR20 of the second reaction section UR20 can be reduced, and even the special short circulating residual oil US20-VR-TOUR20 is eliminated;

the long cycle residual oil US20-VR-TOUR10 with a proper flow ratio can maintain the necessary liquid phase catalyst carrying rate of the second reaction section while fully reducing the consumption of fresh catalyst, because the liquid phase catalyst carrying rate of the second reaction section is equal to the catalyst carrying rate of the discharged residual oil US10-VR-OUT of the first section at the lowest, and the catalyst carrying rate of the discharged residual oil US10-VR-OUT of the first section is usually 3-5 times of the catalyst carrying rate of the total residual oil of the first reaction section;

compared with the second stage short cycle residual oil US20-VR-TOUR20, the long cycle residual oil US20-VR-TOUR10 is mixed with the fresh residual oil UR10F and then is converted into residual oil discharged from the first separation section through the first reaction separation section, and the concentration of carried catalyst solid particles is diluted, so that the catalyst solid (mainly added catalyst solid particles) carrying rate of the second reaction section is reduced to a certain extent, and the solid particle carrying rate is prevented from being too high;

due to the existence of the long-circulation residual oil US20-VR-TOUR10, the second reaction section can conveniently operate according to a mode of low single-pass conversion rate such as 30-50 percent, so that an operation mode of low reaction temperature rise can be realized, and a task can be finished by using an empty-cylinder suspension bed reactor under most conditions.

Based on the flow chart shown in FIG. 2, for a 100 ten thousand tons/year residue suspension bed hydrocracking unit with the same raw residue, the operation results and operation conditions of 2 catalyst additions (fresh residue molybdenum sulfide carrying rate 187.5 μ g/g, and required amount for controlling the total residue molybdenum disulfide carrying rate 2000 μ g/g in the first reaction stage) of fresh residue (with the organometallic sulfide yields of 300 μ g/g respectively) are predicted and shown in Table 3, and other calculation reference conditions include:

two reaction separation sections are used, and 3 ten thousand tons/year long cycle residual oil US20-VR-TOUR10 is used;

Assuming that the hydrocarbons in the long-circulating residue US20-VR-TOUR10 do not react in the first reaction stage UR10, taking into account the particulate matter carrying effect thereof;

the total conversion of the first reaction stage fresh residue UR10F was 97 wt%;

The first reaction stage "fresh resid UR10F and short cycle resid" has a single pass conversion of 68 wt.%;

the overall conversion of the second reaction stage intrinsic feed (unconverted residue of the first reaction stage fresh residue UR 10F) UR20F was 90 wt.%;

The conversion per pass of the total second reaction zone residue (including second reaction zone intrinsic feed, second reaction zone short cycle residue US20-VR-TOUR20, second reaction zone long cycle residue US20-VR-TOUR10) is reported by calculation to be no more than 50 wt.%.

Table 3 is a summary of the operating conditions for the two reaction separation sections for the two run schemes.

TABLE 3 summary of the operating conditions of the two reaction separation sections for the two operating schemes

as can be seen from table 3:

firstly, after long-cycle residual oil US20-VR-TOUR10 is used, under the condition of ensuring that the weight carrying rate of molybdenum disulfide solid particles carried by the total residual oil of a first reaction section is not changed to 2000 mug/g, the consumption of the catalyst is reduced to 17.4% (namely 1/5.74) of the original consumption, 82.6% is reduced, and the reduction range is huge;

secondly, after long-circulation residual oil US20-VR-TOUR10 is used, under the condition that the addition amount of the catalyst is not changed, the weight carrying rate of the molybdenum disulfide solid particles carried by the total residual oil of the first reaction section is improved from 2000 mu g/g to 11480 mu g/g, namely the weight carrying rate is improved by 5.74 times, and the improvement amplitude is large;

the amount of the short circulating residual oil entering the first reaction separation section is 42.65 percent by weight (for fresh residual oil) which is 14.22 times of the amount of the long circulating residual oil which is 3 percent by weight (for fresh residual oil), and the degree of the first reaction section polluted by the inferior residual oil is very low;

And fourthly, the solid weight carrying rate of the total residual oil of the second reaction section is far higher than that of the total residual oil of the first reaction section, so that the operation range of the liquid with high solid concentration is strictly limited in the second reaction separation section, and the first reaction separation section is in a liquid operation state with low solid concentration.

FIG. 3 is a schematic flow chart of the deep vaporization step of the residual oil discharged from the final separation section of the fractional suspended bed hydrocracking reaction separation method for heavy oil according to the present invention.

as shown in fig. 3, a principle flow chart of the deep vaporization step of the discharged residual oil at the final separation section of the fractional suspended bed hydrocracking reaction separation method of the present invention is that a deep vaporization step is used to further reduce the amount of hydrocarbon oil in the discharged residual oil and further concentrate solid particles.

as shown in fig. 3, the discharged heavy oil USEND-VR-OUT discharged from the last separation stage enters the deep vaporization process ENDKS along the pipe 221, and is separated into deep vaporization gas ENDKS-V discharged along the pipe 701 and deep vaporization liquid ENDKS-L discharged along the pipe 702, and at least a part of hydrocarbons in the discharged heavy oil USEND-VR-OUT are vaporized into the deep vaporization gas ENDKS-V; the total weight of the hydrocarbons in the deep vaporization liquid ENDKS-L is lower than that in the discharged heavy oil USEND-VR-OUT; at least a part of the deep boil-off gas ENDKS-V can enter a separation section of a suspension bed hydrogenation thermal cracking reaction separation process of the heavy oil UR10F for combined recovery.

The deep vaporization process ENDKS works in a mode selected from 1 or more of the following modes:

Option 1, a deep reduced pressure vaporization mode is adopted;

Detailed Description

The present invention is described in detail below.

The pressure in the present invention refers to absolute pressure.

The conventional boiling point of the invention refers to the vapor-liquid equilibrium temperature of a substance at one atmospheric pressure.

the conventional boiling range as referred to herein refers to the conventional boiling range of the distillate fraction.

the specific gravity of the present invention refers to the ratio of the density of a liquid at ordinary pressure and 15.6 ℃ to the density of a liquid at ordinary pressure and 15.6 ℃ unless otherwise specified.

The compositions or concentrations or amounts or yield values of the components described herein are weight basis values unless otherwise specified.

the conventional gaseous hydrocarbon refers to hydrocarbon which is gaseous under conventional conditions, and comprises methane, ethane, propane and butane.

The conventional liquid hydrocarbon refers to hydrocarbon which is liquid under conventional conditions, and includes pentane and hydrocarbon with higher boiling point.

the impurity elements in the invention refer to non-hydrogen, non-carbon and non-metal components in the raw oil, such as oxygen, sulfur, nitrogen, chlorine and the like.

the impurity component in the invention refers to the hydrogenation conversion product of non-hydrocarbon component in the raw oil, such as water, ammonia, hydrogen sulfide, hydrogen chloride and the like.

The light hydrocarbon, which is a naphtha component, referred to herein is a conventional liquid hydrocarbon having a conventional boiling point of less than 200 ℃.

The conventional boiling point of the hydrocarbon contained in the diesel component is usually 155-375 ℃, and the conventional boiling point is usually 200-350 ℃.

The normal boiling point of the hydrocarbon contained in the wax oil component is usually 330-575 ℃, and is usually 350-530 ℃.

the heavy oil component of the present invention contains hydrocarbons having a conventional boiling point generally greater than 350 c, generally greater than 450 c, specifically greater than 530 c, and more specifically greater than 575 c.

the atmospheric resid component of the present invention, typically an atmospheric fractionation tower bottoms, contains hydrocarbons having a conventional boiling point typically greater than 330 c, typically greater than 350 c, and particularly greater than 370 c.

The vacuum residue component of the present invention, typically a vacuum fractionation tower bottoms, typically contains hydrocarbons having a conventional boiling point generally greater than 450 c, typically greater than 530 c, and particularly greater than 575 c.

The medium hydrocarbon refers to hydrocarbon with a conventional boiling point of 230-400 ℃.

The heavy hydrocarbon refers to hydrocarbon with a conventional boiling point higher than 350 ℃.

the hydrogen-oil volume ratio refers to the ratio of the standard state volume flow of hydrogen to the volume flow of a specified oil material flow at normal pressure and 20 ℃.

