CN109609185A

CN109609185A - Content of wax oil plant adds hydrogen, adds the combined method of hydrogen, catalyst circulation containing oil of dreg

Info

Publication number: CN109609185A
Application number: CN201811632471.9A
Authority: CN
Inventors: 何巨堂
Original assignee: Luoyang Rui Hua New Energy Technology Development Co Ltd
Current assignee: Luoyang Rui Hua New Energy Technology Development Co Ltd
Priority date: 2018-12-23
Filing date: 2018-12-23
Publication date: 2019-04-12

Abstract

Content of wax oil plant adds hydrogen, containing oil of dreg plus hydrogen, the combined method of catalyst circulation, floating bed hydrogenation modified-reaction process BRA suitable for high aromatic hydrocarbons wax oil BRAF, the floating bed hydrogenation reaction process R10 of decompression residuum R10F, it is easy to the combination of the separation cyclic process XSX0 of mechanically decoupled large-size particles catalyst BP, it is present in the BP of BRA by R10 bis- times uses, BP in R10 product R10P, which isolates to return to BRA rich in BP material and recycle through XSX0, to be added up, powerful BP recycle ratio is maintained to increase amounts of particles and catalyst external surface product, BP provides big individual particle area to prevent heavy asphalt matter HWA package catalyst granules from forming excessive screen effect, reaction process, which can be used simultaneously, is difficult to mechanically decoupled small size particle LP, part contains The product residual oil of LP can return to BRA or with R10 circulative accumulation, can be greatly reduced catalyst consumption, improve overall economics.

Description

Content of wax oil plant adds hydrogen, adds the combined method of hydrogen, catalyst circulation containing oil of dreg

Technical field

The present invention relates to content of wax oil plants to add hydrogen, adds the combined method of hydrogen, catalyst circulation containing oil of dreg, is suitable for high aromatic hydrocarbons The floating bed hydrogenation modified-reaction process BRA of wax oil BRAF, decompression residuum R10F floating bed hydrogenation reaction process R10, be easy to The combination of the separation cyclic process XSX0 of mechanically decoupled large-size particles catalyst BP is present in the BP of BRA by R10 bis- times It uses, the BP in R10 product R10P, which isolates to return to BRA rich in BP material and recycle through XSX0, to be added up, and powerful BP is maintained to follow For ring ratio to increase amounts of particles and catalyst external surface product, BP provides big individual particle area to prevent heavy asphalt matter HWA packet It wraps up in catalyst granules and forms excessive screen effect, reaction process, which can be used simultaneously, is difficult to mechanically decoupled small size particle LP, Part the product residual oil containing LP can return to BRA or with R10 circulative accumulation, can be greatly reduced catalyst consumption, improve macroeconomy Property；Conversion per pass can be effectively improved or reduce reaction temperature, improve technology stability, investment can be reduced, hydrogen consumption, energy consumption, urged Agent consumption, gas recovery ratio improve liquid and receive, improve generation oil quality；The recycling of catalyst height ratio may be implemented, be able to achieve The separation of catalyst and other nano particle solids realizes that secondary operation or recycling, benefit are convenient in the purification of outlet catalyst solid In the technique for forming ultralow residue emission index；Can be used catalyst with base of molybdenum, hydrogen supply dissolvent, diluent, feedstock oil can branch into Material processing；Floating bed hydrogenation heat cracking reaction process R10, fractional distillation process, the operating condition of extraction process and operation knot can be optimized Fruit.

Background technique

The main problem that the present invention is paid close attention to is: in the floating bed hydrogenation reaction process R10 of decompression residuum R10F, joint processing When high aromatic hydrocarbons wax oil BRAF, how to optimize catalyst grain size matching, optimization catalyst granules circulation integrating method, optimization two instead The flow path match for answering process is greatly reduced catalyst consumption, improves catalysis reaction efficiency, especially raising heavy asphalt matter HWA Hydrogenation reaction efficiency, improve product quality, extend the operation cycle, improve yield of light oil, reduce plant investment, improve technique Overall economics.

The present invention is described below in conjunction with decompression residuum floating bed hydrogenation reaction process.

Hydrocarbon floating bed hydrogenation reaction process R10 of the present invention, the raw material of processing usually contain heavy oil component, the heavy oil The normal boiling point of component: usual 350 DEG C of >, 450 DEG C of general >, particularly 530 DEG C, more particularly > 570 DEG C of >.

Heavy oil R10F of the present invention is mainly formed by wax oil or with residual oil, the normal boiling point of main hydrocarbon component: Usual 350 DEG C of >, 450 DEG C of general >, particularly 530 DEG C, more particularly > 570 DEG C of >.

Decompression residuum R10F of the present invention, the usually hydro carbons mainly by normal boiling point higher than 530 DEG C are formed.

Up flow type expanded bed reactor of the present invention is vertical up-flow reactor, expansion is belonged to when using catalyst Bed reactor；The vertical central axis upright for referring to working condition reactor after installing is in ground；Up flow type refers to reacting Process materials main body flow direction travels through reaction compartment or catalyst bed or the catalyst co-flow with uplink from bottom to top； Expanded bed refers to that working condition catalyst bed is in swelling state, and catalyst bed expansion ratio, which is defined as catalyst bed, to be had The height CUH of the empty bed static condition of the maximum height CWH and catalyst bed of working condition when reaction raw materials pass through it Ratio K BED, in general, referred to as slight expanded-bed when KBED is lower than 1.10, referred to as ebullated bed when KBED is between 1.25~1.55, and hang Floating bed is considered as the expanded bed of most extreme form.

The catalyst R10C that the up flow type floating bed hydrogenation reaction process of heavy oil R10F of the present invention uses, was reacting Existing forms in journey are usually sulfide, and common catalyst has iron-based sulfide, molybdenum base sulfide, Ni-based sulfide, cobalt Base sulfide etc..

Up flow type floating bed hydrogenation reactor can be used in up flow type floating bed hydrogenation reaction process of the present invention, can To use the hydrogenation process of suspension bed and ebullated bed combined type hydrogenator.

The up flow type floating bed hydrogenation reaction process of heavy oil R10F of the present invention, the hydrogenation reaction of generation, can be with Hydrofining reaction is main target reaction, can be and reacts by main target of heat from hydrogenation cracking reaction.

Hydrofining reaction of the present invention, can be hydrogenation of unsaturated hydrocarbons saturated reaction or partial hydrogenation saturation is anti- It answers, as olefins hydrogenation reaction, aromatic hydrogenation saturated reaction or aromatic moiety add hydrogen saturated reaction；The hydrofinishing is anti- It answers, can be and add hydrogen removing impurities element (such as sulphur, nitrogen, oxygen, chlorine), hydrodemetallization (such as organic iron, vanadium, nickel)；The present invention The heat from hydrogenation cracking reaction, heat cracking reaction, thermal cracking free radical including hydro carbons generation thermal cracking free radical add hydrogen Stablize reaction.

The up flow type floating bed hydrogenation modified-reaction process R10 of heavy oil R10F of the present invention, main task are to occur At least part heavy oil R10F's adds hydrogen aromatic moiety saturated reaction, at least part plus the qualitative response of hydrogen removing impurities, certainly, usually same When heat cracking reaction, the reaction of thermal cracking free radical stabilized hydrogenation also occurs, generate that the fragrant charcoal rate of at least part is lower, boiling point is lower Hydrocarbon product.

The up flow type floating bed hydrogenation heat cracking reaction process R10 of heavy oil R10F of the present invention, main task are hairs The heat cracking reaction of raw at least part heavy oil R10F, the reaction of thermal cracking free radical stabilized hydrogenation generate the fragrant charcoal of at least part Rate is lower, the lower hydrocarbon product of boiling point, certainly, usually adds hydrogen aromatic moiety saturated reaction, at least part plus hydrogen de- simultaneously Thermal condensation usually also occurs simultaneously and reacts such as coking reaction for impurity reaction.

The up flow type floating bed hydrogenation aromatic hydrocarbons saturated reaction process R10 of heavy oil R10F of the present invention, usually cannot achieve One way reacts whole lightings, and usually its rationally high conversion per pass is usually 15~45%, and in this way plus hydrogen aromatic hydrocarbons saturation is single There are the tail oil of certain amount such as 65~85% (adding hydrogen aromatic hydrocarbons saturated products residual oil) THC-VR in journey reaction product R10P, than Such as, using needle-shape coke raw material hydrogenated bitumen as the floating bed hydrogenation reaction process of the bituminous high temperature coal-tar R10F of productive target R10。

At least part occurs for the up flow type floating bed hydrogenation heat cracking reaction process R10 of heavy oil R10F of the present invention The heat cracking reaction of heavy oil R10F, the reaction of thermal cracking free radical stabilized hydrogenation generate the lower hydro carbons of at least part boiling point and produce Object；Heavy oil up flow type heat from hydrogenation cracking reaction process R10 usually cannot achieve one way and react whole lightings, and usually it is reasonable High conversion per pass is usually 70~85%, and there are certain amounts in such heat from hydrogenation cracking one way reaction product R10P such as 15~30% tail oil (heat from hydrogenation crackate residual oil) THC-VR.

The floating bed hydrogenation heat cracking reaction process R10 of heavy oil R10F of the present invention, using floating bed hydrogenation reactor, Heat cracking reaction, the thermal cracking of residue fraction at least part heavy oil R10F (normal boiling point is higher than 530 DEG C of hydro carbons) occurs The stabilized hydrogenation of free radical reacts, and generates the lower hydrocarbon product of at least part boiling point (gasifiable, retortable component)；Heavy oil The floating bed hydrogenation heat cracking reaction process of R10F, usually also occur the hydrocarbon component hydrofining reaction (alkene plus hydrogen saturation Reaction, aromatic hydrocarbons plus hydrogen saturated reaction), heteroatomic hydrogenolysis, organic metal hydrogenolysis, hydro carbons or hydro carbons also occurs It is pyrolyzed the thermal condensation reaction of free radical；The thermal condensation reaction may generate coke or precursors of coke.

If from the point of view of component structure, up flow type floating bed hydrogenation product residual oil THC-VR inherently raw material R10F The residue of the middle non-lighting of heavy oil macromolecular or the concentrate of conversion product or thermal condensation object macromolecular, with raw material heavy oil R10F's Compared with boiling fraction, in general, gum level therein, asphalt content, carbon residue content can increase in various degree, such as basis It reacts hydrogen partial pressure, reaction temperature, catalyst type, whether use hydrogen supply dissolvent, the difference in reaction time, it may increase 10~ 100%.

In the present invention, it is easy to mechanically decoupled big particle size of catalyst particle BP, grain diameter: usual 100 nanometers of >, one As 300 nanometers of >, particularly 500 nanometers, more particularly > 1000 nanometers of >.

In the present invention, it is difficult to mechanically decoupled small size particle LP, grain diameter: usual 100 nanometers of <, general < 50 Nanometer, particularly 10 nanometers, more particularly < 5 nanometers of <.

The up flow type floating bed hydrogenation reaction process of heavy oil R10F of the present invention is using distributed beaded catalyst Guarantee the dispersed homogeneous degree of distributed beaded catalyst, the liquid phase of the particle containing disperse type catalyzer, be usually formed suspension or And colloid, the efficiency of catalyst can be just given full play in this way.

The up flow type floating bed hydrogenation reaction process of heavy oil R10F of the present invention, using being easy to mechanically decoupled big partial size Catalyst granules BP, therefore, according to liquid phase viscosity, density, the difference of flow velocity, according to density of solid particles, the difference of wetability, There are the upper limits for the appropriate particle size of big particle size of catalyst particle BP, under conditions of catalyst amount is certain, catalyst R10C The increase of degree not only reduces the external surface area (i.e. reduction catalyst efficiency) of catalyst, reduces the granule number of catalyst (i.e. Reduce catalyst dispersed homogeneous degree), it can also cause catalyst granules sedimentation (i.e. destruction suspended state), thereby it is ensured that new addition Or it is the upper limit particle size for limiting big particle size of catalyst particle BP that newly-generated catalyst granules will not be settled in reaction process R10 One hard conditions, certain catalyst granules mentioned here does not include that coking leads to the catalyst granules after particle size growth.? Guarantee the weight of catalyst R10C particle and the long-pending certain premise of catalyst external surface in the liquid phase of the unit volume of reaction process Under, in order to reduce the fresh catalyst of supplement or the dosage of catalyst matrix object, reaction product R10P can be recycled and take out of Catalyst R10C particle, such as use centrifugal sedimentation method, obtain the underflow of enriched catalytic agent particle using cyclone hydraulic separators And reaction process R10 circulative accumulation is returned, and at this moment, the granularity of catalyst R10C particle not Ying Tai little, in favor of separation and recovery.It is comprehensive It closes and states two requirements, can test and learn preferred big particle size of catalyst particle BP particle size range, it has following spy simultaneously Point:

It is recycled 1. can be separated and recovered by high efficiency, usual recycle ratio > 50, general recycle ratio > 100, particularly Recycle ratio > 1000；

2. being capable of providing more granule number (being related to catalyst dispersion degree), larger external surface area (it is anti-to be related to catalyst Answer interfacial area).

For the catalyst R10C that hydrocarbon floating bed hydrogenation reaction process R10 is used, it is easy to mechanically decoupled big partial size The grain graininess of catalyst granules BP: be usually 0.080~3.000 μm (micron), general 0.120~2.000 μm (micron), compared with Good person is 0.240~1.000 μm (micron), the best is 0.500~0.80 μm (micron).

The up flow type floating bed hydrogenation reaction process of heavy oil R10F of the present invention, using being difficult to mechanically decoupled small particle Particle LP is generally separated floating bed hydrogenation and generates the available residual oil or its extraction process material containing LP containing LP of oil, then Return to R10 circulative accumulation.