The hydrogenation reaction space, which refers to a process fluid flow space where the hydrogenation reaction takes place, may be a reaction inner space such as a hollow cylinder reactor zone, a gas stripping hydrogen mixing zone, a liquid collecting cup upper space region, etc., and may be a reactor outer space such as a pipe inner space, a valve inner space, a mixer inner space, a pump inner space, etc.

the aromatic ring number of the polycyclic aromatic hydrocarbon is more than or equal to 3.

in the upflow hydrogenation reactor, the macroscopic flow leading direction of the process medium in the reaction space or the hydrogenation catalyst bed layer is from top to bottom.

the upflow type expanded bed reactor is a vertical upflow type reactor, and belongs to an expanded bed reactor when a catalyst is used; the vertical type means that the central axis of the reactor is vertical to the ground in a working state after installation; the upflow means that the material main body flows in the reaction process from bottom to top to pass through the reaction space or the catalyst bed layer or flow in the same direction with the upward catalyst; the expanded bed means that a catalyst bed layer is in an expanded state in a working state, the expansion ratio of the catalyst bed layer is defined as the ratio KBED of the maximum height CWH of the working state when a reaction material passes through the catalyst bed layer and the height CUH of an empty bed standing state of the catalyst bed layer, generally, when the KBED is lower than 1.10, the bed is called a micro-expanded bed, when the KBED is between 1.25 and 1.55, the bed is called an ebullated bed, and a suspended bed is considered as the most extreme form of the expanded bed.

The back-mixed flow expanded bed reactor refers to an operation mode of using a reaction zone or a main reaction zone of the expanded bed reactor, wherein liquid flow back-mixing or circulating liquid exists; the return flow or the circulating liquid refers to at least one part of liquid phase XK-L in the intermediate product XK or the final product XK at the flow point K as a circulating liquid flow XK-LR to return to an upstream reaction zone of the flow point K, and the reaction product of the circulating liquid flow XK-LR flows through the point K and exists in XK. The mode of forming the back flow can be any suitable mode, such as arranging a built-in inner circulation tube, a built-in outer circulation tube, a built-in liquid collecting cup, a flow guide tube, a circulating pump, an external circulating tube and the like.

the invention discloses a liquid product circulating upflow type expanded bed hydrogenation reactor system, which is characterized in that a liquid product returns to an upstream reaction space for circular processing or liquid product circulation exists in an operation mode of a reaction zone or a main reaction zone of an expanded bed reactor; the liquid product circulation in the hydrogenation reactor refers to that at least a part of the liquid phase XK-L in the intermediate product XK or the final product XK at the flow point K is used as a circulating liquid flow XK-LR to return to a reaction area upstream of the flow XK, and the circulating liquid flow XK-LR passes through the point K and exists in XK. The way of forming the circulation of the liquid product can be any suitable way, but a gas-liquid separation zone must be arranged in the head space in the reactor to obtain the circulating liquid and other products, namely a built-in liquid collecting cup, a diversion pipe and a circulating booster, wherein the circulating booster is usually a circulating pump and can be arranged inside or outside the reactor.

the liquid collecting cup or the liquid collector arranged in the reactor refers to a container which is arranged in the reactor and is used for collecting liquid, the upper part or the upper part of the container is usually provided with an opening on the side surface, and a guide pipe is arranged on the bottom part or the lower part of the container for conveying or discharging the collected liquid; the top liquid collector of the expanded bed reactor is usually arranged in a liquid removal area of gas-liquid materials to obtain liquid and gas-liquid mixed phase material flow containing a small amount of bubbles or obtain liquid and gas, and at least part of liquid phase products are pressurized by a circulating pump and then return to a reaction space for circular processing. Typical examples are the heavy OIL ebullated bed hydrogenation reactor, the HTI coal hydrogenation direct liquefaction reactor used in the H-OIL process.

the thermal high separator refers to a gas-liquid separation device for separating intermediate products or final products of hydrogenation reaction.

The two-stage or multi-stage hydrogenation method of the invention refers to a hydrogenation method comprising two reaction stages or a plurality of reaction stages.

In a specific reaction separation section of the present invention, which comprises a reaction section (or a reaction part) and a separation section (a separation part, usually comprising a vacuum fractionation process), the flow structure of the reaction section may comprise 1 reaction stage or 2 reaction stages operated in series or a plurality of reaction stages operated in series, that is, may be a 1-stage reaction section or a 2-stage reaction section or a multi-stage reaction section.

The hydrogenation reaction stage refers to a flow path section from the beginning of a hydrogenation reaction process of a hydrocarbon raw material to the gas-liquid separation of a hydrogenation product of the hydrocarbon raw material to obtain at least one liquid-phase product consisting of at least one part of generated oil, and comprises the hydrogenation reaction process of the hydrogenation reaction stage and the gas-liquid separation process of at least one part of the hydrogenation reaction product of the hydrogenation reaction stage. Therefore, the primary hydrogenation reaction section refers to a reaction part flow mode that the processing process of the initial hydrocarbon raw material only comprises one hydrogenation reaction step and a gas-liquid separation process of a product of the hydrogenation reaction step, wherein one hydrogenation reaction step can use 1 or 2 or more hydrogenation reactors operated in series according to requirements, so the number and the form of the reactors are not the basis for determining the reaction level, and the reaction step consisting of one or a plurality of series reactors and the product separator are combined together to form the hydrogenation reaction level in the sense of completion.

The second-stage hydrogenation reaction section refers to a reaction part flow mode that the processing flow of the initial hydrocarbon raw material comprises a liquid material processing flow which is operated in series and is formed by two different hydrogenation reaction steps and a gas-liquid separation process of products of the corresponding hydrogenation reaction steps, wherein at least one part of material flow formed by oil generated by first-stage hydrogenation enters the second-stage hydrogenation reaction process.

the three-stage hydrogenation reaction section refers to a reaction part flow mode that the processing flow of an initial hydrocarbon raw material comprises a liquid material processing flow which is operated in series and is formed by three different hydrogenation reaction steps and a gas-liquid separation process of products of the corresponding hydrogenation reaction steps, wherein at least one part of a material flow formed by oil generated by first-stage hydrogenation enters a second-stage hydrogenation reaction process, and at least one part of a material flow formed by oil generated by second-stage hydrogenation enters a third-stage hydrogenation reaction process. The flow structure of the hydrogenation method with more stages can be analogized according to the principle. The multistage hydrogenation reaction section refers to a reaction part flow mode that the processing process of the initial hydrocarbon raw material comprises a liquid material processing flow and is operated in series, wherein the reaction part flow mode comprises three or more different hydrogenation reaction processes and hydrogenation product gas-liquid separation processes.

the three-stage hydrogenation reaction section refers to a reaction partial flow mode that the processing flow of the initial hydrocarbon raw material comprises a liquid material processing flow which is operated in series and comprises three different hydrogenation reaction steps and a gas-liquid separation process of products of the corresponding hydrogenation reaction steps.

the invention relates to a method similar to a two-stage hydrogenation method, which is a method similar to the two-stage hydrogenation method, and is regarded as the two-stage hydrogenation method when the ratio of the flow of a back-mixing liquid phase of a rear-stage upper feeding back-mixing flow expansion bed reactor to the flow of a liquid phase in an upper feeding tends to be infinite.

The heavy oil or residue hydrocracking reaction refers to a hydrocracking reaction of heavy oil or residue under the condition of hydrogen and pressurization, the hydrocracking reaction generates at least a part of products with lower molecular weight, the process comprises a thermal cracking reaction of cracking raw material macromolecular hydrocarbon components to generate radicals with small molecular weight, a secondary thermal cracking reaction of intermediate products, a hydrogenation stabilization reaction of the thermal cracking radicals, and a thermal condensation reaction of condensing the radicals into components with larger molecular weight at a spatial position with untimely active hydrogen supply, at least a part of olefin, aromatic hydrocarbon hydrogenation saturation reaction and/or at least a part of heteroatom (sulfur, nitrogen and oxygen) and organic metal hydrogenation hydrogenolysis reaction are simultaneously generated in the process, and the overall result is that at least a part of hydrocarbon products with conventional boiling point lower than 530 ℃ are generated, and the hydrogenation hydrogenolysis reaction generally comprises conventional gaseous hydrocarbon products, Conventional liquid hydrocarbons (naphtha, diesel, wax oil).

the typical example of the concept of the residual oil suspension bed hydrocracking reaction process of the present invention is a suspension bed hydrocracking reaction process of petroleum-based residual oil, and simultaneously comprises a suspension bed hydrocracking reaction process of a suspension bed hydrocracking reaction product of the petroleum-based residual oil, namely unconverted residual oil.

the reaction product of the residual oil suspension bed hydrogenation thermal cracking reaction is at least gas-liquid two-phase material flow, and most of the reaction products belong to gas-liquid-solid three-phase material flow. The hydrogenation reaction effluent is used for discharging hydrogenation reaction products in the reactor, appears in the form of 1-path or 2-path or multi-path materials, and is gas phase or liquid phase or gas-liquid mixed phase or gas-liquid-solid three-phase material flow.

the parts of the present invention are described in detail below.

The hydrogen donating hydrocarbon (or hydrogen donating hydrocarbon component) DS, the hydrogen donating hydrocarbon precursor DS-BF, the hydrogen donating solvent SHS, the hydrogen-losing and-supplying solvent (or hydrogen donating hydrocarbon precursor, or hydrogen donating hydrocarbon to be reactivated) MFS, and the hydrogenation stabilization reaction process MR for conducting the reactivation process of the hydrogen-losing and-supplying solvent MFS are described below.

The hydrogen-supplying hydrocarbon component DS herein refers to a hydrocarbon component having a hydrogen-supplying function in a heavy oil thermal cracking reaction process (including a heavy oil hydrocracking reaction process), a coal hydrogenation direct liquefaction reaction process, and a kerosene co-refining hydrogenation reaction process, and the hydrogen-supplying hydrocarbon includes a partially saturated bicyclic aromatic hydrocarbon and a partially saturated polycyclic aromatic hydrocarbon (generally, a tricyclic hydrocarbon and a tetracyclic hydrocarbon are preferable). In the hydrogen supply hydrocarbon, the hydrogen supply speed of a dihydro body is higher than that of a tetrahydro body, and the hydrogen supply speed of the dihydro body of tricyclic aromatic hydrocarbon is higher or lower than that of the dihydro body of bicyclic aromatic hydrocarbon; tests have demonstrated that polycyclic aromatic hydrocarbons, although not having a hydrogen donating ability, have the ability to transfer hydrogen. The relative hydrogen supply rates at 400 ℃ for the following components were as follows:

For the hydrogen donor solvents SHS used in industry, which are usually mixed hydrocarbons containing a hydrogen donor hydrocarbon component DS and or a hydrogen donor hydrocarbon precursor hydrocarbon component DS-BF, common sources of hydrogen donor solvents SHS are:

firstly, hydrocarbon fractions with the conventional boiling point of 220-480 ℃ of low-temperature coal tar;

Secondly, the normal boiling point of the medium-temperature coal tar is 220-480 ℃ hydrocarbon fraction;

thirdly, hydrocarbon fractions with the conventional boiling point of 220-480 ℃ of the high-temperature coal tar;

fourthly, pyrolyzing the hydrocarbon fraction of the tar with the conventional boiling point of 220-480 ℃ by using the pulverized coal;

Hydrocarbon fraction of ethylene tar at 220-480 ℃;

Sixthly, obtaining hydrocarbon fractions at 220-480 ℃ in a petroleum-based heavy oil thermal processing process, wherein the thermal processing process is a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;

seventhly, hydrocarbon fractions at 220-480 ℃ obtained in the direct coal hydrogenation liquefaction reaction process are obtained;

Eighty percent of hydrocarbon fractions with the conventional boiling points of 450-570 ℃;

ninthly, other mixed hydrocarbons which are rich in a hydrogen-donating hydrocarbon component DS and/or a hydrogen-donating hydrocarbon precursor hydrocarbon component DS-BF.

Taking the hydrocracking reaction process of heavy oil as an example, in the hydrocracking reaction process of hydrocarbons, the hydro-stabilization process of obtaining active hydrogen from hydrocarbon thermal cracking radicals is carried out, the hydrocarbon thermal cracking radicals belong to hydrogen-capturing agents, and meanwhile, the hydrocarbon components with excellent hydrogen-donating capability release active hydrogen atoms (called hydrogen loss) to become hydrocarbons with higher aromatic carbon rate and poorer hydrogen-donating capability; because the hydrogen supply hydrocarbon has special composition and higher price, for reducing the cost, for the occasion that a large amount of hydrogen supply hydrocarbon needs to exist, in order to reduce the consumption of the externally supplied hydrogen supply hydrocarbon, the DS-BF of the hydrogen loss and supply hydrocarbon (or a hydrogen supply hydrocarbon precursor or the hydrogen supply hydrocarbon to be reactivated) is generally required to be recovered in a certain way to obtain the MFS of the hydrogen loss and supply solvent, and the hydrogen supply capacity of the MFS of the hydrogen loss and supply solvent is recovered through the MR in the hydrogenation stable reaction process and then recycled; it is obvious that the hydrogen-losing hydrogen-donating solvent MFS is also a mixed hydrocarbon in general and is usually mixed with the product having the same boiling point in the heavy oil hydrogenation process, so that if the product having the same boiling point in the heavy oil hydrogenation process belongs to the hydrogen-donating hydrocarbon component DS and/or the hydrogen-donating hydrocarbon precursor hydrocarbon component DS-BF, the amount of the hydrogen-donating solvent may be increased, and if the product having the same boiling point in the heavy oil hydrogenation process does not belong to the hydrogen-donating hydrocarbon component DS and/or the hydrogen-donating hydrocarbon precursor hydrocarbon component DS-BF, the concentration of the hydrogen-donating hydrocarbon in the hydrogen-donating solvent may be decreased, and for a stable production system in which the hydrogen-donating solvent is circulated, a recycled material in which the hydrocarbon component is substantially stable may be formed.

because the hydrogen donor solvent can rapidly provide active hydrogen and rapidly transfer the active hydrogen in the hydro-thermal processing aromatic hydrocarbon hydrogenation saturation reaction process of heavy oil and the hydro-thermal cracking reaction process of heavy oil (for example, the active hydrogen on the surface of the catalyst is rapidly transferred so as to improve the efficiency of the catalyst for generating the active hydrogen and improve the utilization rate of the active hydrogen), if the hydrogen donor hydrocarbon component DS can transfer more active hydrogen in a reasonable flow manner (for example, through more hydrocarbon hydrogenation reaction processes), the utilization efficiency of the active hydrogen can be improved, so that the efficient use method of the active hydrogen is formed, and the invention also utilizes the concept.

the beneficial effect of the hydrogen donor hydrocarbon component DS in the hydro-thermal cracking reaction process of the hydrocarbons is mainly shown as follows:

Firstly, in the process of converting into a hydrogen loss solvent, molecular-level is uniformly dispersed in the whole reaction space under proper conditions, active hydrogen is rapidly provided for free radicals in a liquid-phase reaction space, and the catalyst has hydrogen supply capacity, functions of a hydrogen supply agent and a coking inhibitor, and distribution uniformity which cannot be realized by the existing nano-scale catalyst with the minimum granularity is provided;

the whole process of providing active hydrogen for the hydrocarbon belongs to hydrogen transfer between hydrocarbon molecules, basically does not generate reaction heat, and has the function of reducing the reaction heat in the hydrogenation process of the target hydrocarbon oil;

the temperature of the hydrocarbon thermal cracking reaction can be reduced, and the function of a dynamic coking inhibitor is realized;

Fourthly, the cleavage energy of the molecular hydrogen can be reduced, and the dissociation speed of the molecular hydrogen is accelerated;

rapidly transferring active hydrogen (for example, rapidly transferring active hydrogen on the surface of the catalyst so as to improve the efficiency of the catalyst for generating active hydrogen and improve the utilization rate of the active hydrogen);

Sixthly, under the proper condition and under the action of hydrogenation catalyst, the state of hydrogen-supplying hydrocarbon and hydrogen-supplying hydrocarbon precursor can be repeatedly converted, and the hydrogen-supplying hydrocarbon and hydrogen-supplying hydrocarbon precursor can repeatedly play the role of active hydrogen transfer agent.

firstly, the thermal cracking reaction can be induced, the thermal cracking reaction temperature is reduced, and the thermal condensation reaction amount is reduced, so that the operation stability is improved, and the operation period is prolonged;

secondly, the reaction process time can be shortened, and the thermal condensation reaction amount is reduced, so that the operation stability is improved, and the operation period is prolonged;

The total temperature rise of the reaction can be reduced;

The retention rate of pyrolysis molecules can be improved, and the yield of thermal condensation compounds such as coke is reduced, namely the yield of light oil products is improved, and the energy consumption of solid-liquid separation is saved;

the operation stability can be improved, and the operation period can be prolonged; improving the efficiency of the catalyst

sixthly, the overall thermal cracking conversion rate of the heavy oil can be improved.

The hydrogenation reaction zone MR targeted for the production of hydrogen-donating hydrocarbons is described in detail below.