Gluey pitch shape component contained by petroleum base decompression residuum is usually with dispersed phase existing for supramolecular structure, analysis Statistics indicate that glue asphaltic substances dispersed phase therein is that molecular weight is up to thousands of to tens of thousands of or even hundreds of thousands rock-steady structure Group, by taking molecular weight is up to the rock-steady structure group more than tens of thousands of i.e. heavy asphalt matter HWA as an example, these groups contain a large amount of thick Cycloaromatics unit simultaneously contains the elements such as metal, sulphur, nitrogen, is associated matter structure with multi-layer structure group, lighting process The main task of (heat from hydrogenation cracking process) is to disassociate these macromoleculars, hydrogen saturation, cracking is added to be few compared with its original object charcoal number Ten times, hundred times or even thousand times of small molecule, lighting reaction step quantity is most, the reaction time longest needed；These are heavy The molecular dimension (width or length or thickness) of matter asphalitine HWA dispersed phase is even more big up to tens~several hundred nanometers, for The catalyst granules of undersized (such as 0.020~0.100 μm of grain graininess <) will form package screen effect, on the one hand meeting Formed lack hydrogen environment to cause thermal condensation reaction, coking reaction, be on the other hand unfavorable for catalyst surface it is quick substitute from And reduce catalysis reaction efficiency；The molecular dimension (width or length or thickness) of these heavy asphalt matter HWA dispersed phases is up to several Ten~several hundred nanometers are even more big, in order to which the synchronous contact that the surface of heavy asphalt matter HWA is allowed to surface area as big as possible is unfolded And heavy catalyst surface, carries out efficient catalytic hydrogenation reaction, the catalyst granules for needing surface area (or granularity) to match, i.e., The catalyst granules that asphalitine HWA efficient catalytic hydrogenation reaction matches is unsuitable too small, and particle is suitable for preferably big fineness ratio If grain graininess is preferably 0.080~0.500 μm even more big；During reaction, catalyst granules and heavy asphalt matter HWA In condensed-nuclei aromatics unit, aromatic hydrocarbons, sulphur, the interaction such as nitrogen, existing attraction makes it mutually adsorb and extend effecting reaction Time, while catalyst grain size is larger, can prevent the package screen effect of asphalitine group, and wall surface is inhibited to form scarce hydrogen environment To inhibit thermal condensation reaction, coking reaction.In other words, under conditions of there are small grain size catalyst, it is suitable for big for existing simultaneously The heat from hydrogenation cracking reaction effect of the catalyst of granularity, heavy asphalt matter HWA will significantly improve.This is tested and is demonstrate,proved It is real.

Certainly, it contained by most petroleum base decompression residuum for gluey pitch shape component dispersed phase, usually contains big The molecular weight of amount about between 1,000 to 10,000 light asphalt matter LWA rock-steady structure group, they are usually gluey pitch shape groups The major part (by weight) divided, these groups contain condensed-nuclei aromatics unit and containing elements such as metal, sulphur, nitrogen, have Its lighting process (heat from hydrogenation cracking process) of associated matter structure group of small layers structure (such as only 2 layers of structure) it is main Task is to disassociate these macromoleculars, hydrogen saturation, cracking is added to be several times few compared with its original object charcoal number, tens times small molecules, Lighting reaction step quantity is more, and the reaction time needed is longer；The molecular dimension of these light asphalt matter LWA dispersed phases Only about 8~100 nanometers of (width or length or thickness), molecular amounts are huge, they are uniformly distributed extensively in the liquid phase, for reality The synchronism or uniformity of the heat from hydrogenation cracking reaction of existing light asphalt matter MWA, it is desirable to use the small grain size of enormous amount is urged Catalyst particles form colloidal solution, improve catalyst granules dispersion degree, particle exterior surface product, i.e., efficient with light asphalt matter LWA The catalyst granules that catalytic hydrogenation reaction matches preferably is suitable for small, for example grain graininess is preferably 8~100 nanometers；Certainly, due to it The ability for forming package screen effect to catalyst granules is far below heavy asphalt matter HWA, with light asphalt matter LWA efficient catalytic The catalyst granules that hydrogenation reaction matches can also be replaced with the particle of smaller particle size, for example that grain graininess can be used is suitable It is 5.0~10 nanometers of < (i.e. 0.005~0.010 micron), 3 nanometers of length is approximately equivalent to 10 phenyl ring length arranged side by side.

Certainly, for gluey pitch shape component dispersed phase, usually also contain contained by most petroleum base decompression residuum A large amount of molecular weight is between 300 (21 hydrocarbon of carbon that 360 DEG C of normal boiling point) to the wax oil of 560 (40 hydrocarbon of carbon that 540 DEG C of normal boiling point) Component VGO molecule and the low hydro carbons macromolecular of other fragrant charcoal rates, in most cases part wax oil component VGO (from feedstock oil, Recycle oil) heat from hydrogenation cracking reaction is needed, these molecules contain a large amount of aromatic hydrocarbons and containing the elements such as sulphur, nitrogen, lighting processes The main task of (heat from hydrogenation cracking process) is that these wax oil molecules are added to hydrogen saturation, cracking, becomes diesel oil, naphtha, routine The small molecule of carburet hydrogen；Only about 2~6 nanometers of these wax oils component VGO molecule (width or length or thickness), molecular amounts are huge Greatly, they are uniformly distributed extensively in the liquid phase, in order to realize wax oil component VGO heat from hydrogenation cracking reaction synchronism or uniformly Property, it is desirable to use the catalyst granules of the small grain size of enormous amount forms colloidal solution, improves catalyst granules dispersion degree, particle External surface area, i.e., the catalyst granules to match with wax oil component VGO molecule efficient catalytic hydrogenation reaction is preferably small as far as possible, such as Grain granularity is preferably 5.0~10 nanometers of < (i.e. 0.005~0.010 micron).

For decompression residuum floating bed hydrogenation heat cracking reaction process, essentially, it is only improved heavy asphalt matter HWA Hydrogenation reaction conversion ratio, can be effectively reduced unconverted pitch yield, reduce condensation pitch yield, reduce free carbon produce Rate, and then improve the constitutive property (reduce asphaltene concentration, reduction carboloy residue, raising catalyst and carry ratio) of circulation residual oil, And then the recycle ratio (reducing catalyst make-up amount) of recycle oil is improved, therefore, how to improve the hydrogenation reaction of heavy asphalt matter HWA Conversion ratio is a crucial technical problem of decompression residuum floating bed hydrogenation heat cracking reaction process.

For the hydrogenation reaction of heavy asphalt matter HWA, from contact mechanism of catalytic reaction, high surface area catalyst Particle can be heavy asphalt matter HWA structure cluster expansion, and small surface area catalyst can be inserted into heavy asphalt matter HWA structure collection The internal voids of group can be attached to outer surface, and flexible contacting heavy asphalt matter HWA structure group is contained to be condensed aromatic ring unit, virtue Ring element；High surface area (bulky grain) catalyst, small surface area (little particle) catalyst is applied in combination simultaneously, it is bigger than being used alone Small surface area (little particle) catalyst is used alone in surface area (bulky grain) catalyst, has more efficiently synergistic effect.Deng Under the conditions of catalyst weight, the surface area of large granular catalyst can be far below the surface area of catalyst particle, therefore, in order to drop Low large granular catalyst dosage, it is necessary to carry out separation and recovery and recycle.

In order to make full use of the secondary large-size particles catalyst BP using huge internal circulating load, can BP (be newly added material, be followed Ring material) the floating bed hydrogenation modified-reaction process BRA production hydrogen supply dissolvent of the high aromatic hydrocarbons wax oil BRAF of introducing, then floating bed hydrogenation The floating bed hydrogenation reaction process R10 that BP and hydrogen supply dissolvent in modified-reaction product BRAP enter decompression residuum R10F makes With.

So far, it has been proposed that basic conception of the invention: content of wax oil plant adds hydrogen, adds hydrogen, catalyst circulation containing oil of dreg Combined method, the suspension of floating bed hydrogenation modified-reaction process BRA, decompression residuum R10F suitable for high aromatic hydrocarbons wax oil BRAF Bed hydroprocessing reaction process R10, the combination for separating cyclic process XSX0 for being easy to mechanically decoupled large-size particles catalyst BP, are deposited It is that the BP of BRA is used by R10 bis- times, the BP in R10 product R10P is isolated through XSX0 and returned to BRA circulation rich in BP material It is accumulative, powerful BP recycle ratio is maintained to increase amounts of particles and catalyst external surface product, and BP provides big individual particle area To prevent heavy asphalt matter HWA package catalyst granules from forming excessive screen effect, reaction process can be used simultaneously the machine of being difficult to Tool separation small size particle LP, partially the product residual oil containing LP can return to BRA or with R10 circulative accumulation, can be greatly reduced and urge Agent consumption improves overall economics；Conversion per pass can be effectively improved or reduce reaction temperature, improve technology stability, it can Investment, hydrogen consumption, energy consumption, catalyst consumption, gas recovery ratio are reduced, liquid is improved and receives, improves generation oil quality；Catalyst may be implemented Height ratio is recycled, and is able to achieve the separation of catalyst Yu other nano particle solids, realizes the purification of outlet catalyst solid Convenient for secondary operation or recycling, conducive to the technique for forming ultralow residue emission index；Can be used catalyst with base of molybdenum, hydrogen supply dissolvent, Diluent, feedstock oil can branch charging processing；Floating bed hydrogenation heat cracking reaction process R10 can be optimized, fractional distillation process, extracted The operating condition and operating result of journey.

There are many floating bed hydrogenation heat cracking reaction separation methods of existing heavy oil or residual oil, wherein there is industrialization to operate The dreg-oil suspension bed hydrogenation cracking reaction separation method of achievement have Canadian CANMET hydrogenation of residual oil suspended bed thermocracking process (after To be integrated into the Uniflex technology of Uop Inc., the U.S.), the EST hydrogenation of residual oil suspended bed hot tearing chemical industry of Italian eni company Skill.Other dreg-oil suspension bed hydrogenation cracking reaction separation methods have BPVCC technology, the country, Venezuela of British Petroleum Company The HDHPLUS technology of oil company (PDVSA), VRSH technology of U.S. Chevron etc..The beaded catalyst used gradually by Bulky grain (partial size be based on several microns to tens microns) is to little particle (partial size is even less than 10 nanometers less than 200 nanometers) transition.

The Uniflex technology of Canadian CANMET hydrogenation of residual oil suspended bed thermocracking process and Uop Inc., the U.S. uses iron The EST hydrogenation of residual oil suspended bed thermocracking process of base catalyst, Italian eni company uses catalyst with base of molybdenum, and being two kinds has generation The technique of table, the two are compared, the several hundred PPm of the catalyst loading of EST technique (usually 200~300PPm), only About 1 the percent of CANMET catalyst loading 1~3% (to feed residue weight), only Uniflex technology catalyst adds About 1st/50th of dosage 1.0~1.5% (to feed residue weight), and heat cracking reaction temperature is lower than ferrum-based catalyst 30~50 DEG C, gas yield is only the 30~60% of ferrum-based catalyst gas yield, is higher by 8~10% (to feed residue weight) Pitch conversion ratio, correspondingly, the hydrogen consumption of unit raw material is low, product hydrogen content is high, reaction process system stability is good.

The heavy oil floating bed hydrogenation heat cracking reaction separation method of one Reaction Separation throttling journey is only set, if setting contains The thermal cracking of solid particle, circulation heavy oil containing unconverted residue fraction recycles hydrogenation system, in conversion zone, raw material in order to prevent The asphalitine for being difficult to thermal cracking that oil carries or thermal condensation coke or precursors of coke build up to form high concentration asphalitine Circulation residual oil deteriorate the first conversion zone property of liquid phase (make carbon residue increase, viscosity number increase, average hydrogen content decline), be Sulfide solid that the metal for preventing feedstock oil from carrying generates, other ash contents, existing for the first heat from hydrogenation cracking reaction process The solids such as catalyst solid particle build up to form high concentration containing residual oil is recycled admittedly, and certain ratio must be discharged in the first segregation section The outlet decompression residuum of rate；Compared with fresh residual oil R10F, the solid particle carrying rate of the first segregation section outlet decompression residuum is more Height, asphaltene concentration are higher, asphalitine is more difficult to heat from hydrogenation cracking processing.

The slurry hydrocracking reaction process 20 described in Chinese patent ZL200980145006.5 can combine processing weight Decompression residuum, that is, logistics 4 of oil 12, decompressed wax oil, that is, logistics 5a of heavy oil 12,20 product of slurry hydrocracking reaction process point The fractionation fraction wax oil i.e. logistics 2 of the coking product of fraction wax oil i.e. logistics 3, coking 30, above-mentioned a few road material mixing It carries out combining slurry hydrocracking reaction together, has passed through whole slurry hydrocracking reaction process 20.In the method, The catalyst granules of discharge reactor eventually enters into coke product 10, is not recycled and returned to slurry hydrocracking part, therefore Catalyst amount is very big, and catalyst cost is too high.

Chinese patent ZL201080035430.7 from slurry hydrocracking vacuum gas oil (VGO) and composition for separating The method and apparatus of pitch, discloses a kind of for heavy hydrocarbon charge to be converted to the method and apparatus compared with lighter hydrocarbons product, will weigh Matter hydrocarbon charging particulate solid material pulp is to form heavy hydrocarbon slurry and be hydrocracked in slurry hydrocracking unit to produce Raw vacuum gas oil (VGO) (VGO) and pitch.First vacuum column is by VGO and separated from bitumen, and the second vacuum column is further by more heavy VGO and separated from bitumen.The VGO of similar 15 weight % can be recovered and recycled to slurry hydrocracking portion by the second vacuum column Point.It obtains can be made into particle and is not bonded to bituminous composition together when transporting.In the method, the catalyst of reactor is discharged Particle eventually enters into asphaltic products, is not recycled and returned to slurry hydrocracking part, therefore catalyst amount is very big, catalyst Cost is too high.

The hydrogenation of residual oil suspended bed heat cracking reaction separation of the unconverted residual oil cycling hot cracking system containing solid particle is set Method, representative processes are the EST hydrogenation of residual oil suspended bed thermocracking process of Italian eni company.