According to the invention, the stream SHS containing the hydrogen-donating hydrocarbon SH which is recycled is a stream of a hydrogenation reaction effluent MRP obtained by converting a hydrogen-donating hydrocarbon precursor stream SHSBF rich in bicyclic aromatic hydrocarbons and/or polycyclic aromatic hydrocarbons in a hydrogenation reaction zone MR targeted for hydrogen-donating hydrocarbon preparation; the hydrogenation reaction zone MR, which is targeted for the production of hydrogen-donating hydrocarbons, can be operated under any suitable conditions.

the hydrogenation stabilizing reaction process MR can adopt a particle catalyst bed layer (a down-flow fixed bed, an up-flow fixed bed and an up-flow micro-expansion bed) reaction mode, and generally operates under the reaction conditions that the temperature is 280-440 ℃, the pressure is 6.0-20.0 MPa, the volume space velocity of the hydrogenation catalyst MR-CAT is 0.05-10.0 hr < -1 >, and the volume ratio of hydrogen to raw oil is 300: 1-3000: 1.

the hydrogenation stabilizing reaction process MR can adopt a moving bed or fluidized bed hydrogenation reaction mode using a particle catalyst, and is usually operated under the reaction conditions that the temperature is 280-440 ℃, the pressure is 6.0-20.0 MPa, the volume space velocity of the hydrogenation catalyst MR-CAT is 0.05-10.0 hr < -1 >, and the volume ratio of hydrogen to raw oil is 100: 1-1200: 1.

the hydrogenation stabilizing reaction process MR can even adopt a suspension bed hydrogenation reaction mode, and generally operates under the reaction conditions that the temperature is 280-440 ℃, the pressure is 6.0-20.0 MPa, the added hydrogenation catalyst is preferably an oil-soluble catalyst or a water-soluble catalyst with high dispersity, and the volume ratio of hydrogen to raw oil is 100: 1-1200: 1.

the aromatic hydrogenation partial saturation reaction in the hydrogenation reaction zone MR aimed at hydrogen supply hydrocarbon preparation of the present invention refers to a hydrogen-consuming reaction process in the presence of hydrogen and a suitable hydrogenation catalyst MR-CAT (catalyst having aromatic hydrogenation partial saturation function) for the occurrence of a hydrocarbon material SHSBF rich in bicyclic aromatic hydrocarbons and/or polycyclic aromatic hydrocarbons, wherein the minimum reaction depth has the minimum industrial significance: the hydrogenation reaction depth is determined according to the aromatic hydrocarbon component structure in the SHSBF and the expected aromatic hydrocarbon partial saturation degree, the higher the hydrogen supply hydrocarbon weight concentration value SHN in the hydrocarbon fraction with the conventional boiling point of 350-480 ℃ in the effluent MRP of the hydrogenation reaction is, the better the SHN is, the SHN is usually more than 6 wt%, and generally more than 10 wt%.

the hydrogenation reaction zone MR targeted for hydrogen supply hydrocarbon preparation has wide variation range of operation conditions due to different properties of raw materials (metal content, oxygen content, olefin content, sulfur content, nitrogen content, aromatic hydrocarbon content, distillation range and specific gravity) and different hydrogenation reaction (hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation and hydrogenation partial saturation) depths, and is determined according to specific process conditions.

For the reaction mode of the granular catalyst bed layer (downflow fixed bed, upflow micro-expansion bed), the hydrogenation reaction zone MR targeted for preparing the hydrogen-supplied hydrocarbon, the hydrogenation catalyst MR-CAT used can be one or the combination and the mixed loading of two or more kinds of hydrogenation refining catalysts, can be a special catalyst for specific raw materials, and can also be a hydrogenation refining catalyst which is used in the proper petroleum refining heavy diesel oil type or wax oil type hydrogenation refining process and has the functions of hydrogenation demetallization, hydrogenation deoxidation, hydrogenation desulfurization, hydrogenation denitrification, hydrogenation saturation and the like, and the combination thereof. The catalyst for the aromatic hydrocarbon hydrogenation partial saturation reaction process of producing the coal liquefaction solvent oil by using the coal liquefaction crude oil and the deep hydrofining catalyst of the coal tar light fraction can be generally used.

the hydrogenation reaction zone MR targeted for hydrogen supply hydrocarbon preparation uses a hydrogenation catalyst MR-CAT which at least comprises an aromatic hydrogenation saturation catalyst and usually also comprises a hydrodemetallization catalyst (the position of the process may be before the bed layer of the aromatic hydrogenation saturation catalyst).

any make-up sulphur may be added to the hydrogenation reaction zone MR targeted for hydrogen-donating hydrocarbon production, as required, to ensure the minimum hydrogen sulphide concentration necessary in the reaction section, such as 500ppm (v) or 1000ppm (v), to ensure that the hydrogen sulphide partial pressure necessary for the catalyst does not fall below the minimum necessary value. The supplementary sulfur may be hydrogen sulfide or a material which can be converted into hydrogen sulfide and has no adverse effect on the hydroconversion process, such as hydrogen sulfide-containing gas or oil, or carbon disulfide or dimethyl disulfide which generates hydrogen sulfide after contacting with high-temperature hydrogen.

a hydrogen supply solvent is used in the upflow hydrogenation reaction process of the heavy oil, so that free radicals can be rapidly eliminated, the hydrogen content of a thermal cracking product can be increased, and the thermal cracking reaction can be inhibited, namely the thermal cracking conversion rate is reduced; while the improvement in residue quality of the upflow hydroprocessing process for heavy oils allows for further hydropyrolysis (such as cyclic hydropyrolysis) thereby increasing the overall thermal cracking conversion. As for the overall effect of the primary thermal cracking of the heavy oil and the secondary thermal cracking of the tail oil of the primary thermal cracking of the heavy oil, the hydrogen supply solvent can be used for effectively improving the overall hydrogenation thermal cracking conversion rate and effectively reducing the yield of the tail oil containing solid in an external throwing manner, thereby improving the process economy.

the residue slurry hydrocracking technology is described in detail below.

the development of residual oil suspension bed hydrocracking technology is based on the coal hydrogenation direct liquefaction technology of 20 th century 40 s, and is a process of residual oil thermal cracking reaction and thermal cracking free radical hydrogenation stable reaction which are caused under high temperature and high pressure by leading reaction under the condition of coexistence of hydrogen and fully dispersed catalyst and/or additive. In the hydrocracking reaction process of the suspension bed, the dispersed catalyst and/or additive is fine-particle powder which is suspended in the reactants and can effectively inhibit the generation of coke. The residual oil suspension bed hydrogenation technology has almost no limit to the content of mechanical impurities of the raw materials, and can process asphalt and oil sand.

typical residual oil suspension bed hydrocracking technologies with industrial operation performance include CANMET residual oil suspension bed hydrocracking process in Canada and EST residual oil suspension bed hydrocracking process in Eini, Italy. Other residual oil suspension bed hydrocracking technologies include BPVCC technology route from British oil company, BPVCC technology from British oil company, HDHPLUS technology from Venezuela national oil company (PDVSA), Uniflex technology from UOP in the United states, VRSH technology from Chevron in the United states, and the like.

In order to overcome the defects of the particle catalyst hydrogenation technology, the suspension bed hydrogenation technology thoroughly abandons the mode of using a huge amount of inner surfaces of particle catalysts as hydrogenation reaction sites, and the technical key points are that the outer surfaces of high-dispersity particle catalysts are used as the hydrogenation reaction sites, so that the problem of a diffusion path for colloid asphaltene to reach the hydrogenation reaction sites is thoroughly solved, the colloid asphaltene can be used for treating inferior heavy oil with higher metal content and higher carbon residue content, and certainly, the inferior heavy oil with extremely high metal content and extremely high carbon residue content is preferably treated by a coking process such as a delayed coking process; the bed expansion rate of the reaction space of the suspension bed hydrogenation reactor reaches the maximum value, and the addition amount of the solid catalyst is usually lower than 10 percent (based on the weight of the raw oil), thereby forming the advantages of 'having coke carrier capacity' and 'discharging free channel of suspended particle impurities'. However, in fact, the suspension bed hydrogenation reactor does not have the bed concept, the reaction space completely loses the advantages of high activity, high interception rate and uniform material hydrogenation conversion depth of the fixed bed hydrogenation catalyst, and the fixed bed hydrogenation catalyst has the dual characteristics of high liquid phase back mixing and high liquid phase short circuit, so that the product quality is greatly reduced compared with the fixed bed technology, and the suspension bed hydrogenation technology can only be used as a pretreatment process of poor oil, but cannot produce high-quality products.