In EST hydrogenation of residual oil suspended bed thermocracking process, in decompression residuum in suspended-bed reactor, it is catalyzed in molybdenum base It is hydrocracked, is turned under agent presence and the operating condition (temperature is about 400~425 DEG C, pressure is about 15~17MPa) mitigated Turn to light product.The oil converted enters separation system, with gas recovery, naphtha, intermediate distillates and wax oil, hydrogen gas phase Product enters amine after isolating light product and washes part, and cleaning hydrogen gas is recycled back to after second compression again and hydrogen make-up Reaction process recycles distillate from liquid phase.It is female using a kind of oil-soluble in EST hydrogenation of residual oil suspended bed thermocracking process Body be converted into the form of micron particles or nanometer thin layers in the reactor existing for DNAcarrier free MoS₂.Because feed residue is taken In metal form independent phase in the deposition of sulfides that reaction process generates, do not interfere exposed MoS₂Activated centre, so Catalyst, which is practically without, during whole operation changes, can be with recycled for multiple times because without aging.Due to catalysis Agent exists in the form of nanometer thin layers, has great external surface area, high dispersion degree, activation hydrogen, induction aromatic ring side The efficiency of chain fracture is very high.

In EST hydrogenation of residual oil suspended bed thermocracking process, for catalyst, the influence very little of green coke, surface area are big Be not present mass transfer diffusional resistance so that EST catalyst than carried catalyst have higher activity.Very high specific activity is (single The activity of position quality) make the concentration of EST catalyst only need to maintain thousands of μ g/g levels, it is anti-that good catalysis can be formed Answer condition.Because catalyst in feed residue dispersedly very well, reaction process, exothermic heat of reaction be spatially it is uniform, because The control of this temperature is uniformly without hot-spot occurs.Therefore, the residual oil that tenor is high, asphalt content is high is selected This DNAcarrier free suspension bed catalyst is especially effective.Residuum conversion process is generated free radicals by thermal response by the fracture of C-C key Start, free radical is quickly obtained reactive hydrogen and realizes stabilized hydrogenation, avoids the occurrence of the β fission and their continuous combination of free radical And lead to green coke.The MoS in suspension bed₂Distance between thin layer than carried catalyst between oil molecule at a distance from small several quantity Therefore grade shortens free radical and generates time and free radical arrival catalyst surface and complete stabilized hydrogenation process required time, Also just reduce green coke.MoS₂With the hydrogen catalyzed ability for being allowed to be changed into reactive hydrogen (hydrogen atom), also there is activated aromatic ring Ability, so that aromatic hydrogenation, carbon residue are reduced, and it is de- hydrodesulfurization, hydrodenitrogeneration plus hydrogen can be carried out by C- heteroatomic bond hydrogenolysis The reactions such as oxygen, hydrodemetallization remove hetero atom.

In EST hydrogenation of residual oil suspended bed thermocracking process, the catalyst of unconverted residual oil and dispersion, other solids one Road is recycled back into reactor.Technique severity (reaction time and reaction temperature) is optimized, portion according to feed residue quality Point unconverted residual oil (its quality is more worse than the same boiling range component of fresh feed residual oil, and hydrogen content is lower, carbon residue is higher) and new Fresh residual oil mixing carries out circulation heat from hydrogenation cracking reaction, and the asphalitine on the one hand making it possible to lighting, which is repeatedly reacted, realizes depth Lighting is converted, the multiple thermal response of the asphalitine for being difficult to lighting is on the one hand caused to form thermal condensation product accumulation, is maintaining one Under conditions of fixed outlet residual oil ratio, timely discharge part is difficult to the asphalitine or coke precursor converted, so that circulation slag The property of oil is chronically in stable state, and circulation residual oil, the first conversion zone liquid phase generation asphaltene precipitation is avoided to cause to give birth to Burnt and equipment scaling, such realization recycle heat from hydrogenation cracking and convert up to close to complete, what close complete conversion described herein referred to It is that outlet tail oil is less rather than residual oil raw material 100% realizes lighting.It is (main in order to limit the metal in feed residue It is vanadium, nickel, iron) circulative accumulation of sulfide, it is necessary to the unconverted slag of a small amount of (to the ratio of about 3 weight % of fresh residual oil) is discharged Oil, metal sulfide grain and other solids containing residual oil hydro carbons, carrying in unconverted residual oil.

In EST hydrogenation of residual oil suspended bed thermocracking process, the suspension bed hydrogenation catalyst of early application is micron order Grain, the suspension bed hydrogenation catalyst that the later period uses are the particles that partial size is lower than 10 nanometers, and catalyst circulation pattern is that separation suspends It is available containing the residual oil of catalyst granules or its extraction process material that bed hydroprocessing generates oil, then returns to R10 circulative accumulation.? In EST technique, the catalyst granules and return to rich catalyst granules material that mechanically decoupled reaction product carries are not accounted for The scheme of the circulative accumulation of floating bed hydrogenation reaction process.

By taking the EST hydrogenation of residual oil suspended bed thermocracking process of Italian eni company as an example, outlet oil containing solid slag VR- Hydrocarbon ils quantity in OUTS is normally no higher than 5%, is typically only 2.5~3.3 weight % of feed residue weight, presses 3 weights below It measures % to calculate, while residual oil conversion per pass presses 68 weight %.For 1,000,000 tons/year of residual oil raw materials, quantity is 30,000 Ton/year, since catalyst molybdenum disulfide amount of solids is some thousandths of to the ratio of feedstock oil quantity in reaction process liquid phase, press 2/1000ths calculate, and contain 30,000 tons/year of hydrocarbon ils, 0.00625 times of hydrocarbon ils of catalysis in such outlet oil containing solid slag VR-OUTS Agent molybdenum disulfide solid particle (187.5 tons/year).Since catalyst with base of molybdenum is expensive, even if only according to 1,000,000 yuan of people Coin/ton calculates, and the price of molybdenum disulfide solid particle (187.5 tons/year) is up to 1.875 hundred million yuans/year, therefore, is protecting Under the premise of card operating effect is constant, reducing catalyst make-up measurer has huge economic value, even catalyst will be reduced Magnitude of recruitment reduces only 10%, and the cost saved is also surprising (18,750,000 yuan/year).

The existing heavy oil floating bed hydrogenation heat cracking reaction separation side that a Reaction Separation throttling journey is only set above-mentioned In method, the composition of outlet tail oil containing catalyst and the residual oil containing catalyst circulation be it is identical, therefore, from general reaction product The yield of catalyst and the distribution ratio angle of discharge amount say, substantially one stage catalyzing dose of concentrate circular response mode, because An allocation step is only existed, this heavy oil floating bed hydrogenation heat cracking reaction separation method at least has the disadvantage in that

1. under the premise of the catalyst amount of maintenance reaction process is certain, in order to reduce fresh catalyst magnitude of recruitment, The quantity of the residual oil containing catalyst circulation must be increased, still, necessarily cause colloid in residual oil containing catalyst circulation, asphalitine by Ratio increases, and the property of liquid phase of deteriorative reaction process is urged；

That is, under conditions of maintaining the catalyst concn in reaction process liquid phase certain, in order to reduce catalyst Magnitude of recruitment and when increasing catalyst circulation amount, can not reduce or control simultaneously colloid, the asphalitine quantity in reaction process；

2., can be with when increasing catalyst circulation amount maintaining the catalyst concn in reaction process liquid phase certain Catalyst make-up amount is reduced, if at the same time it is wished that reduction or colloid, asphalitine quantity in control reaction process, must just reduce Containing the colloid in catalyst, the recycle oil containing residual oil, asphaltene concentration, according to the prior art, it can only just increase outlet containing catalysis The high the hydrocarbon component of ratio colloid, asphalitine hydrogen-carbon ratio in agent tail oil, it is evident that can only reduce the totality of raw material heavy oil R10F to turn Rate；

3. outlet tail oil containing catalyst is the mixture of high viscosity Vacuum Residue Fractions Yu high degree of dispersion beaded catalyst, no Just the physical separation such as sedimentation separation, centrifuge separation；

4. the molecular dimension (width or length or thickness) of heavy asphalt matter HWA dispersed phase reachable tens~several hundred nanometers are very To more greatly, package shielding effect will form for the catalyst granules of undersized (such as 0.080~0.150 μm of grain graininess <) It answers, will form scarce hydrogen environment on the one hand to cause thermal condensation reaction, coking reaction, be on the other hand unfavorable for catalyst surface Quickly substitute to reduce catalysis reaction efficiency；And EST nano-scale particle catalyst grain size it is too small (0.3~0.5 nanometer of thickness, 3~5 nanometers of width), the surface that heavy asphalt matter HWA can not be unfolded is allowed to the synchronous contact catalyst table of surface area as big as possible Face, it is difficult to carry out efficient catalytic hydrogenation reaction, lack the catalyst granules that surface area (or granularity) matches；

5. not accounting for that big particle size of catalyst and small particle catalyst is applied in combination, do not account for returning with mechanical separation method Receipts recycle big particle size of catalyst.

It is a kind of improve catalyst utilization mode be that outlet tail oil containing catalyst is separated into catalysis with polarity extracting agent The extract liquor of agent particle and polar solvent and residual oil, but it is with high costs, uneconomical.

In fact, causing having its source in for above-mentioned technology crux: in single Reaction Separation throttling journey, being based on fractionating technology A separating step, (outlet is residual by the overall non-conversion of residual oil R10F for the catalyst concn in circulation residual oil isolated Night ratio) it is determined, the recycle oil containing residual oil, while there is the dual master of circulation Vacuum Residue Fractions and recycling catalyst component Body function exists restrain coupling therebetween, and reducing catalyst loading requirement as far as possible reduces outlet residual oil ratio (outlet catalyst ratio), but reducing outlet residual oil ratio (outlet catalyst ratio) necessarily causes to be enriched in unconverted residual oil The asphalitine of hardly possible conversion.Since the engineering technology of hydrogenation of residual oil suspended bed thermocracking process needs comprehensive many factors to optimize Consider, therefore, for difficult process residual oils, extremely difficult processing work residual oil, needs that both cumulative effects are utilized respectively or are coped with, from And form classification processing or classification joint processing to a certain extent.

Above-mentioned analysis implies that two main functionalities for needing to recycle residual oil and circulation specified particle diameter catalyst solve Coupling selects suitable workflow position logistics if increasing the separating step of effective a catalyst and Vacuum Residue Fractions, should The lighter the hydrocarbon component of ratio Vacuum Residue Fractions in logistics is preferably to need to recycle plus the hydrocarbon component such as heavy wax oil of hydrogen, evaporate entirely Point wax oil (including heavy wax oil, lightweight wax oil, even heavy diesel fuel), density low based on high temperature, hydrocarbon material viscosity is low and catalyst particles Grain relative density is very big, and the high cracking rate R10 of residual oil needs largely to recycle cracking tail oil again in addition, to containing catalyst, group containing residual oil The suitable high temperature hydrocarbon material of the initial boiling point divided, is returned with the rich catalyst granules liquid material KSX that rotary filter press system high efficiency is isolated Residual night VS, residual night VS or the rich catalyst separating liquid of its rotation point are obtained after R10, the poor solid particless liquid material depth isolated distillation or vaporization R10 is returned, may make up and constitute 2 grades or multiple catalysts concentrate circular response mode.

That is, a kind of decoupling method is will to contain catalyst, the specific workflow position containing residue fraction (with low viscous Degree, low-density) heavy oil (actually upstream separation, fractionation process separating resulting, to catalyst, decompression residuum group Point it is concentrated), the level-one relative separation of catalyst and residue fraction is carried out using centrifuge separation, isolates level-one rich in urging Liquid material (being used as level-one richness catalyst circulation oil), the liquid material of the poor catalyst of level-one of catalyst particles, then proceed to urge poor to level-one The liquid material of agent, the lock out operation for being distilled or being evaporated realize the secondary concentration of catalyst, isolate second level rich in catalyst Liquid material (can be used as second level richness catalyst circulation oil, second level richness catalyst residual oil), the liquid material of the poor catalyst of second level of particle, and 3rd level catalyst concentration (catalyst is separated with the three-level of residue fraction) can be carried out to the liquid material of the poor catalyst of second level, separation Liquid material (can be used as three-level richness catalyst circulation oil, three-level richness catalyst residual oil), three-level of the three-level rich in catalyst granules are poor out The liquid material of catalyst, the liquid material of the poor catalyst of three-level is used as the rich asphaltene bottoms of the poor catalyst of outlet, to realize asphalitine Highly selective discharge.

It therefore, include to be easy to mechanically decoupled larger grain particles BP and difficulty based on the discrete particles catalyst R10C used With the concept of mechanically decoupled smaller particle size particle LP, it usually needs mechanically decoupled process is arranged, isolates big particle size of catalyst It is recycled.

Material containing agent of the present invention refers to the hydrocarbon-bearing material containing distributed beaded catalyst R10C.

Mechanically decoupled process of the present invention is referred to being not belonging to distillation, be evaporated, the use seperator of chemical separation process The separation process of tool or equipment.

In fact, being reacted and being produced using the heavy oil floating bed hydrogenation of catalyst with base of molybdenum due to the excellent performance of catalyst with base of molybdenum The viscosity of the residual oil of object is usually lower, therefore, can use catalyst granules specific gravity much larger than residual oil specific gravity, slag oil asphalt component Between interaction force larger feature, by the separation process heavy-fluid based on R10P, fractional distillation process heavy-fluid, fraction products heavy oil Extract liquor etc. is separated into the object that at least 2 strands of catalyst concns, asphaltene concentrations are different containing the liquid material of catalyst, bituminous component Material, the circulation loop with respectively suitable recycle ratio, respectively suitable return to the flexible cyclic process in suitable procedure position.