The reaction efficiency of the catalyst surface of the suspension bed hydrogenation reactor strongly depends on the renewal frequency of the catalyst surface and the stable replacement rate of the reaction space, so the renewal means and the replacement means of the catalyst surface are important technical means which can not be lost and can improve the catalyst efficiency, and the existing reactor of the industrial heavy oil suspension bed hydrogenation device adopts a bubbling bed without a circulating pump, which is a huge technical defect, and the result is that: the internal back-mixing liquid phase quantity is uncontrollable, the internal back-mixing catalyst quantity (catalyst deposition quantity) is uncontrollable, the suitable particle size range of the catalyst is too narrow to be controlled, the liquid phase retention time is uncontrollable, the uncontrollable performance is stronger along with the enlargement of the diameter of the reactor, and the effects are proved by the industrial operation result of the trial production poor-quality heavy oil suspended bed hydrogenation device. The present invention recommends the use of a suspended bed reactor with liquid product circulation in order to achieve the desired renewal frequency of the catalyst surface and a stable rate of replacement of the reaction space.

the reaction efficiency of the catalyst surface of the suspension bed hydrogenation reactor is also influenced by the adsorption occupation of polar impurities in gas phase in the reactor, and a large amount of polar impurities such as H2O, NH3, CO and CO2 generated in the coal tar hydrogenation process and the tar and coal CO-refining process can be strongly adsorbed on the catalyst surface to form a shielding effect, so that the international well-known oil product technology supplier CHEVRON provides a scheme of arranging a gas-liquid separator in the middle of the reactor to timely discharge impurity gas and introduces high-purity hydrogen into the lower part of a subsequent suspension bed hydrogenation reactor, but the independent gas-liquid separator has large investment, difficult liquid level control and large operation risk; therefore, the project recommends that a 'gas short-flow' technology can be adopted, under the condition of not adding a gas-liquid separator, gas-liquid mixed phase materials containing gas are introduced into the space at the top of the suspension bed reactor for gas-liquid separation, gas phase is directly discharged, most of liquid phase enters the liquid phase reaction space through a circulating pipe, high-purity hydrogen material flow is introduced into the lower part of a subsequent suspension bed hydrogenation reactor, a gas phase environment with extremely low impurities is formed, meanwhile, the condition of high hydrogen volume concentration is formed, conditions are created for fully exerting the activity of the catalyst, and the method is favorable for reducing the total pressure of the device, improving the conversion rate per pass, reducing the thermal cracking gas-making reaction and reducing the thermal condensation reaction; the scheme for timely discharging the impurity gas also has the advantages of timely discharging the low-boiling-point hydrocarbon components and reducing the thermal cracking rate, and is favorable for improving the liquid yield and reducing the hydrogen consumption.

A typical heavy oil lightening reaction which occurs inside a suspension bed hydrogenation reactor for poor-quality heavy oil is essentially a series process of performing double bond hydrogenation of liquid-phase macromolecules into single bonds, cracking of the single bonds into free radicals and stable free radical hydrogenation in a liquid phase, a large number of free radicals are generated in the whole aggregation-state liquid phase at a high thermal cracking temperature (400-480 ℃) and are relatively uniformly distributed in the whole liquid phase space, the free radical hydrogenation is stabilized at the fastest speed for preventing thermal condensation, obviously, the purpose cannot be achieved by virtue of active hydrogen on the surface of a catalyst (because the probability of liquid-phase hydrocarbon molecules contacted by the catalyst is too low, the moving process of the active hydrogen can also be combined into inactive hydrogen molecules), preferably, the active hydrogen and the free radicals uniformly exist adjacently, and are synchronously released when the free radicals are generated, so as to realize high-efficiency active hydrogen supply. The timely addition of the hydrogen donor with proper boiling point can just over-meet the requirement, prevent thermal condensation and improve the retention rate of light products, and the effects are proved by the successful long-term operation results of the Shenhua coal hydrogenation direct liquefaction device which runs for 8 years and uses the hydrogen donor. For the heavy fraction with huge molecular size and strong polarity, which has the conventional boiling point higher than 530 ℃, if active hydrogen can not be provided timely, a large amount of thermal cracking free radicals of colloid and asphaltene can condense condensates larger than the cracking precursors thereof, so that the yield of hydrogenated thermal cracking distillate oil (hydrocarbons with the conventional boiling point lower than 530 ℃) is reduced, and even thermal condensates such as coke or coke precursors which are dissolved and carried by the liquid phase in the reaction process are generated to cause rapid shutdown of the device, and the effects are proved by a large number of experimental results. The invention uses the operation mode of sufficient hydrogen donor, aims to provide the raw material residual oil with more rigorous thermal cracking conversion rate or processing property by timely providing sufficient active hydrogen to inhibit coking, enlarges the application range of the process and improves the operation stability and the economical efficiency of the process.

the first reaction stage UR10 of the heavy oil UR10F of the present invention is described in detail below.

the following describes a heavy oil hydrocracking reaction process which may be carried out in the first reaction stage UR10 of the heavy oil UR10F of the present invention.

The conventional boiling point of the hydrocarbons of the feedstock heavy oil UR10F of the slurry bed hydrocracking reaction process of heavy oil UR10F of the present invention is generally > 470 ℃, generally > 500 ℃, particularly > 530 ℃; in the process of the first reaction section suspension bed hydro-thermal cracking reaction of the heavy oil UR10F, at least part of thermal cracking reaction and thermal cracking free radical hydrogenation stabilization reaction of the heavy oil UR10F occur, and at least part of hydrocarbon products with lower boiling points are generated; the first heavy oil reaction section UR10 generally cannot achieve total light single-pass reaction, generally has a reasonably high single-pass thermal cracking depth of 60-80%, and a reasonably high overall thermal cracking depth of 90-97%, so that a certain amount of discharged residual oil, for example, 3-10%, exists in the hydrocracking reaction product.

Although the first reaction stage UR10 of the heavy oil UR10F targets thermal cracking reaction and thermal cracking radical hydrogenation stabilization reaction of macromolecular hydrocarbons, some hydrofining reaction must occur in the first reaction stage UR10 of the heavy oil UR10F because the hydrogenation catalyst generally used in the first reaction stage UR10 of the heavy oil UR10F has a hydrofining function itself and active hydrogen is present to induce the hydrofining reaction of hydrocarbon molecules.

In the first reaction stage UR10 of heavy oil UR10F, when the supply of active hydrogen is not timely, the thermal cracking radicals of colloid and asphaltene undergo condensation reaction to produce molecules or structural groups with higher molecular weight, and the end result of repeated dehydrogenation and condensation reaction is the generation of coke, which is, of course, a negative reaction to be suppressed or reduced, and for this purpose, a highly active catalyst such as nano-sized molybdenum disulfide platelet-shaped crystal particles with high dispersity is used.

The first reaction stage UR10 of heavy oil UR10F uses 1 or 2 or more reactors, and 2-4 reactors are commonly used; the first reaction stage UR10 of heavy oil UR10F uses a reactor operating mode which can be any suitable type, and the whole reaction zone of a single suspension bed reactor can be considered as being divided into 2 or more reaction zones. The control mode of the inlet temperature of any reaction zone of the suspension bed reactor can be used for adjusting the temperature and/or flow of hydrogen and can be used for adjusting the temperature and/or flow of oil products.

The first reaction stage UR10 of heavy oil UR10F, uses a reactor whose volume ratio of liquid phase to gas phase (or vapor phase) in the reaction space, which may be the case of liquid phase dominant, defines "actual volume of liquid phase/(actual volume of liquid phase + actual volume of gas phase)" in the reaction space as the liquid phase fraction KL of the reaction space, which is usually greater than 0.45, typically greater than 0.55, and even greater than 0.70, creating a virtually enhanced liquid phase hydrogenation mode, which may require 2 or more additions of hydrogen at different levels of the reactor in order to maintain a sufficiently high hydrogen partial pressure in the reaction space.

the first reaction stage UR10 of heavy oil UR10F is generally set to have an upper limit of hydrocracking cracking rate to prevent hydrogen saturation of hydrocarbon components in the liquid phase from being too high to reduce the solubility of asphaltenes, which would result in asphaltene precipitation.

The reactor configuration of the second or downstream reaction zone of the present invention may be of any suitable configuration and one or more of these may be used.

The colloidal asphalt-like component contained in petroleum-based residual oil is usually a dispersed phase existing in a supermolecular structure, and analysis data shows that the colloidal asphalt-like component dispersed phase is a stable structure group with the molecular weight as high as thousands to tens of thousands or even hundreds of thousands, and the group contains a large number of polycyclic aromatic hydrocarbon units and contains elements such as metal, sulfur, nitrogen and the like, and the main task of the lightening process is to dissociate, hydrogenate and saturate and crack the macromolecules into small molecules which are ten times, hundred times or even thousands times less than the original carbon, so that the thermal cracking task of the suspension bed hydrocracking reaction process is obviously dominant.

the second or downstream reaction zone of the present invention is described in detail below.

the downstream reaction section of the present invention generally processes the discharged residuum of the upstream separation section. Generally, the quality of the discharged residual oil of any reaction separation section is inferior to that of the reaction section raw material residual oil of the reaction separation section, and the inferior residual oil means that: under the condition of not using a hydrogen supply solvent and under the condition of the same other operation conditions (reaction pressure, reaction temperature, catalyst composition, addition amount, existence amount, retention time, hydrogen-oil volume ratio and reactor operation mode), the coking tendency of the inferior residual oil in the hydrocracking reaction process is more serious than that of the inferior residual oil in the hydrocracking reaction process, namely the coking rate is higher and/or the hydrocracking conversion rate is lower; typically, the carbon residue value of hydrocarbons having a normal boiling point above 530 ℃ in a more poor residue is higher than the carbon residue value of hydrocarbons having a normal boiling point above 530 ℃ in a poor residue.

compared with the first reaction section or the upstream reaction section, the downstream reaction section has the main aim that in the presence of a catalyst, a possibly used hydrogen supply solvent and a possibly used asphaltene diluent wax oil, inferior residual oil undergoes more hydrogenation saturation reactions and sufficient thermal cracking free radical hydrogenation stable reactions to form mild hydro-thermal cracking reaction conditions, so that the carbon residue value of unconverted residual oil in the reaction section is effectively reduced, and the operation period is prolonged.

in the second or downstream reaction stage of the present invention, an important reaction task is to perform hydrodecarbonization of the inferior residual oil, i.e. the hydrogenation saturation of heavy aromatics or colloids and asphaltenes, and, of course, at the same time, hydrofining reactions (including demetallization hydrogenolytic reaction, olefin hydrogenation saturation reaction, hydrogenation impurity removal (oxygen, sulfur, nitrogen) reaction, hydrogenation aromatics saturation or partial saturation reaction, hydrogenation decarburization reaction) and/or hydrocracking reactions can occur.