The present invention realizes lightweight residue fraction circulation, heavy oil residue component circulation, little particle catalysis to a certain extent Agent circulation, large granular catalyst recycle the decoupling of multiple main functionalities, while realizing consolidating for design granularity to a certain extent Body catalyst and the self-produced nano level metal sulfide of residual oil R10F floating bed hydrogenation heat cracking reaction process, ash content, free carbon Relative separation, conducive to realize outlet catalyst solid purification, the present invention has the advantages that

1. in a first aspect, can flexibly increase substantially the recycle ratio of large granular catalyst for catalyst with base of molybdenum Rate with reduce outlet tail oil yield, be greatly lowered in outlet residue heavy asphalt matter concentration, reduce catalyst concn, thus Fresh catalyst magnitude of recruitment thoroughly is greatly lowered, considerably reduces catalyst costs, while can realize vacuum residuum feed The high overall conversion of R10F；

2. second aspect is used only a small amount of fresh catalyst and mends for poor residuum deep hydrogenation thermal cracking process Charge can be realized that reaction process catalyst concn is sufficiently high, so as to increase substantially the conversion per pass of heavy asphalt matter Rate improves circulation residual oil hydrogen content (reducing residual carbon content), and circulation residual oil ratio is finally greatly lowered, device is greatly lowered Scale, investment and energy consumption, which is greatly lowered, to be reduced；

3. the third aspect, for using needle-shape coke raw material hydrogenated bitumen as the bituminous high temperature coal-tar R10F's of productive target For floating bed hydrogenation heat cracking reaction process R10, reaction process can be realized using only a small amount of fresh catalyst magnitude of recruitment and urge Agent concentration is suitable for height, so as to be precisely controlled the aromatic hydrogenation fractional saturation reaction depth of high temperature coal-tar asphalitine, is obtained Lower needle-shape coke raw material-the hydrogenated bitumen of catalyst content for being suitable for fragrant charcoal rate realizes the accurate plus hydrogen of asphalitine；

4. the molecular dimension (width or length or thickness) of heavy asphalt matter HWA dispersed phase reachable tens~several hundred nanometers are very To more greatly, package shielding effect will form for the catalyst granules of undersized (such as 0.080~0.150 μm of grain graininess <) It answers, will form scarce hydrogen environment on the one hand to cause thermal condensation reaction, coking reaction, be on the other hand unfavorable for catalyst surface Quickly substitute to reduce catalysis reaction efficiency；And bulky grain is applied in combination while using catalyst particle in the present invention Catalyst can effectively increase substantially the hydrogenation efficiency of heavy asphalt matter HWA, and mechanical separation method recycling can be used and follow Ring utilizes big particle size of catalyst.

Content of wax oil plant of the present invention adds hydrogen, adds the combined method of hydrogen, catalyst circulation containing oil of dreg, applied to residual oil R10F's When the fractional distillation process U10 of the hot high score oil of floating bed hydrogenation heat cracking reaction process R10 and product R10P, main purpose exists In, maintain reaction process liquid phase in catalyst concn it is certain under conditions of, increase and urge to reduce catalyst make-up amount When agent internal circulating load, while colloid, the asphalitine quantity in reaction process are reduced or being controlled, can get in following target effects 1 or several:

1. catalyst benefit can be greatly lowered under conditions of maintaining the catalyst concn in reaction process liquid phase certain Charge reduces catalyst cost；

2. can significantly be mentioned under conditions of catalyst make-up amount is certain, feed residue R10F overall conversion is certain Catalyst concn in high reaction process liquid phase is conducive to improve conversion per pass, to reduce circulation residual oil quantity, that is, has drop Low unit scale, the advantage for reducing investment；

3. can significantly be mentioned under conditions of catalyst make-up amount is certain, feed residue R10F overall conversion is certain Catalyst concn in high reaction process liquid phase is conducive to improve conversion per pass, to reduce circulation residual oil quantity, can reduce Circulation residual oil brings the colloid of reaction process R10, asphalitine quantity into, that is, has and improve operational stability, extend continuous operation behaviour Make the advantage in period；

4., can under conditions of catalyst make-up amount is certain, feed residue R10F overall conversion, conversion per pass are certain To increase substantially the catalyst concn in reaction process liquid phase, it is conducive to reduce reaction temperature, to reduce thermal condensation negative reaction Quantity reduces colloid, asphalitine quantity in circulation residual oil, can reduce circulation residual oil and bring the colloid of reaction process R10, drip into Green prime number amount has the advantage for improving operational stability, extending the continuous operation operation cycle；

5. catalyst make-up amount is certain, feed residue R10F overall conversion, conversion per pass are certain, react in liquid phase Under conditions of asphaltene concentration is certain, the catalyst concn in reaction process liquid phase can be increased substantially, is conducive to reduce reaction Temperature reduces colloid, asphalitine quantity in circulation residual oil, can reduce circulation slag to reduce thermal condensation negative reaction quantity Oil brings the colloid of reaction process R10, asphalitine quantity into, therefore, can process it is more inferior (asphaltene concentration is higher, carbon residue more It is high) feed residue, that is, be conducive to expand Raw material processing range, reduce feedstock oil cost；

6., can under conditions of catalyst make-up amount is certain, feed residue R10F overall conversion, conversion per pass are certain To increase substantially the catalyst concn in reaction process liquid phase, it is conducive to reduce reaction temperature, to reduce thermal condensation negative reaction Quantity reduces colloid, asphalitine quantity in circulation residual oil, can reduce circulation residual oil and bring the colloid of reaction process R10, drip into Green prime number amount, can be greatly lowered based on catalyst cost, can expand the strong hydrogenation catalyst of hydrofining reaction function Such as the application range of high dispersive catalyst with base of molybdenum；

7., can under conditions of catalyst make-up amount is certain, feed residue R10F overall conversion, conversion per pass are certain It is such as high using the strong hydrogenation catalyst of hydrofining reaction function to increase substantially the catalyst concn in reaction process liquid phase When dispersing catalyst with base of molybdenum, conducive to the floating bed hydrogenation modified-reaction process of building economy；

The floating bed hydrogenation modified-reaction process, goal response are to carry out aromatic hydrogenation part to high aromatic hydrocarbons material R10F Saturated reaction plus hydrogen removing impurities matter (sulphur, nitrogen, oxygen, chlorine, metal etc.) reaction, desired control carbon reactant atomicity is constant, cyclic annular knot It is few as far as possible to become, hydrogenation wax oil can be obtained in high yield, residue fraction (is dripped such as the hydrogenation high-temperature coal of needle-shape coke raw material oil It is green), it reduces gas recovery ratio, reduce hydrogen consumption；

The present invention can be added by each conversion zone of variation or operating condition, the Process flow of segregation section by joint The other hydrocarbon-bearing materials for being suitable for combining processing of work can pass through the downstream processing methods of hydrocarbon ils in a variety of hot high score gas of joint, shape At multiple combinations technique, such as following technique:

1. realizing hydrogenation modification by carrying out aromatic hydrogenation modified-reaction to high aromatic hydrocarbons material R10F, while controlling carbon reactant Atomicity is constant, cyclic annular knot is few as far as possible becomes, and therefore, when hydrogen consumption is larger, reaction heat is larger, in default of heat absorptivity The heat absorption vaporescence of heat cracking reaction, product small molecule can be used dilution hydrocarbon to reduce temperature rise, the increasing of hydrogen supply hydrocarbon can be used Add the hydrogen conversion reaction between the hydrocarbon liquid phase of low reaction heat, to reduce the gas phase hydrogen consumption reaction of high reaction heat；

2. high aromatic hydrocarbons material R10F carries out aromatic hydrogenation modified-reaction and realizes hydrogenation modification, it is conducive to inhibit thermal condensation reaction, leads to Often, the hydrogenation catalyst for preferably using hydrofining reaction function strong such as high dispersive catalyst with base of molybdenum can use dilution hydrocarbon or and hydrogen supply Hydrocarbon inhibits thermal cracking, thermal condensation reaction to reduce reaction temperature；

3. the lower supplement hydrogenation process R10K of the settable reaction temperature of R10, to reduce thermal response in final product The high component such as alkene of property；

4. high aromatic hydrocarbons material R10F can branch charging reaction to reduce dilution hydrocarbon or dosage with hydrogen supply hydrocarbon improve process Economy；

5. the generation oil distillate of hydrogenation modification reaction process R10 can return to hydrogenation modification reaction process R10 circulation plus hydrogen Reaction, pressurization is mixed with high aromatic hydrocarbons material R10F can simplify process, reduces investment, reduces energy consumption；

6. the generation oil distillate of hydrogenation modification reaction process R10 can return to the intermediate mistake of hydrogenation modification reaction process R10 Cheng Jinhang complementarity recycles hydrogenation reaction, serves as flux oil, quench oil, can reduce the quenching hydrogen gas consumption amount, dedicated of reaction process Chilling oil consumption；

7. adding for the suspension bed for the hydrogenation catalyst such as high dispersive catalyst with base of molybdenum for using hydrofining reaction function strong Enrichment is obtained in hydrogen modified-reaction process R10, autoreaction intermediate product or final reacting product or the isolate of reaction product to urge Then the rich catalyst feed of agent solid particle returns to R10 and is recycled, fresh catalyst supplement can be greatly lowered Amount reduces catalyst cost；

8. intermediate liquid product or final Liquid product recycle system is arranged in hydrogenation modification reaction process R10, it is conducive to reduce Reactor series improves liquid flow velocity in reactor, prevents solids particles precipitate；

The process that intermediate liquid product circulation returns to first reactor entrance is arranged in hydrogenation modification reaction process R10, can be with Recycling initial stage hydrogenation reaction heat makees circulation hydrogen supply dissolvent using intermediate liquid product, reduces raw material preheating temperature；

9. intermediate liquid product or final liquid product can be used or reaction generates the distillate of oil, as self-control hydrogen supply Solvent is recycled；

10. hydrogen supply dissolvent reaction process DSR can be applied in combination, the hydrogen supply dissolvent of production enters the hydrogenation modification of high aromatic hydrocarbons During reaction process R10, the hydrogenation modification reaction process R10 that hydrogen supply dissolvent reaction process DSR can be located at high aromatic hydrocarbons is used Hydrogen material upstream or downstream, high aromatic hydrocarbons hydrogenation modification reaction process R10 production oil or its distillate can be used as Hydrogen supply dissolvent reaction process DSR raw material uses.

It, can be with for the hydrocarbon component carried in the hot high score of the hydrogenation modification reaction process R10 product R10P of high aromatic hydrocarbons Hydro-upgrading reaction process 9R is applied in combination, hydro-upgrading reaction process 9R can be located at the hydrogenation modification reaction process of high aromatic hydrocarbons The upstream or downstream for the hydrogen material that R10 is used.

For the hot high score device of the hydrogenation modification reaction process R10 product R10P of high aromatic hydrocarbons, it is de- solid that gas phase can be set The washing and depositing section of body；

High fragrant charcoal rate wax oil is processed conducive to joint, first by the circulation residual oil of rich catalyst, introduces high fragrant charcoal rate wax oil Add hydrogen partial saturated reaction process to be translated into hydrogen supply hydrocarbon, was then reacted together into the floating bed hydrogenation of residual oil R10F Journey makes the secondary use of catalyst, is utilized hydrogen supply hydrocarbon, and also reduce high fragrant charcoal rate wax oil is hydrogenated into this；

In order to improve the processing efficiency of device, preferably increase the conversion per pass of heavy oil R10F；And the one way of heavy oil R10F The raising of conversion ratio necessarily reduces residue oil fraction quantity in reaction product, while increasing thermal condensation object colloid, asphalitine, liquid phase Coke quantity, this " increase of colloid, asphalitine, the quantity of liquid phase coke " with " colloid, asphalitine, liquid phase coke solvent The reduction of oily quantity " develops to over-saturation degree or critical degree of saturation, will lead to colloid, asphalitine, liquid phase coke from stabilization Colloidal solution system in be precipitated become over-saturation pitch mutually be second liquid phase, lead to quick coking in the containers such as reactor, compel Device is set to stop work.

" conversion per pass for improving heavy oil R10F necessarily increases thermal condensation object colloid, asphalitine, liquid phase coke quantity " The fact that under the premise of, avoid " colloid, asphalitine, liquid phase coke be precipitated " method, necessarily reduce heavy oil R10F one way Conversion ratio introduces external solvent naphtha, is passively method due to reducing heavy oil R10F conversion per pass, can reduce device and add Therefore work efficiency rate " introduces external suitable colloid, asphalitine, the solvent naphtha of liquid phase coke and its application method ", just at One important technical problem, it is related to the economy of the up flow type expanded bed heat from hydrogenation cracking reaction process R10 of heavy oil R10F Property, and core of the invention target is, recognize " introduce external suitable colloid, asphalitine, liquid phase coke solvent naphtha " Under the premise of, existing solvent naphtha application method is proposed to improve to reduce solvent naphtha dosage, to rationally reduce R10 and product Separation system scale is to save significantly on investment, reduce hydrogen consumption, reduce the quantity that KVGO condensation is residual oil, improves the economy of R10.

Richness aromatic hydrocarbons wax oil KVGO of the present invention, the conventional boiling range of main hydro carbons is usually 370~570 DEG C, general It is 400~570 DEG C, in particular 450~550 DEG C.

Matter wax oil KVGO in richness aromatic hydrocarbons of the present invention, the conventional boiling range of main hydro carbons is usually 400~520 DEG C, Generally 425~510 DEG C, in particular 450~510 DEG C.

In heavy oil up flow type expanded bed heat from hydrogenation cracking reaction process, the application method of conventional wax oil solvent naphtha such as China Patent ZL200980118107.3, Chinese patent ZL200980145006.5, Chinese Patent Application No. 200980145007.X, in State patent ZL201080035430.7, be by selection rich aromatic hydrocarbons wax oil KVGO and initial feed heavy oil R10F mix into Row Unionfining thermal cracking.