In the second or downstream reaction stage of the present invention, asphaltene diluent wax oil can be added for dispersion and dissolution of colloid, asphaltene, liquid phase coke, preventing the yield of thermal condensate such as asphaltene from exceeding a limit due to excessively high thermal cracking rate and causing the generation of a second liquid phase (asphaltic phase), therefore, the conversion rate of the residue once-through hydrocracking of the second or downstream reaction stage is generally lower than that of the first reaction stage.

In the second or downstream reaction stage of the present invention, when the supply of active hydrogen is not timely, thermal cracking radicals of colloid or asphaltene undergo condensation reaction to produce molecules or structural groups having a larger molecular weight, and the end result of repeated dehydrogenation and condensation reaction is the generation of coke, which is, of course, a negative reaction to be suppressed or reduced, and the use of a hydrogen-donating solvent can effectively solve this problem.

In the second reaction section or the downstream reaction section of the present invention, 1 or 2 or more reactors can be used, the operation mode of the reactor can be any suitable mode, and generally, the reactor is an upflow suspended bed reactor or an upflow suspended bed reactor with liquid product circulation, and the whole reaction zone of a single upflow suspended bed reactor can be considered to be divided into 2 or more reaction zones. The control mode of the inlet temperature of any reaction zone of the upflow suspension bed reactor can be the regulation of the temperature and/or the flow of hydrogen, and can be the regulation of the temperature and/or the flow of oil products.

the second or downstream reaction zone of the present invention, which uses a reactor whose volume ratio of liquid phase to gas phase (or vapor phase) in the reaction space can be the case of liquid phase being the main one, defines "actual volume of liquid phase/(actual volume of liquid phase + actual volume of gas phase)" in the reaction space as the liquid phase fraction KL of the reaction space, the fraction KL being usually greater than 0.5, usually greater than 0.65, even greater than 0.80, forming a practically enhanced liquid phase hydrogenation mode, and in order to keep the hydrogen partial pressure of the reaction space sufficiently high, it may be necessary to add hydrogen gas 2 or more times at different height positions of the reactor.

The following describes in detail the possible stripping process XHBM for the hot high pressure separation process or for the warm high pressure separation process of the present invention.

in the gas stripping process XHBM, the countercurrent contact separation times of the liquid hydrocarbon material and the stripping hydrogen XBH are as follows: generally 1 to 8 times, usually 2 to 4 times; the quantity of the stripping hydrogen XBH is determined according to the requirement of the separation target of the XHBM component in the stripping process; the operating pressure of the XHBM of the stripping process, typically slightly below that of its feed; the operation temperature of the gas stripping process XHBM is determined according to the requirement of the gas stripping process XHBM component separation target, and is usually 180-480 ℃, and is usually 250-440 ℃.

The suspension bed reactor of the invention has the following working modes:

Firstly, a suspension bed hydrogenation reactor;

② a combined hydrogenation reactor of a suspension bed and a boiling bed.

the invention can be used for processing heavy oil catalytic cracking diesel oil andor heavy cycle oil andor clarified oil in a combined manner.

the catalytic thermal cracking reaction process of hydrocarbons refers to a thermal cracking reaction process taking carbon-carbon bond breakage as a main purpose of raw material hydrocarbons in the presence of a thermal cracking catalyst, and includes a conventional catalytic cracking reaction process or a conventional catalytic cracking reaction process, main raw material oil which is usually processed is wax oil and atmospheric residue oil, and a document T001 which describes the technology is as follows: the publication name: catalytic cracking process and engineering; searching and encoding by using a book: ISBN encoding: 7-80043 and 537-7; china edition library CIP data check word: (2004) 131193 No; thirdly, main weaving: chenjunwu; fourthly, the publisher: china petrochemical press. The document T001 "catalytic cracking process and engineering" on pages 459 to 488 describes physical property data of typical catalytic cracking light diesel oil (light cycle oil), catalytic cracking cycle oil (heavy cycle oil), and catalytic cracking clarified oil. According to the different operation conditions and product separation schemes of the specific device, the boiling range ranges of the catalytic cracking light diesel oil (light cycle oil), the catalytic cracking cycle oil (heavy cycle oil) and the catalytic cracking clarified oil fluctuate within a certain range, but based on the invention, the yield of the heavy wax oil of the oil generated by the catalytic thermal cracking reaction can be improved, and then the heavy wax oil goes to the upflow hydrogenation modification process for hydrogenation reaction.

The invention can be used for combined processing of heavy oil coking reaction product heavy wax oil, in particular heavy oil coking reaction product heavy wax oil containing partial solid particles.

The heavy oil coking reaction process of the invention refers to a thermal processing process of deep thermal cracking and condensation reaction under the conditions of high temperature and long reaction time by taking heavy oil (such as vacuum residue oil, cracked residue oil and the like) poor in hydrogen as a raw material, and the raw material is converted into gas, naphtha, gasoline, diesel oil, heavy distillate oil (coked light wax oil, coked heavy wax oil) and coke. The process types of the coking process comprise kettle type coking, open hearth coking, delayed coking, contact coking, fluid coking and flexible coking. The modern heavy oil coking process comprises delayed coking, contact coking, fluid coking, flexible coking and other processes. One document describing such techniques, T002, is: the publication name: delayed coking process and engineering; searching and encoding by using a book: ISBN encoding: 978-7-80229-456-1; china edition library CIP data check word: (2007) 168082 No; thirdly, main weaving: fringed pink; fourthly, the publisher: china petrochemical press. The document T002 "delayed coking Process and engineering" at pages 188 to 254 describes physical data of typical delayed coking waxy oil. According to the operation condition of a specific device and different product separation schemes, the boiling range of the coking wax oil fluctuates in a certain range, and based on the invention, the yield of heavy wax oil of coking generated oil can be improved, and then the heavy wax oil goes to an up-flow hydrogenation modification process for hydrogenation reaction.

The catalytic cracking recycle oil (heavy cycle oil), catalytic cracking clarified oil and coking wax oil have poor quality, so that direct catalytic cracking or hydrocracking is difficult to realize, or the direct catalytic cracking or coking coke production rate is high, so that the economy is poor, and the optimized processing is realized by adopting the combined hydrogenation of the invention.

the characteristic parts of the present invention are described in detail below.

option 1, an empty-tube bubbling bed suspended bed reactor system;

Option 1, an empty-tube bubbling bed suspended bed reactor system;

option 1, a deep reduced pressure vaporization mode is adopted;

The general control principle of the gas phase hydrogen sulfide concentration in the hydrogenation reaction process of the present invention is described in detail below.

any make-up sulfur may be added to any of the hydrogenation processes as desired, but is typically added to the uppermost hydrogenation process inlet to ensure that the minimum hydrogen sulfide concentration required for the reaction process, such as a desired value of 500ppm (v), or 1000ppm (v), or 3000ppm (v), is not below the minimum specified value to ensure the required hydrogen sulfide partial pressure for the catalyst to be below the minimum specified value to ensure the required sulfidation profile for the catalyst. The supplementary sulfur may be hydrogen sulfide or a material which can be converted into hydrogen sulfide and has no adverse effect on the hydroconversion process, such as hydrogen sulfide-containing gas or oil, or liquid sulfur or carbon disulfide or dimethyl disulfide which generates hydrogen sulfide after being contacted with high-temperature hydrogen gas.

The general principles of the high pressure separation process of the hydrogenation reaction effluent of the present invention are described in detail below.

the high-pressure separation process of the hydrogenation reaction effluent generally comprises a cold high-pressure separator, when the hydrocarbon oil in the hydrogenation reaction effluent has high density (for example, the density is close to the water density) or high viscosity or is emulsified with water and difficult to separate or contains solid particles, a hot high-pressure separator with the operation temperature generally being 150-450 ℃ is also needed, at the moment, the hydrogenation reaction effluent enters the hot high-pressure separator to be separated into hot high-molecular gas mainly comprising hydrogen in volume and hot high-molecular oil liquid mainly comprising conventional liquid hydrocarbon and possibly existing solids, the hot high-molecular gas enters the cold high-pressure separator with the operation temperature generally being 20-80 ℃ to be separated into cold high-molecular oil and cold high-molecular gas, and as a large amount of high-boiling-point components enter the hot high-molecular oil liquid, the following aims are achieved: the cold high-fraction oil becomes less dense or less viscous or easily separated from water. The high-pressure separation process of the hydrogenation reaction effluent is provided with the hot high-pressure separator, and the high-pressure separation process also has the advantage of reducing heat loss because the hot high-pressure separation oil liquid can avoid the cooling process of using an air cooler or a water cooler for hot high-pressure separation gas. Meanwhile, part of the hot high-oil liquid can be returned to the upstream hydrogenation reaction process for recycling, so as to improve the overall raw material property of the hydrogenation reaction process receiving the circulating oil, or the circulating hot high-oil can be subjected to circulating hydrogenation.

Between the hot high pressure separation part and the cold high pressure separation part, a temperature high pressure separation part can be arranged according to the requirement, at the moment, the hot high pressure separation gas is cooled to form a gas-liquid two-phase material, the gas is separated into a temperature high pressure separation gas mainly comprising hydrogen in volume and a temperature high pressure separation oil liquid mainly comprising conventional liquid hydrocarbon and possibly existing solid in a temperature high pressure separator, and the temperature high pressure separation gas enters the cold high pressure separation part for cooling and gas-liquid separation.

before the hydrogenation reaction effluent or the hot high-pressure gas or the warm high-pressure gas enters the cold high-pressure separation part, the temperature is usually reduced (generally, heat exchange with the reaction part feed) to about 220 to 100 ℃ (the temperature is higher than the crystallization temperature of the ammonium hydrosulfide and the crystallization temperature of the ammonium chloride in the gas phase of the hydrogenation reaction effluent), then washing water is usually injected into the reaction effluent to form the hydrogenation reaction effluent after water injection, 2 or more water injection points may be needed to be arranged, the washing water is used for absorbing ammonia and other impurities such as hydrogen chloride and the like which may be generated, and the water solution after absorbing the ammonia necessarily absorbs the hydrogen sulfide. In the cold high-pressure separation part, the effluent of the hydrogenation reaction after water injection is separated into: a cold high-molecular gas mainly composed of hydrogen in volume, a cold high-molecular oil mainly composed of conventional liquid hydrocarbon and dissolved hydrogen, and a cold high-molecular water mainly composed of water and dissolved with ammonia and hydrogen sulfide. The cold high-moisture water generally contains 0.5-15% (w), preferably 1-8% (w) of ammonia. One purpose of the washing water injection is to absorb ammonia and hydrogen sulfide in the hydrogenation reaction effluent, prevent the formation of ammonia hydrosulfide or ammonia polysulfide crystals from blocking the heat exchanger channels, and increase the pressure drop of the system. The injection amount of the washing water is determined according to the following principle: on the one hand, the washing water is divided into vapor phase water and liquid phase water after being injected into the hydrogenation reaction effluent, and the liquid phase water amount is required to be more than zero, and is preferably 30 percent or more of the total amount of the washing water; in yet another aspect, the wash water is used to absorb ammonia from the hydrogenation effluent, to prevent the high partial gas from having too high an ammonia concentration, and to reduce catalyst activity, and generally the lower the ammonia volume concentration of the high partial gas, the better, the lower the ammonia volume concentration of the high partial gas, the more typically no greater than 200ppm (v), and most preferably no greater than 50ppm (v). The operating pressure of the cold high-pressure separator is the difference between the pressure of the hydrogenation reaction part and the actual pressure drop, and the difference between the operating pressure of the cold high-pressure separator and the hydrogenation reaction pressure is not too low or too high, generally 0.35-3.2 MPa, and generally 0.5-1.5 MPa. The hydrogen volume concentration value of the cold high-molecular gas should not be too low (leading to a rise in the operating pressure of the plant), and should generally be not less than 70% (v), preferably not less than 80% (v), and most preferably not less than 85% (v). At least one part of the cold high-molecular gas, which is usually 85-100%, is returned to the hydrogenation part for recycling so as to provide the hydrogen amount and the hydrogen concentration necessary for the hydrogenation part; in order to increase the investment efficiency of the plant, it is necessary to ensure that the recycle hydrogen concentration does not fall below the aforementioned lower limit, for which reason, depending on the specific feedstock properties, reaction conditions, product distribution, a portion of the cold high-molecular gas may be removed to remove methane and ethane produced by the reaction. For discharged cold high-molecular gas, conventional membrane separation process or pressure swing adsorption process or oil washing process can be adopted to realize the separation of hydrogen and non-hydrogen gas components, and the recovered hydrogen is used as new hydrogen. For the recycled cold high-pressure gas, the conventional membrane separation process or pressure swing adsorption process or oil washing process can be adopted to realize the separation of hydrogen and non-hydrogen gas components, and the recovered hydrogen is used as new hydrogen

fresh hydrogen is fed into the hydrogenation section to replenish hydrogen consumed during the hydrogenation reaction, and the higher the concentration of fresh hydrogen, the better, the more preferably the concentration of fresh hydrogen is not lower than 95% (v), and the more preferably not lower than 99% (v). All of the fresh hydrogen may be introduced into any of the hydrogenation sections, preferably the first hydrogenation reactor.

In any reaction process, the used hydrogen material flow can be all new hydrogen, can be all recycle hydrogen, and can be the mixed gas of the new hydrogen and the recycle hydrogen.

for the direct coal hydrogenation liquefaction reaction process, because the yields of conventional gases, namely hydrocarbon, CO and CO2 are huge, most of cold high-fraction gas is usually about 70-100% of the cold high-fraction gas, the permeation hydrogen obtained after purification through a membrane separation process is pressurized and then returned to the hydrogenation reaction process, and the non-permeation gas is pressurized and returned to the hydrogenation reaction process for recycling after PSA hydrogen extraction or after 'steam conversion hydrogen production + PSA hydrogen extraction'.

Claims

1. The fractional heavy oil suspension bed hydrogenation thermal cracking reaction separation method is characterized by comprising the following steps:

2. the method of claim 1, wherein:

At least a portion of the first hydrogen-rich gas, US10H, is returned to the first reaction stage UR10 for use.

3. The method of claim 1, wherein:

at least a portion of the second hydrogen-rich gas, US20H, is returned to the second reaction stage UR20 for use.

4. the method of claim 1, wherein:

at least a portion of the first hydrogen-rich gas, US10H, is directed to the second reaction stage UR20 for use.

5. the method of claim 1, wherein:

At least a portion of the second hydrogen-rich gas, US20H, is introduced into the first reaction stage UR10 for use.

6. The method of claim 1, wherein:

Heavy oil UR10F consists mainly of hydrocarbon components with conventional boiling points above 450 ℃.

7. The method of claim 1, wherein:

heavy oil UR10F consists mainly of hydrocarbon components with conventional boiling points above 530 ℃.

8. The method of claim 1, wherein:

in the first reaction stage UR10, the first solid particulate catalyst UR10-CAT used contains at least a molybdenum-based catalyst whose operating state is molybdenum disulfide.

9. the method of claim 1, wherein:

in the first reaction stage UR10, the first solid particulate catalyst UR10-CAT used contains at least a molybdenum-based catalyst whose operating state is nano-scale plate-like crystals.

10. the method of claim 1, wherein:

in the first reaction stage UR10, a first solid particulate catalyst UR10-CAT is used which contains at least a molybdenum-based catalyst whose operating state is molybdenum disulfide;

11. the method of claim 1, wherein:

12. the method of claim 1, wherein:

13. the method of claim 1, wherein:

in the first reaction stage UR10, the total conversion rate of hydrocarbon components with conventional boiling point higher than 530 ℃ in the heavy oil UR10F is 60-98 wt%.

14. the method of claim 1, wherein:

in the first reaction stage UR10, the total conversion of hydrocarbon components having conventional boiling points above 530 ℃ is from 50 to 80% by weight, based on the total flow of heavy oil UR10F and possibly short cycle heavy oil US10-VR-TOUR 10.

15. the method of claim 1, wherein:

In the second reaction stage UR20, the total conversion rate of hydrocarbon components with conventional boiling point higher than 530 ℃ in the heavy oil UR20F is 60-90 wt%.

16. the method of claim 1, wherein:

in the second reaction stage UR20, the total conversion of hydrocarbon components with conventional boiling points above 530 ℃ is 30 to 60 wt.%, based on the total stream of heavy oil UR20F and possibly short cycle heavy oil US20-VR-TOUR 20.

17. The method of claim 1, wherein:

heavy oil UR10F consists mainly of hydrocarbon components with a conventional boiling point above 500 ℃;

18. the method of claim 1, wherein:

defining the ratio of the weight of the second external heavy oil US20-VR-OUT US20-VR-OUT-WT to the weight of the heavy oil UR10F UR10F-WT as K500;

k500 is (US20-VR-OUT-WT)/(UR10F-WT) and K500 is 0.001-0.02.