The present invention can be applied in combination with other any appropriate hydrogenation of residual oil suspended bed thermocracking process, constitute corresponding Group technology, possible combination technique at least:

1. the floating bed hydrogenation process of fresh heavy oil, anti-by initial stage heat from hydrogenation cracking using Liquid product recycle reactor It answers heat to be transferred to raw material heavy oil, so that its preheating temperature is reduced to 360~400 DEG C, prevents heavy oil heater tube coking, A small amount of (such as the 5~10% of heavy oil amount) hydrogen supply dissolvent further pre- anti-coking can be used；

2. using high dispersive high activated catalyst such as molybdenum series catalyst, while hydrogen supply dissolvent can be used, work is quickly provided Property hydrogen, inhibit the thermal condensation of the incipient thermal cracking process of heavy oil feedstock, this is a kind of active approach substantially, can significantly be changed It is apt to a heat from hydrogenation cracking tail oil property；

3. preventing heat cracking reaction process latter stage solution system from over-saturation pitch occur, mutually i.e. second liquid phase, this requirement are reasonable It controls conversion per pass and improves reactor exit hydrocarbon liquid phase using Liquid product recycle reactor in 65~80% ranges Aromaticity, while the high light hydrocarbon of degree of saturation is discharged in time and prevents its drop for penetrating air lift hydrogen in use reactor end reaction area Low solution aromaticity, being also prevented from its excessively circulation thermal cracking reduces liquid yield；And the presence of excessively more hydrogen supply dissolvents is reduced, Not only hot tearing rate can be improved but also the hot tearing rate of hydrogen supply dissolvent can be reduced；

4. may need rear portion conversion zone to be added, safely by the drip in liquid phase in reactor using high aromatic hydrocarbons wax oil Unconverted asphalitine in safe range, and is safely carried out reactor by green matter concentration control；

5. reducing tail oil yield, process economics are improved, the tail oil hydro-upgrading for being set using hydrogen supply dissolvent oil reacted Journey CR is carried out under conditions of high oil ratio, high catalyst concn, low reaction temperature with aromatic hydrogenation saturated reaction For the hydro-upgrading process of main target reaction, then product CRP is imported in floating bed hydrogenation heat cracking reaction process AR Rear portion reaction zone ARB carries out the heat from hydrogenation cracking reaction of appropriateness, prevents the too high initiation of modification tail oil one way hot tearing rate excessive Thermal condensation reaction controls reaction type in the whole circulation hydrogenation process of a tail oil THC-VR (add hydrogen saturation, be hydrocracked) Ratio, properly increase plus hydrogen saturated reaction ratio, reduce heat from hydrogenation cracking reaction ratio, by way of increasing internal circulating load, Realization repeatedly converts in batches, controls the stability of solution, reduces outlet tail oil quantity, improves outlet tail oil quality；It is optimal The result is that outlet tail oil amount seldom (for example be lower than 3~5%), is only used for discharge solid particle (including catalyst granules, raw material weight Oily metal sulfide, minimal amount of coking particle) prevent it from building up in reaction system；

Meanwhile batch feed technology can be used, further increase the coke forming property for inhibiting tail oil circulation hydrogenation process；

6. tail oil circulation hydro-upgrading reaction process of the invention and fresh heavy oil floating bed hydrogenation heat cracking reaction process Combined method, can reduce tail oil circulation hydro-upgrading reaction process cost, improve process economics, it is molten due to foring hydrogen supply The secondary or even multiple series circulation of agent uses, therefore is remarkably improved the hydrogenation zone hydrogen supply speed of the circulating path of hydrogen supply dissolvent Degree, overall hydrogen supply capacity, improve and recycle efficiency；

7. providing the efficient circulation path of hydrogen supply dissolvent, its circulating path length can be shortened, reduce circulation loop investment And energy consumption, it reduces hydrogen supply dissolvent and is contaminated degree, can effectively reduce cycle cost；

8. can combine the dedicated resurrection step of hydrogen supply dissolvent with distillate hydrogenation upgrading step, process collection is further increased Cheng Du reduces the investment and energy consumption of overall craft；

9. heavy-oil hydrogenation process uses floating bed hydrogenation reactor, it is preferred to use Liquid product recycle formula floating bed hydrogenation is anti- Answer device；

10. forming joint work with heavy oil catalytic cracking process or with coking heavy oil process in the main-process stream of processing of heavy oil Skill, the heat from hydrogenation cracking turn for reducing coking yield, increasing lightweight oil yield, the heavy oil feedstock for improving heat from hydrogenation cracking reaction process Rate, the operation cycle for extending heavy-oil hydrogenation heat cracking reaction process.

The present invention, when the hydrogen supply dissolvent precursor used is Rfcc Products diesel oil, heavy-cycle oil, actually group At the group technology of heavy oil catalytic cracking process and heavy-oil hydrogenation thermal cracking process.

The present invention, it is that Rfcc Products wax oil is (heavy-cycle oil, clear that the asphalitine that uses, which carries the high aromatic hydrocarbons wax oil of agent, Edible vegetable oil) when, the group technology of heavy oil catalytic cracking process Yu heavy-oil hydrogenation thermal cracking process is actually constituted, heavy oil is realized The hydrogenation modification of catalytic cracking production wax oil (heavy-cycle oil, clarified oil) and heat from hydrogenation cracking, on the one hand reduce catalytic cracking The machining load of reaction process reduces coke yield, increases liquid receipts, on the other hand increases heavy-oil hydrogenation thermal cracking process Hydrogen supply dissolvent quantity, reduce heavy-oil hydrogenation heat cracking reaction process thermal condensation object (colloid, asphalitine, coke) production Rate increases liquid receipts, increases the quantity of the carrying solvent naphtha of gum asphalt in heavy-oil hydrogenation hot cracked product, is conducive to improve Heavy-oil hydrogenation thermal cracking conversion ratio is conducive to improve fraction oil yield, reduces coke output, significantly improve process in general Economy.

Residual hydrogenation hot cracked product light wax oil can go catalytic cracking reaction process or catalytic cracking reaction process, with Voluminous catalytically cracked gasoline or and catalytic cracking diesel oil, and the precursor that catalytic cracking diesel oil may be used as lightweight hydrogen supply dissolvent makes With.

The present invention actually constitutes weight when the asphalitine carrying high aromatic hydrocarbons wax oil of agent used is coking product wax slop The group technology of oily coking and heavy-oil hydrogenation thermal cracking process, the hydrogenation modification and heat from hydrogenation for realizing coking wax slop are split Change, on the one hand reduces the machining load of pyrogenetic reaction process, reduce coke yield, increase liquid receipts, on the other hand increase The hydrogen supply dissolvent quantity of heavy-oil hydrogenation thermal cracking process, the thermal condensation object (glue for reducing heavy-oil hydrogenation heat cracking reaction process Matter, asphalitine, coke) yield, increase liquid receipts, the carrying for increasing gum asphalt in heavy-oil hydrogenation hot cracked product is molten The quantity of agent oil is conducive to improve heavy-oil hydrogenation thermal cracking conversion ratio, in general, is conducive to improve fraction oil yield, reduces coke Yield significantly improves the economy of process.

Particularly, using the heavy-oil hydrogenation heat cracking reaction process of hydrogen supply dissolvent, with the routine weight without using hydrogen supply dissolvent Oily heat from hydrogenation cracking reaction process is compared, under the conditions of identical heat from hydrogenation cracking conversion rate, the hydrogen of heat from hydrogenation cracked residue Content can dramatically increase, carbon residue can significantly reduce, which is then easier to as circulation heat from hydrogenation cracked residue In heat from hydrogenation cracking, which may be used as high-quality gasificationization raw material as outer oil extraction, as coking original Then coke yield is lower when material, thus be conducive to improve coking distillate yield, if coking such as delayed coking In feedstock oil, the hydrogenation modification oil for refining a certain proportion of high aromatic hydrocarbons wax oil is also mixed as hydrogen supply dissolvent, then forms hydrogen supply coke Change reaction process, which allows heavy-oil hydrogenation heat cracking reaction process to process (carbon residue content is higher) more inferior, price Lower residual oil.The group technology of the heavy-oil hydrogenation thermal cracking process and coking heavy oil process adds particularly suitable for newly-built heavy oil The combination of hydrogen thermal cracking process and existing coking heavy oil process.

Heavy-oil hydrogenation thermal cracking wax slop or its hydrogenation modification oil, Rfcc Products wax oil (heavy-cycle oil, clarification Oil) hydrogenation modification oil, coking heavy oil product wax slop hydrogenation modification oil, such as delayed coking of coking reaction process can be gone anti- Process or fluid coking reaction process or flexicoking reaction process are answered, serving as the hydrogen supply dissolvent oil with certain hydrogen supply capacity makes With, combine with heavy-oil hydrogenation thermal cracking residue carry out pyrogenetic reaction process, the pyrogenetic reaction process usually also joint processing straight run Decompression residuum with control overall coking raw material oil carbon residue content or with content of ashes, the tenor in product char, and weigh Oily heat from hydrogenation cracking process carries agent using that can reduce heavy-oil hydrogenation hot cracking catalyst solid and coke after hydrogen supply dissolvent The dosage of solid, to be conducive to the operating effect of the pyrogenetic reaction process of optimization heavy-oil hydrogenation thermal cracking residue.

Based on logistics composition, catalyst granules characteristic, residue fraction characteristic in process, if from distillation of the invention, rotation From the point of view of subassembly separation, the synergistic effect between above-mentioned element is advantageous, objective reality, in fact, the present invention It proposes catalyst grain size and catalyst rotation divides the relationship of concentration technology, illustrating catalyst grain size, there are a kind of suitable granularity models It encloses, suitable particle diameter assembles, this point, for low-metal content, low ash content, high asphaltene concentration or high aromatic carbon rate heavy oil Floating bed hydrogenation reaction process, have the function of great optimization operation.

Problem andsolution proposed by the present invention be existing for the poor residuum heat from hydrogenation cracking reaction process of pole one it is general All over problem and the technical solution generally used, since influential effect of the invention is huge, appearance of the invention is inevitable.

It can be realized the process flow of target of the present invention, be suitable available scheme, the invention proposes some specific Process program.

The method of the invention has not been reported.

Therefore, the purpose of the present invention is to propose that content of wax oil plant adds hydrogen, adds the combination side of hydrogen, catalyst circulation containing oil of dreg Method can greatly reduce catalyst make-up amount, improve reaction process catalyst concn, improve technique overall economics；It can be effective Improve conversion per pass or reduce reaction temperature, improve technology stability, can reduce investment, hydrogen consumption, energy consumption, catalyst consumption, Gas recovery ratio improves liquid and receives, improves generation oil quality；May be implemented catalyst height ratio recycling, be able to achieve catalyst with The separation of other nano particle solids realizes that secondary operation or recycling are convenient in the purification of outlet catalyst solid, is conducive to be formed super The technique of low residue emission index；Catalyst with base of molybdenum, hydrogen supply dissolvent, diluent can be used, feedstock oil can branch charging processing；It can Optimize floating bed hydrogenation heat cracking reaction process R10, fractional distillation process, the operating condition of extraction process and operating result.

Summary of the invention

Content of wax oil plant of the present invention adds hydrogen, adds the combined method of hydrogen, catalyst circulation containing oil of dreg, it is characterised in that comprising with Lower step:

(1) in the floating bed hydrogenation modified-reaction process BRA of the component materials of wax oil containing aryl BRAF, there are hydrogen, often Advise liquid hydrocarbon, dispersing type large-size particles catalyst BP simultaneously there may be hydrogen supply hydrocarbon, there may be dilution hydrocarbon, there may be divide Under conditions of dissipating type small size particle catalyst LP, it is fragrant to contain containing for solid particle containing double ring arene or with the possibility of polycyclic aromatic hydrocarbon Base wax oil component materials BRAF carries out hydrogenation reaction BRR in hydrogenation modification reaction process BRA and at least part aromatic hydrogenation occurs Fractional saturation reaction is converted into the hydrogenation modification reaction product BRAP rich in hydrogen supply the hydrocarbon component BRA-DSC；

Flow B RAP-BP-X comprising distributed large-size particles catalyst BP of at least part based on product BRAP, Reaction is participated in by least part reaction compartment of floating bed hydrogenation reaction process R10, with floating bed hydrogenation reaction process R10 Charging R10F or its hydro-conversion object contact；

(2) in floating bed hydrogenation reaction process R10, there are hydrogen, conventional liq, distributed large-size particles catalyst BP simultaneously there may be hydrogen supply hydrocarbon, there may be dilution hydrocarbon, there may be under conditions of distributed small size particle catalyst LP, At least part occurs at least part heavy hydrocarbon containing the material R10F progress hydrogenation reaction R10R that normal boiling point is higher than 530 DEG C of hydrocarbon and adds Hydrogen reaction is converted into hydrogenation reaction product R10P；

Based on the material of hydrogenation reaction product R10P, it is used as logistics R10-ENDP；

(3) hydrogen rich gas gas SRV is obtained in removal process SU10, returned logistics R10P-X, obtains distributed big partial size The material that grain catalyst BP may contain distributed small size particle catalyst LP, may contain conventional liquid hydrocarbon simultaneously；

In removal process SU10, thermal high separation process THPS may be set, it may setting separation fractional distillation process DU10；

In the thermal high separation process THPS that may be arranged, the reaction effluent R10- of hydrogenation process R10 is recycled The heat that ENDP obtains the conventional liquid hydrocarbon containing hydrogen, impurity hydrogenation products, conventional gas hydrocarbon and normal boiling point lower than 350 DEG C is high Divide gas THPS-V, obtains urging containing the distributed particle that contains of dissolution hydrogen, conventional liquid hydrocarbon of the normal boiling point higher than 350 DEG C The hot high score liquid THPS-L of agent R10C；

May setting separation fractional distillation process DU10, R10C containing catalyst based on hot high score liquid THPS-L, containing often The hydrogenation reaction generation oil R10P-Y that boiling point is higher than 450 DEG C of the hydrocarbon components is advised, isolating at least one includes that normal boiling point is higher than 450 DEG C the hydrocarbon component narrow fraction DU10-HL, at least one include narrow fraction DU10- of the normal boiling point lower than 450 DEG C of the hydrocarbon component LL obtains at least one R10C containing catalyst, is higher than the material DU10-SHL of 450 DEG C of the hydrocarbon components containing normal boiling point；It may set The separation fractional distillation process DU10 set may use solvent extraction；

It is higher than the object of 450 DEG C of the hydrocarbon components there may be at least part catalyst containing small size particle LP, containing normal boiling point Expect DU10-SHL, returns to hydrogenation process R10 circular response；

(3) distributed particle may be contained simultaneously in mechanically decoupled process XSX0, distributed large-size particles catalyst BP to urge Agent LP, the XSX0-F containing liquid phase material for being higher than 450 DEG C of the hydrocarbon components containing normal boiling point, are separated at least 2 road materials: rich catalyst Material KSX, the poor catalyst liquid material XSX0-F-LP that gas phase may be contained；

The richness catalyst feed KSX, rich in distributed large-size particles catalyst BP；

The poor catalyst liquid material XSX0-F-LP that gas phase may be contained is rich in small size particle catalyst that may be present LP；

Recycle the material of machinery separation process XSX0 discharge；

Recycling may contain the poor catalyst liquid material XSX0-F-LP of gas phase, may recycle solid component therein or with it is non-solid Body component；

The way of recycling of material KSX, selected from one or more of following method:

Selection 1, the material containing distributed large-size particles catalyst BP based on material KSX at least partially, as following Ring material KSX-TOBRA returns to floating bed hydrogenation modified-reaction process BRA and passes through at least one by return course KSX-LOOP Part reaction compartment participates in reaction, with the charging richness aromatic hydrocarbons wax oil BRAF of floating bed hydrogenation reaction process R10 or its hydro-conversion Object contact；

2 are selected, at least partially the material containing distributed large-size particles catalyst BP based on material KSX, under being used as The XSY0-F containing liquid phase material of the concentration and separation process XSY0 containing catalyst material of trip；

Selection 3, the material containing distributed large-size particles catalyst BP based on material KSX, is used as again at least partially Secondary material KSX2-TOSOLID to be concentrated takes off liquid process SPU10 into solid, deviates from least part hydrocarbon material SPU10-HC, obtain It is used as distributed big partial size to the higher desiccation material VR-R10C-OUT of solid concentration, at least part desiccation material VR-R10C-OUT The outlet material of beaded catalyst BP；

2 that may be present or multiple mechanically decoupled processes XSX0, XSY0 containing catalyst material, it is therefore possible to use serial flow behaviour Make；

One or more of following materials may be selected from by isolated material XSX0-F in mechanically decoupled process XSX0:

Selection 1, the material containing liquid material of the intermediate reaction product based on floating bed hydrogenation reaction process R10 are used as material XSX0-F；

Selection 2, the material containing liquid material of the final reacting product based on floating bed hydrogenation reaction process R10 are used as material XSX0-F；

Selection 3 is used as material XSX0-F based on the material containing liquid material of hot high score liquid THPS-L that may be present；

Selection 4 separates the material containing liquid material that hot high score liquid THPS-L that may be present is obtained, and is used as material XSX0-F；

Selection 5 is fractionated the material containing liquid material that hot high score liquid THPS-L that may be present is obtained, and is used as material XSX0-F；

Selection 6 separates what the hydrogenated oil R10P-OIL that may be present based on hydrogenation reaction effluent R10P was obtained Material containing liquid material is used as material XSX0-F；

Selection 7 is fractionated what the hydrogenated oil R10P-OIL that may be present based on hydrogenation reaction effluent R10P was obtained Material containing liquid material is used as material XSX0-F；

Selection 8 contains liquid material in the hydrogenated oil R10P-OIL that may be present based on hydrogenation reaction effluent R10P The separation process of material, obtain being higher than containing distributed beaded catalyst R10C, containing normal boiling point 450 DEG C of the hydrocarbon components containing colloid or With the hydrocarbon-bearing material S888 of asphalitine, in the solvent extraction and separation process VS-EU using solvent segregation, what is obtained contains dispersing type Beaded catalyst R10C, the material containing liquid material for being higher than 450 DEG C of the hydrocarbon components containing normal boiling point, are used as material XSX0-F；

Selection 9 contains liquid material in the hydrogenated oil R10P-OIL that may be present based on hydrogenation reaction effluent R10P The fractional distillation process using fractionating column of material, what is obtained is higher than 450 DEG C of hydrocarbon containing distributed beaded catalyst R10C, containing normal boiling point Component containing colloid or with the hydrocarbon-bearing material S888 of asphalitine, using solvent segregation solvent extraction and separation process VS-EU, What is obtained is higher than the material containing liquid material of 450 DEG C of the hydrocarbon components containing distributed beaded catalyst R10C, containing normal boiling point, is used as material XSX0-F；

In mechanically decoupled process XSX0, separating effect is selected from one or more of following method:

Concentration of the large-size particles catalyst BP in rich catalyst feed KSX is realized in selection 1；

Selection 2, realizes the filtering of large-size particles catalyst BP, and the large-size particles catalyst BP being collected by filtration is present in In rich catalyst feed KSX.

The present invention, in general, (1) is in floating bed hydrogenation modified-reaction process BRA, existing dispersing type particle hydrogenation catalyst Agent, including being easy to mechanically decoupled large-size particles catalyst BP and that may be present being difficult to mechanically decoupled small size particle and urge Agent LP；

In floating bed hydrogenation modified-reaction process BRA, exist when being difficult to mechanically decoupled small size particle catalyst LP, BP Average grain diameter is higher than 5 times of LP average grain diameter.

In floating bed hydrogenation modified-reaction process BRA, exist when being difficult to mechanically decoupled small size particle catalyst LP, it is small The size distribution of particles catalyst LP can be selected from one of the following or several:

Selection 1,100 nanometers of the partial size < of small size particle catalyst LP；

Selection 2,50 nanometers of the partial size < of small size particle catalyst LP；

Selection 3,10 nanometers of the partial size < of small size particle catalyst LP；

Selection 4,5 nanometers of the partial size < of small size particle catalyst LP；

The size distribution of large-size particles catalyst BP can be selected from one of the following or several:

Selection 1, the partial size of large-size particles catalyst BP are 80~3000 nanometers；

Selection 2, the partial size of large-size particles catalyst BP are 120~2000 nanometers；

Selection 3, the partial size of large-size particles catalyst BP are 240~1000 nanometers；

Selection 4, the partial size of large-size particles catalyst BP are 500~800 nanometers.

In floating bed hydrogenation modified-reaction process BRA, exist when being difficult to mechanically decoupled small size particle catalyst LP, hangs In the liquid phase of floating bed hydrogenation modification reaction process BRA small size particle catalyst LP there are weight LP-W and liquid phase state hydrocarbon weight Ratio LP-K100, LP-K100=(LP-W)/(YXT-W) for measuring YXT-W, can be selected from one of the following:

Select 1, LP-K100 0.000500: 1~0.002000: 1；

Select 2, LP-K100 0.002000: 1~0.005000: 1；

Select 3, LP-K100 0.005000: 1~0.020000: 1.

In the liquid phase of floating bed hydrogenation modified-reaction process BRA large-size particles catalyst BP there are weight BP-W and liquid Ratio BP-K100, BP-K100=(BP-W)/(YXT-W) of phase state hydrocarbon weight YXT-W, can be selected from one of the following:

Select 1, BP-K100 0.000500: 1~0.002000: 1；

Select 2, BP-K100 0.002000: 1~0.005000: 1；

Select 3, BP-K100 0.005000: 1~0.020000: 1；

Select 4, BP-K100 0.020000: 1~0.200000: 1.

Select 1, LP-K100 0.000500: 1~0.002000: 1；

Select 2, LP-K100 0.002000: 1~0.005000: 1；

Select 3, LP-K100 0.005000: 1~0.020000: 1；

Select 1, BP-K100 0.000500: 1~0.002000: 1；

Select 2, BP-K100 0.002000: 1~0.005000: 1；

Select 3, BP-K100 0.005000: 1~0.020000: 1；

Select 4, BP-K100 0.020000: 1~0.200000: 1.

In floating bed hydrogenation modified-reaction process BRA, exists when being difficult to mechanically decoupled small size particle catalyst LP, add The catalyst substrate 100-LP of the formation small size particle catalyst LP added, using active metal as mete-wand, catalyst substrate Normal boiling point is higher than the weight R10F-KC- of 350 DEG C of the hydrocarbon components in the addition weight 100-LP-W and hydrocarbon-bearing material R10F of 100-LP Ratio 100-LP-K100,100-LP-K100=(100-LP-W)/(R10F-KC-W) of W can be selected from one of the following:

Select 1,100-LP-K100 0.000200: 1~0.000500: 1；

Select 2,100-LP-K100 0.000100: 1~0.000200: 1；

Select 3,100-LP-K100 0.000050: 1~0.000100: 1；

Select 4,100-LP-K100 0.000010: 1~0.000050: 1.

The catalyst substrate 200-BP of the formation large-size particles catalyst BP of addition, using active metal as mete-wand, Normal boiling point is higher than the weight of 350 DEG C of the hydrocarbon components in the addition weight 200-BP-W and hydrocarbon-bearing material R10F of catalyst substrate 200-BP Ratio 200-BP-K100,200-BP-K100=(200-BP-W)/(R10F-KC-W) for measuring R10F-KC-W, can be selected from following One of:

Select 1,200-BP-K100 0.000200: 1~0.000500: 1；

Select 2,200-BP-K100 0.000100: 1~0.000200: 1；

Select 3,200-BP-K100 0.000050: 1~0.000100: 1；

Select 4,200-BP-K100 0.000010: 1~0.000050: 1.

Select 1,100-LP-K100 0.000200: 1~0.000500: 1；

Select 2,100-LP-K100 0.000100: 1~0.000200: 1；

Select 3,100-LP-K100 0.000050: 1~0.000100: 1；

Select 4,100-LP-K100 0.000010: 1~0.000050: 1；

Select 1,200-BP-K100 0.000200: 1~0.000500: 1；

Select 2,200-BP-K100 0.000100: 1~0.000200: 1；

Select 3,200-BP-K100 0.000050: 1~0.000100: 1；

Select 4,200-BP-K100 0.000010: 1~0.000050: 1.

Small size particle catalyst LP that may be present includes at least molybdenum disulfide MoS₂Particle；

Large-size particles catalyst BP includes at least molybdenum disulfide MoS₂Particle.

The present invention, (1) in floating bed hydrogenation modified-reaction process BRA, existing dispersing type particle hydrogenation catalyst, including It is easy to mechanically decoupled large-size particles catalyst BP and that may be present is difficult to mechanically decoupled small size particle catalyst LP；

Small size particle catalyst LP that may be present can include at least magnetic iron ore phase Fe1-xS particle；

Large-size particles catalyst BP can include at least magnetic iron ore phase Fe1-xS particle.

The present invention, (3) in mechanically decoupled process XSX0, separating effect is to realize that dispersing type beaded catalyst R10C is urged in richness Concentration in agent material KSX, enriching service method can be selected from one of the following or several:

Selection 1, settling methods use settlement separation tank；

Selection 2, centrifugal settling method, the fixed hydrocyclone of use device；

Selection 3, centrifugal settling method, the sedimentation centrifuge of use device rotation.

The present invention, (3) in mechanically decoupled process XSX0, separating effect can be the mistake for realizing large-size particles catalyst BP Filter, the large-size particles catalyst BP being collected by filtration are present in rich catalyst feed KSX, and filtration method can be selected from down One or more of column:

Selection 1, uses granular membrane；

Selection 2, uses key joint web filter；

Selection 3, centrifugal filtration process uses centrifugal filter；

Selection 4, filter press technique uses pressure filter；

Selection 5, vacuum filtration process uses vacuum filter.

The present invention, in general, the BP of catalyst containing large-size particles, (3) are higher than in mechanically decoupled process XSX0 containing normal boiling point The XSX0-F containing liquid phase material of 450 DEG C of the hydrocarbon components is selected from one of the following or several:

Selection 1, in material XSX0-F institute hydrocarbon components, the weight content of the hydrocarbon component of the normal boiling point lower than 300 DEG C is lower than 10%；

Selection 2, in material XSX0-F institute hydrocarbon components, the weight content of the hydrocarbon component of the normal boiling point lower than 350 DEG C is lower than 10%；

Selection 3, in material XSX0-F institute hydrocarbon components, the weight content of the hydrocarbon component of the normal boiling point lower than 400 DEG C is lower than 10%；

Selection 4, in material XSX0-F institute hydrocarbon components, the weight content of the hydrocarbon component of the normal boiling point lower than 450 DEG C is lower than 10%；

Selection 5, in material XSX0-F institute hydrocarbon components, the weight content of the hydrocarbon component of the normal boiling point lower than 500 DEG C is lower than 10%；

Selection 6, in material XSX0-F institute hydrocarbon components, the weight content of the hydrocarbon component of the normal boiling point lower than 530 DEG C is lower than 10%；

Selection 7, in material XSX0-F institute hydrocarbon components, the weight content of the hydrocarbon component of the normal boiling point lower than 550 DEG C is lower than 10%.

The present invention, in general, the BP of catalyst containing large-size particles, (3) are higher than in mechanically decoupled process XSX0 containing normal boiling point The XSX0-F containing liquid phase material of 450 DEG C of the hydrocarbon components is separated at least 2 road materials: rich catalyst feed KSX, may contain gas phase Poor catalyst liquid material XSX0-F-LP；

In mechanically decoupled process XSX0, using centrifugal settling method, the fixed hydrocyclone of use device or device rotation Sedimentation centrifuge, separating effect can be selected from one of the following or several:

1. by weight, 50% or more of the distributed beaded catalyst R10C in material XSX0-F, is enriched in richness and urges In agent material KSX；

2. by weight, 80% or more of the distributed beaded catalyst R10C in material XSX0-F, is enriched in richness and urges In agent material KSX；

3. by weight, 95% or more of the distributed beaded catalyst R10C in material XSX0-F, is enriched in richness and urges In agent material KSX；

4. by weight, 99% or more of the distributed beaded catalyst R10C in material XSX0-F, is enriched in richness and urges In agent material KSX；

5. by weight, 99.9% or more of the distributed beaded catalyst R10C in material XSX0-F, is enriched in richness In catalyst feed KSX.