19. The method of claim 18, wherein:

K500 is 0.003 to 0.01.

20. The method of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19, wherein:

(4) in the second separation section US20, stream UR20P-X is separated to obtain a second heavy oil US20-VR containing hydrocarbon components having a conventional boiling point above 530 ℃ and solid particulate catalyst;

21. The method of claim 20, wherein:

Defining the ratio of the weight of the long circulating heavy oil US20-VR-TOUR10 US20-VR-TOUR10-WT to the weight of the second external row heavy oil US20-VR-OUT US20-VR-OUT-WT as K700;

K700 is (US20-VR-TOUR10-WT)/(US20-VR-OUT), and K700 is 0.01-100.

22. the method of claim 21, wherein:

k700 is 0.1-70.

23. The method of claim 21, wherein:

k700 is 20 to 50.

24. the method of claim 20, wherein:

in the first reaction stage UR10, a first solid particulate catalyst UR10-CAT is used, comprising a molybdenum-based catalyst whose operating condition is molybdenum disulfide;

K900 (US10-IN-MO-WT) 1000000/(UR10F-WT), K900 is 5-300.

25. the method of claim 24, wherein:

K900 is 10-150.

26. The method of claim 24, wherein:

k900 is 20-50.

27. the method of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19, wherein:

the heavy oil UR10F is mainly composed of hydrocarbon components with normal boiling point higher than 450 ℃, metal content is 10-1200 mu g/g, and carbon residue content is 10-30 wt%.

28. the method of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19, wherein:

The heavy oil UR10F is mainly composed of hydrocarbon components with normal boiling point higher than 530 ℃, metal content is 10-1200 mu g/g, and carbon residue content is 20-40 wt%.

29. the method of claim 20, wherein:

30. the method of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19, wherein:

the carbon residue value of the first discharged heavy oil US10-VR-OUT is 1.5 times lower than that of the heavy oil UR 10F;

31. the method of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19, wherein:

The carbon residue value of the first discharged heavy oil US10-VR-OUT is 1.3 times lower than that of the heavy oil UR 10F;

32. the method of claim 20, wherein:

33. the method of claim 20, wherein:

34. The method of claim 1, wherein:

the operating conditions of the suspension bed hydrogenation thermal cracking reaction section are as follows: the reaction temperature is 390-445 ℃, the reactor pressure is 6-25 MPa, the volume concentration of gas-phase hydrogen is 50-95%, the volume ratio of gas to liquid is 100-2000 standard cubic meters per ton, and the reaction residence time is 5-150 minutes.

35. The method of claim 1, wherein:

the first reaction stage UR10 uses a hydrogen donating hydrocarbon.

36. The method of claim 1, wherein:

The second reaction stage UR20 uses a hydrogen donating hydrocarbon.

37. the method of claim 1, wherein:

the recovery system of hydrogen-containing gas UR20-VPX obtained by separating the intermediate product or the final product of the second reaction stage UR20 is partially or totally combined with the recovery system of hydrogen-containing gas UR10-VPX obtained by separating the intermediate product or the final product of the first reaction stage UR 10.

38. the method of claim 1, wherein:

the hydrogen-containing gas UR20-VPX obtained by separating the intermediate product or the final product of the second reaction stage UR20 passes through part or all of the flow path of the first reaction stage UR10 to be used in series.

39. The method of claim 1, wherein:

The hydrocarbon-containing oil gas obtained in the second separation section US20, US20-VPX, is jointly recovered in the first separation section US 10.

40. the method of claim 1, wherein:

The hydrocarbon-containing oil gas obtained in the second separation section US20, US20-VPX, enters the first separation section US10 and is jointly recovered with the material with the composition close to that of the gas phase.

41. the method of claim 1, wherein:

the feed containing solid particles, containing hydrocarbon components having a conventional boiling point above 530 c, obtained in the second separation stage US20, is not fed to the flow scheme of the first separation stage US 10.

42. the method of claim 1, wherein:

the first externally discharged heavy oil US10-VR-OUT is mainly composed of hydrocarbon components with conventional boiling points higher than 450 ℃;

43. The method of claim 1, wherein:

The first externally discharged heavy oil US10-VR-OUT is mainly composed of hydrocarbon components with conventional boiling points higher than 530 ℃;

44. the method of claim 1, wherein:

the working mode of the suspension bed hydrogenation reactor used in the suspension bed hydrogenation reaction process is selected from 1 or more of the following types:

option 1, an empty-tube bubbling bed suspended bed reactor system;

45. The method of claim 1, wherein:

Heavy oil UR10F comprising and consisting essentially of hydrocarbon components having a conventional boiling point above 530 ℃; comprising an organometallic and or an asphaltene;

the hydrocracking reaction separation process in the suspension bed of heavy oil UR10F includes at least 3 reaction separation nodes, including the first reaction separation node UT10, the second reaction separation node UT20 and the third reaction separation node UT 30;

46. the method of claim 45, wherein:

The process for separating the reaction and the thermal cracking in the suspension bed of the heavy oil UR10F comprises at least 4 reaction separation sections, namely a first reaction separation section UT10, a second reaction separation section UT20, a third reaction separation section UT30 and a fourth reaction separation section UT 40;

47. the method of claim 45 or 46, wherein:

the operating conditions of any suspension bed hydrogenation thermal cracking reaction section are as follows: the reaction temperature is 390-445 ℃, the reactor pressure is 6-25 MPa, the volume concentration of gas-phase hydrogen is 50-95%, the volume ratio of gas to liquid is 100-2000 standard cubic meters per ton, and the reaction residence time is 5-150 minutes.

48. the method of claim 45 or 46, wherein:

1 or more suspension bed hydrocracking reaction stages use hydrogen supplying hydrocarbon.

49. the method of claim 45 or 46, wherein:

the recovery system of the hydrogen-containing gas obtained by separating the intermediate product or the final product of the downstream reaction section is partially or completely combined with the recovery system of the hydrogen-containing gas obtained by separating the intermediate product or the final product of the upstream reaction section.

50. the method of claim 45 or 46, wherein:

the hydrogen-containing gas obtained by separating the intermediate product or the final product of the downstream reaction section passes through part or all of the flow path of the upstream reaction section to form serial use.

51. the method of claim 45 or 46, wherein:

The hydrocarbon-containing oil gas obtained in the downstream separation section enters the upstream separation section for combined recovery.

52. the method of claim 45 or 46, wherein:

the hydrocarbon-containing oil gas obtained in the downstream separation section enters the upstream separation section to be jointly recovered with the material with the composition close to that of the gas phase.

53. The method of claim 45 or 46, wherein:

the material containing solid particles and hydrocarbon components with the conventional boiling point higher than 530 ℃ obtained in the downstream separation section does not enter the flow path of the upstream separation section.

54. the method of claim 45 or 46, wherein:

The carbon residue value of the discharged heavy oil of the downstream separation section is 1.5 times lower than that of the discharged heavy oil of the upstream separation section.

55. The method of claim 45 or 46, wherein:

the carbon residue value of the discharged heavy oil of the downstream separation section is 1.3 times lower than that of the discharged heavy oil of the upstream separation section.

56. The method of claim 45 or 46, wherein:

the discharged heavy oil of any downstream separation section consists essentially of hydrocarbon components having a conventional boiling point above 450 ℃.

57. the method of claim 45 or 46, wherein:

The discharged heavy oil of any downstream separation section consists essentially of hydrocarbon components having a conventional boiling point above 530 ℃.

58. The method of claim 45 or 46, wherein:

In any downstream reaction section, the total conversion rate of hydrocarbon components with the conventional boiling point higher than 530 ℃ in the heavy oil feed without the circulating oil is 60-90 wt%.

59. the method of claim 45 or 46, wherein:

any downstream reaction section, wherein the overall conversion of hydrocarbon components having a normal boiling point above 530 ℃ is from 30 to 60 wt%, based on the total heavy oil feed.

60. The method of claim 45 or 46, wherein:

Option 1, an empty-tube bubbling bed suspended bed reactor system;

61. the method of claim 1, wherein:

the discharged heavy oil USEND-VR-OUT discharged from the last separation section enters a deep vaporization process ENDKS to be separated into deep vaporization gas ENDKS-V and deep vaporization liquid ENDKS-L, and at least part of hydrocarbons in the discharged heavy oil USEND-VR-OUT are vaporized and enter the deep vaporization gas ENDKS-V; the total weight of the hydrocarbons in the deep vaporization liquid ENDKS-L is lower than that in the discharged heavy oil USEND-VR-OUT;

62. The method of claim 61, wherein:

Option 1, a deep reduced pressure vaporization mode is adopted;

63. The method of claim 20, wherein:

64. the method of claim 63, wherein:

Option 1, a deep reduced pressure vaporization mode is adopted;

65. The method of claim 45 or 46, wherein:

66. the method of claim 65, wherein:

option 1, a deep reduced pressure vaporization mode is adopted;