1. by weight, 10% of the hydrocarbon in material XSX0-F is hereinafter, enter in rich catalyst feed KSX；

2. by weight, 5% of the hydrocarbon in material XSX0-F is hereinafter, enter in rich catalyst feed KSX；

3. by weight, 2.5% of the hydrocarbon in material XSX0-F is hereinafter, enter in rich catalyst feed KSX；

4. by weight, 1.0% of the hydrocarbon in material XSX0-F is hereinafter, enter in rich catalyst feed KSX；

5. by weight, 0.1% of the hydrocarbon in material XSX0-F is hereinafter, enter in rich catalyst feed KSX.

1. the grain diameter of 50% or more ratio is greater than 10.0 microns of large-size particles catalyst BP, into rich catalyst In material KSX；

2. the grain diameter of 50% or more ratio is greater than 3.00 microns of large-size particles catalyst BP, into rich catalyst In material KSX；

3. the grain diameter of 50% or more ratio is greater than 1.00 microns of large-size particles catalyst BP, into rich catalyst In material KSX；

4. the grain diameter of 50% or more ratio is greater than 0.50 micron of large-size particles catalyst BP, into rich catalyst In material KSX；

5. the grain diameter of 50% or more ratio is greater than 0.20 micron of large-size particles catalyst BP, into rich catalyst In material KSX.

In mechanically decoupled process XSX0, using centrifugal settling method, the fixed hydrocyclone of use device or device rotation Sedimentation centrifuge, one of the following or several can be selected from separating effect:

1. the weight concentration of large-size particles catalyst BP, is higher than 0.10% in rich catalyst feed KSX；

2. the weight concentration of large-size particles catalyst BP, is higher than 0.50% in rich catalyst feed KSX；

3. the weight concentration of large-size particles catalyst BP, is higher than 2.50% in rich catalyst feed KSX；

4. the weight concentration of large-size particles catalyst BP, is higher than 12.5% in rich catalyst feed KSX；

5. the weight concentration of large-size particles catalyst BP, is higher than 25.0% in rich catalyst feed KSX；

6. the weight concentration of large-size particles catalyst BP, is higher than 50.0% in rich catalyst feed KSX.

The present invention, in general, (3) containing distributed beaded catalyst R10C, contain normal boiling point height in mechanically decoupled process XSX0 In the XSX0-F containing liquid phase material of 450 DEG C of the hydrocarbon components, it is separated at least 2 road materials: gas phase rich catalyst feed KSX, may be contained Poor catalyst liquid material XSX0-F-LP；

In mechanically decoupled process XSX0, using centrifugal filtration process, using centrifugal filter, separating effect can be selected from following One or more of:

1. intercepted grain diameter is greater than 10.0 microns of large-size particles catalyst BP, into rich catalyst feed In KSX；

2. intercepted grain diameter is greater than 3.00 microns of large-size particles catalyst BP, into rich catalyst feed In KSX；

3. intercepted grain diameter is greater than 1.00 microns of large-size particles catalyst BP, into rich catalyst feed In KSX；

4. intercepted grain diameter is greater than 0.20 micron of large-size particles catalyst BP, into rich catalyst feed In KSX；

5. intercepted grain diameter is greater than 0.05 micron of large-size particles catalyst BP, into rich catalyst feed In KSX.

The present invention, in general, the BP of catalyst containing large-size particles, (3) are higher than in mechanically decoupled process XSX0 containing normal boiling point The XSX0-F containing liquid phase material of 450 DEG C of the hydrocarbon components, the operation temperature of material XSX0-F can be selected from one of the following or several Kind:

1. 120~200 DEG C；

2. 200~250 DEG C；

3. 250~300 DEG C；

4. 300~350 DEG C；

5. 350~400 DEG C；

6. 400~450 DEG C.

The present invention, in general, the BP of catalyst containing large-size particles, (3) are higher than in mechanically decoupled process XSX0 containing normal boiling point The component of large-size particles catalyst BP in the XSX0-F containing liquid phase material of 450 DEG C of the hydrocarbon components, material XSX0-F, can be selected from One of the following is several:

1. the sulfide of molybdenum；

2. the sulfide of iron；

3. the sulfide of nickel；

4. the sulfide of vanadium；

5. the sulfide of tungsten.

The present invention, in general, the BP of catalyst containing large-size particles, (3) are higher than in mechanically decoupled process XSX0 containing normal boiling point The size distribution of large-size particles catalyst BP in the XSX0-F containing liquid phase material of 450 DEG C of the hydrocarbon components, material XSX0-F, can be with Selected from one of the following or several:

1. partial size is higher than 80% between the weight ratio of 2.00~10.0 microns of particle；

2. partial size is higher than 80% between the weight ratio of 0.50~2.00 micron of particle；

3. partial size is higher than 80% between the weight ratio of 0.10~0.50 micron of particle；

4. partial size is higher than 80% between the weight ratio of 0.05~0.10 micron of particle；

5. partial size is higher than 80% between the weight ratio of 0.01~0.05 micron of particle.

The present invention, in general, (1) in hydrogenation process R10, at least uses a floating bed hydrogenation reactor；It is suspending It is molybdenum disulfide MoS there are body of work form in liquid phase in bed hydroprocessing reactor₂Molybdenum base particle dispersion hydrogenation catalyst Agent large-size particles catalyst BP；

Hydrocarbon-bearing material R10F, mainly the hydrocarbon component by normal boiling point higher than 450 DEG C forms.

The present invention, in general, (3) are boiled in mechanically decoupled process XSX0 by isolated large-size particles catalyst BP, containing conventional Point is higher than the XSX0-F containing liquid phase material of 450 DEG C of the hydrocarbon components, can be selected from one or more of following materials:

Selection 1, the intermediate reaction product of floating bed hydrogenation reaction process R10 are used as material XSX0-F；

Selection 2, the material containing liquid material that the intermediate reaction product of separation floating bed hydrogenation reaction process R10 obtains, is used as Material XSX0-F；

Selection 3, the liquid material that the intermediate reaction product of separation floating bed hydrogenation reaction process R10 obtains, is used as material XSX0- F；

Selection 4, the final reacting product of floating bed hydrogenation reaction process R10 are used as material XSX0-F；

Selection 5, the material containing liquid material that the final reacting product of separation floating bed hydrogenation reaction process R10 obtains, is used as Material XSX0-F；

Selection 6, the liquid material that the final reacting product of separation floating bed hydrogenation reaction process R10 obtains, is used as material XSX0- F；

Selection 7, it is understood that there may be hot high score liquid THPS-L, be used as material XSX0-F；

Selection 8, it is understood that there may be hot high score liquid THPS-L the obtained hot low liquid separation body TLPS-L of decompression flash process, As material XSX0-F；

Low point of gas TLPS-V of heat and the low liquid separation of heat are separated into heat low separation process TLPS, hot high score liquid THPS-L Body TLPS-L；

Selection 9, in the decompression flash separation without using fractionating column of hot high score liquid THPS-L that may be present, obtains That arrives is higher than 450 DEG C of the hydrocarbon components containing distributed beaded catalyst R10C, containing normal boiling point based on hot high score liquid THPS-L Material containing liquid material is used as material XSX0-F；

Selection 10, in the decompression flash separation without using fractionating column of hot high score liquid THPS-L that may be present, What is obtained is higher than 450 DEG C of the hydrocarbon components containing distributed beaded catalyst R10C, containing normal boiling point based on hot high score liquid THPS-L Liquid material, be used as material XSX0-F；

Selection 11, in the fractional distillation process using fractionating column of hot high score liquid THPS-L that may be present, obtain based on It is higher than the material containing liquid material of 450 DEG C of the hydrocarbon components containing distributed beaded catalyst R10C, containing normal boiling point, is used as material XSX0-F；

Selection 12, in the fractional distillation process using fractionating column of hot high score liquid THPS-L that may be present, obtain based on It is higher than the liquid material of 450 DEG C of the hydrocarbon components containing distributed beaded catalyst R10C, containing normal boiling point, it may be possible to which fractionating column feeds flash tank After the heating of the decompression flash oil or fractionation column base oil of tank bottom oil or fractionation column base oil or fractionation column base oil flash oil or The air lift flash oil of fractionation column base oil is used as material XSX0-F；

Selection 13, in the fractional distillation process using fractionating column of hot high score liquid THPS-L that may be present, containing for obtaining divides Dispersing granule catalyst R10C, be higher than containing normal boiling point 450 DEG C of the hydrocarbon components containing colloid or with the hydrocarbon-bearing material S888 of asphalitine, In the solvent extraction and separation process VS-EU using solvent segregation, it is separated into light phase material VS-EU-L and heavy phase material VS-EU-H；

It is isolated after being mixed with extractant in extraction separation process VS-EU, material S888 containing extractant, containing relatively low The liquid material VS-EU-ML of light phase containing agent of molecular weight hydrocarbon component is isolated containing extractant, the hydrocarbon component containing relatively high molecular weight, enrichment The liquid material of heavy phase containing the agent VS-EU-MH of distributed beaded catalyst R10C；

At least part liquid material VS-EU-MH of heavy phase containing agent, is used as material XSX0-F；

Selection 14, in the fractional distillation process using fractionating column of hot high score liquid THPS-L that may be present, containing for obtaining divides Dispersing granule catalyst R10C, be higher than containing normal boiling point 450 DEG C of the hydrocarbon components containing colloid or with the hydrocarbon-bearing material S888 of asphalitine, In the solvent extraction and separation process VS-EU using solvent segregation, it is separated into light phase material VS-EU-L and heavy phase material VS-EU-H；

In the fractional distillation process of the liquid material of heavy phase containing the agent VS-EU-MH of distillation abjection extractant, the liquid material of heavy phase containing agent VS-EU- Become heavy phase material VS-EU-H after MH distillation removing extractant；

At least part heavy phase material VS-EU-H is used as material XSX0-F；

Selection 15, in the fractional distillation process using fractionating column of hot high score liquid THPS-L that may be present, containing for obtaining divides Dispersing granule catalyst R10C, be higher than containing normal boiling point 450 DEG C of the hydrocarbon components containing colloid or with the hydrocarbon-bearing material S888 of asphalitine, In the solvent extraction and separation process VS-EU using solvent segregation, it is separated into light phase material VS-EU-L and heavy phase material VS-EU-H；

It is mixed into after mixture QQ77 and is isolated containing extraction with extractant in extraction separation process VS-EU, material S888 The liquid material VS-EU-ML of the light phase containing agent of solvent, the hydrocarbon component containing relatively low molecular weight is isolated containing extractant, containing opposite macromolecule The liquid material of heavy phase containing the agent VS-EU-MH for measuring the hydrocarbon component, being enriched with distributed beaded catalyst R10C；

At least part mixture QQ77 is used as material XSX0-F.

The reaction effluent R10-ENDP's of hydrogenation process R10 recycled in removal process SU10 in the present invention, (2) The fractional distillation process using fractionating column of oil is generated, obtained large-size particles catalyst BP, is higher than 450 DEG C of hydrocarbon groups containing normal boiling point Point containing colloid or with the hydrocarbon-bearing material S888 of asphalitine, can using solvent segregation solvent extraction and separation process VS- EU, obtained material containing liquid material, the feed material XSX0-F as mechanically decoupled process XSX0；

The method for isolating light liquid phase and heavy-fluid phase using the separation process VS-EU of solvent segregation can be selected from following In a kind or several:

1. solvent-sedimentation, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present；

2. solvent-centrifugal process, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present；

3. solvent-filtration method, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present；

4. solvent-flocculence, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present；

5. solvent-extraction process, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present；

6. supercritical extraction, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present.

It in mechanically decoupled process XSX0, is worked using centrifuge separation principle, working method can a kind in following:

Selection 1, centrifugal settling method, the fixed hydrocyclone of use device；

Selection 2, centrifugal settling method, the sedimentation centrifuge of use device rotation；

Selection 3, centrifugal filtration process uses centrifugal filter；

In mechanically decoupled process XSX0, worked using centrifuge separation principle, the series of step with centrifugal separation can be selected from down 1 kind in column:

1. level-one partition method；

2. the two-stage partition method of serial operation contains 2 step with centrifugal separation；

3. the three-level rotation of serial operation divides partition method, contain 3 step with centrifugal separation.

In mechanically decoupled process XSX0, being worked using centrifuge separation principle, the series of step with centrifugal separation can be two-stage, Containing 2 step with centrifugal separation, working method can a kind in following:

1. material XSX0-F is separated into 2 road materials: the first rich large-size particles in first order step with centrifugal separation XSX0-1 The XSX0-1-BTM containing liquid phase material of catalyst BP, may contain gas phase the first poor large-size particles catalyst BP containing liquid phase object Expect XSX0-1-TOP；

In second level step with centrifugal separation XSX0-2, the XSX0- containing liquid phase material of the first poor large-size particles catalyst BP 1-TOP is separated into 2 road materials: the XSX0-2-BTM containing liquid phase material of the second rich large-size particles catalyst BP, may contain gas phase The second poor large-size particles catalyst BP XSX0-2-TOP containing liquid phase material；

The XSX0-1-BTM containing liquid phase material of first rich large-size particles catalyst BP at least partially, is used as rich catalyst Material KSX；

At least part may contain the XSX0-2-TOP containing liquid phase material of the second poor large-size particles catalyst BP of gas phase, As the poor large-size particles catalyst BP liquid material XSX0-F-LP that may contain gas phase；

There may be an XSX0-2-BTM containing liquid phase material of the rich large-size particles catalyst BP of at least part second, return the First-stage centrifugal separating step XSX0-1 multi-cycle separation；

2. material XSX0-F is separated into 2 road materials: the first rich large-size particles in first order step with centrifugal separation XSX0-A The XSX0-A-BTM containing liquid phase material of catalyst BP, may contain gas phase the first poor large-size particles catalyst BP containing liquid phase object Expect XSX0-A-TOP；

In second level step with centrifugal separation XSX0-B, the XSX0- containing liquid phase material of the first rich large-size particles catalyst BP A-BTM is separated into 2 road materials: the XSX0-B-BTM containing liquid phase material of the second rich large-size particles catalyst BP, may contain gas phase The second poor large-size particles catalyst BP XSX0-B-TOP containing liquid phase material；

The XSX0-B-BTM containing liquid phase material of second rich large-size particles catalyst BP at least partially, is used as rich big partial size Beaded catalyst BP material KSX；

At least part may contain the XSX0-A-TOP containing liquid phase material of the first poor large-size particles catalyst BP of gas phase, As the poor large-size particles catalyst BP liquid material XSX0-F-LP that may contain gas phase；

There may be at least part that may contain the XSX0- containing liquid phase material of the second poor large-size particles catalyst BP of gas phase B-TOP returns to first order step with centrifugal separation XSX0-A multi-cycle separation.

The BP of catalyst containing large-size particles, the present invention, (3) are higher than 450 DEG C containing normal boiling point in mechanically decoupled process XSX0 The XSX0-F containing liquid phase material of the hydrocarbon component is separated at least 2 road materials: rich large-size particles catalyst BP material KSX, Ke Nenghan The poor large-size particles catalyst BP liquid material XSX0-F-LP of gas phase；

In mechanically decoupled process XSX0, worked using centrifuge separation principle, the series of step with centrifugal separation be can with three-level, Containing 3 step with centrifugal separation, working method can a kind in following:

In third level step with centrifugal separation XSX0-3A, containing for the second poor large-size particles catalyst BP of gas phase may be contained Liquid phase material XSX0-2-TOP is separated into 2 road materials: the XSX0-3A- containing liquid phase material of third richness large-size particles catalyst BP The XSX0-3A-TOP containing liquid phase material of the poor large-size particles catalyst BP of BTM, the third that gas phase may be contained；

The XSX0-1-BTM containing liquid phase material of first rich large-size particles catalyst BP at least partially, is used as rich big partial size Beaded catalyst BP material KSX；

At least part may contain the XSX0-3A- containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase TOP, as the poor large-size particles catalyst BP liquid material XSX0-F-LP that may contain gas phase；

There may be the XSX0-2-BTM containing liquid phase material of the rich large-size particles catalyst BP of at least part second, be used as richness Large-size particles catalyst BP material KSX；

There may be the XSX0-3A-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, be used as Rich large-size particles catalyst BP material KSX；

There may be the XSX0-3A-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, return First order step with centrifugal separation XSX0-1 multi-cycle separation；

There may be the XSX0-3A-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, return Second level step with centrifugal separation XSX0-2 multi-cycle separation；

2. material XSX0-F is separated into 2 road materials: the first rich large-size particles in first order step with centrifugal separation XSX0-1 The XSX0-1-BTM containing liquid phase material of catalyst BP, may contain gas phase the first poor large-size particles catalyst BP containing liquid phase object Expect XSX0-1-TOP；

In third level step with centrifugal separation XSX0-3B, the XSX0- containing liquid phase material of the second rich large-size particles catalyst BP 2-BTM is separated into 2 road materials: the XSX0-3B-BTM containing liquid phase material of third richness large-size particles catalyst BP, may contain gas phase The poor large-size particles catalyst BP of third XSX0-3B-TOP containing liquid phase material；

At least part may contain the XSX0-3B- containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase TOP, as the poor large-size particles catalyst BP liquid material XSX0-F-LP that may contain gas phase；

At least part may contain the XSX0-3B- containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase TOP returns to first order step with centrifugal separation XSX0-1 multi-cycle separation；

At least part may contain the XSX0-3B- containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase TOP returns to second level step with centrifugal separation XSX0-2 multi-cycle separation；

There may be the XSX0-3B-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, be used as Rich large-size particles catalyst BP material KSX；

There may be the XSX0-3B-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, return First order step with centrifugal separation XSX0-1 multi-cycle separation；

There may be the XSX0-B3A-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, return Second level step with centrifugal separation XSX0-2 multi-cycle separation；

3. material XSX0-F is separated into 2 road materials: the first rich large-size particles in first order step with centrifugal separation XSX0-A The XSX0-A-BTM containing liquid phase material of catalyst BP, may contain gas phase the first poor large-size particles catalyst BP containing liquid phase object Expect XSX0-A-TOP；

In third level step with centrifugal separation XSX0-C1, the XSX0- containing liquid phase material of the second rich large-size particles catalyst BP B-BTM is separated into 2 road materials: the XSX0-C1-BTM containing liquid phase material of third richness large-size particles catalyst BP, may contain gas phase The poor large-size particles catalyst BP of third XSX0-C1-TOP containing liquid phase material；

The XSX0-C1-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP is used as rich big grain Diameter beaded catalyst BP material KSX；

There may be at least part that may contain the XSX0- containing liquid phase material of the second poor large-size particles catalyst BP of gas phase B-TOP, as the poor large-size particles catalyst BP liquid material XSX0-F-LP that may contain gas phase；

There may be at least part that may contain the XSX0- containing liquid phase material of the second poor large-size particles catalyst BP of gas phase B-TOP returns to first order step with centrifugal separation XSX0-A multi-cycle separation；

There may be at least part that may contain the XSX0- containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase C1-TOP returns to first order step with centrifugal separation XSX0-A multi-cycle separation；

There may be at least part that may contain the XSX0- containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase C1-TOP returns to second level step with centrifugal separation XSX0-B multi-cycle separation；

4. material XSX0-F is separated into 2 road materials: the first rich large-size particles in first order step with centrifugal separation XSX0-A The XSX0-A-BTM containing liquid phase material of catalyst BP, may contain gas phase the first poor large-size particles catalyst BP containing liquid phase object Expect XSX0-A-TOP；

In third level step with centrifugal separation XSX0-C2, containing for the second poor large-size particles catalyst BP of gas phase may be contained Liquid phase material XSX0-B-TOP is separated into 2 road materials: the XSX0-C2- containing liquid phase material of third richness large-size particles catalyst BP The XSX0-C2-TOP containing liquid phase material of the poor large-size particles catalyst BP of BTM, the third that gas phase may be contained；

At least part may contain the XSX0-B-TOP containing liquid phase material of the second poor large-size particles catalyst BP of gas phase, Return to first order step with centrifugal separation XSX0-A multi-cycle separation；

At least part may contain the XSX0-C2- containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase TOP, as the poor large-size particles catalyst BP liquid material XSX0-F-LP that may contain gas phase；

At least part may contain the XSX0-C2- containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase TOP returns to first order step with centrifugal separation XSX0-A multi-cycle separation；

At least part may contain the XSX0-C2- containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase TOP returns to second level step with centrifugal separation XSX0-B multi-cycle separation；

There may be the XSX0-C2-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, be used as Rich large-size particles catalyst BP material KSX；

There may be the XSX0-C2-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, return First order step with centrifugal separation XSX0-A multi-cycle separation；

There may be the XSX0-C2-BTM containing liquid phase material of at least part third richness beaded catalyst R10C, return to second Grade step with centrifugal separation XSX0-B multi-cycle separation.

It can be set the preprocessing process of material XSX0-F, working method can a kind in following:

1. the flash liberation process of material XSX0-F is separated into degassing oil, flashed vapour, obtained degassing oil enters mechanical point From process XSX0；

Part low boiling component is vaporized 2. material XSX0-F in air lift flash process, is contacted with gas stripping gas, is separated into de- Gas and oil, air lift flashed vapour, obtained degassing oil enter mechanically decoupled process XSX0；

Vaporize part low boiling component 3. material XSX0-F first passes through heating up process, then in flash liberation process It is separated into degassing oil, flashed vapour, obtained degassing oil enters mechanically decoupled process XSX0；

The temperature of material is set to become supercooling liquid material lower than bubble point temperature 4. material XSX0-F first passes through the process of cooling, so Supercooling liquid material enters mechanically decoupled process XSX0 afterwards.

The present invention, in general, the BP of catalyst containing large-size particles, (3) are higher than in mechanically decoupled process XSX0 containing normal boiling point The XSX0-F containing liquid phase material of 450 DEG C of the hydrocarbon components is separated at least 2 road materials: rich large-size particles catalyst BP material KSX, The poor large-size particles catalyst BP liquid material XSX0-F-LP of gas phase may be contained；

In a mechanically decoupled step, it can be used and at least divide the separative unit packaging type that parallel operation forms by 2 rotations Rotation divides separator.

In a mechanically decoupled step, it can be used and at least divide the separative unit packaging type that parallel operation forms by 2 rotations Rotation divides separator, working method, can a kind or several in following:

1. branch divides separative unit transferring raw material to each rotation using charging general pipeline；

Using underflow discharge general pipeline, each underflow revolved and separative unit is divided to isolate is received；

Discharge general pipeline is flowed using top, receives each top stream for revolving and separative unit being divided to isolate；

2. using packaging shell, by 2 or multiple rotations divide separative unit, are installed in parallel, and constitute charging distributor chamber, underflow converges Collect room, top stream merging chamber；

All rotation divides the feed inlet of separative unit to be connected to charging distributor chamber；

All rotation divides the underflow opening of separative unit to be connected to underflow merging chamber；

All rotation divides the top head piece of separative unit to be connected to top stream merging chamber；

Distributor chamber and top stream merging chamber are fed, is isolated with first partition；

Distributor chamber and underflow merging chamber are fed, is isolated with second partition；

Distributor chamber is fed, positioned at the middle section of packaging shell, and the inlet communication with the charging total material for entering packaging shell；

Underflow merging chamber, positioned at the side of charging distributor chamber, and with the corresponding underflow total material discharge gate that leaves packaging shell Connection；

Top stream merging chamber flows total material discharge positioned at the other side of charging distributor chamber, and with the corresponding top for leaving packaging shell Mouth connection；

3. using packaging shell, by 2 or multiple rotations divide separative unit, are installed in parallel, and constitute charging distributor chamber, underflow converges Collect room, top stream merging chamber；

Underflow merging chamber, positioned at the center of packaging shell, and the discharge gate with the underflow total material for leaving packaging shell Connection；

4. using packaging shell, by 2 or multiple rotations divide separative unit, are installed in parallel, and constitute charging distributor chamber, underflow converges Collect room, top stream merging chamber；

Top stream merging chamber, positioned at the center of packaging shell, and the discharge gate with the top stream total material for leaving packaging shell Connection.

In a mechanically decoupled step, divide separator using rotation, the rotation that can be used divides the separation axis of cone line of separative unit Working condition mounting means, can a kind or several in following:

1. being horizontally mounted；

2. right angle setting；

3. inclination installation, i.e., separation axis of cone line working condition and horizontal plane angle, neither 0 degree angle, be also not 90 Spend angle.

The present invention, in general, dividing process XSX0 in rotation, the rotation used divides separative unit, is manufactured with wear-resistant material or using resistance to Mill material makees liner.

The present invention, hydrocarbon-bearing material R10F are the materials for being higher than 450 DEG C of the hydrocarbon components comprising normal boiling point, can be selected from following One or more of material:

Option 1, the high hydrocarbon ils of gluey pitch shape constituent content；

Option 2, the high hydrocarbon ils of content of ashes；

Option 3, the high hydrocarbon ils of easy coking constituent content；

Option 4, the high hydrocarbon ils of the easy reactant content of high temperature；

Option 5, the hydrocarbon ils of high aromatic carbon rate.

1. mainly the hydrocarbon component by normal boiling point higher than 350 DEG C forms；

2. mainly the hydrocarbon component by normal boiling point higher than 450 DEG C forms；

3. mainly the hydrocarbon component by normal boiling point higher than 530 DEG C forms；

4. mainly the hydrocarbon component by normal boiling point higher than 550 DEG C forms.

Option 1, the hydrocarbon material based on coalite tar are coalite tar or its distillate or its extraction oil or its hot-working Oil product obtained by process, hot procedure are that distillation process or thermal cracking process or coking or catalytic cracking process or catalysis are split Solution preocess；

Option 2, the hydrocarbon material based on medium temperature coal tar are medium temperature coal tar or its distillate or its extraction oil or its hot-working Oil product obtained by process, hot procedure are that distillation process or thermal cracking process or coking or catalytic cracking process or catalysis are split Solution preocess；

Option 3, the hydrocarbon material based on high temperature coal-tar are high temperature coal-tar or its distillate or its extraction oil or its hot-working Oil product obtained by process, hot procedure are that distillation process or thermal cracking process or coking or catalytic cracking process or catalysis are split Solution preocess；

Option 4 is oil product obtained by direct hydrogenation liquefaction of coal liquefaction process based on the hydrocarbon material of direct hydrogenation liquefaction of coal product oil Or oil product obtained by its extraction oil or its hot procedure, direct hydrogenation liquefaction of coal liquefaction process includes the coal using hydrogen supply dissolvent oil Add hydrogen direct liquefaction liquefaction process, oil coal refines process altogether, coal faces hydrogen thermosol liquefaction process, hot procedure is distillation process or heat Cracking process or coking or catalytic cracking process or catalytic pyrolysis process；

Option 5, the hydrocarbon material based on petroleum based heavy fuel oils are petroleum based heavy fuel oils or its distillate or its extraction oil or its hot-working Oil product obtained by process, hot procedure are that distillation process or thermal cracking process or coking or catalytic cracking process or catalysis are split Solution preocess；

Oil obtained by option 6, the hydrocarbon material based on shale oil, shale oil or its distillate or its extraction oil or its hot procedure Product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis process；

Option 7 is tar sand base weight oil or its distillate or its extraction oil or its heat based on the hydrocarbon material of tar sand base weight oil Oil product obtained by process, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or urge Change cracking process；

Option 8, the hydrogenation process of ethylene cracking tar；

Option 9, other colloid weight contents are higher than 15% or are higher than 5.0% hydrocarbon ils with asphalitine weight content.

The present invention can be set guide and take off solid particle step:

Take off solid particle step in guide, finally enter floating bed hydrogenation modified-reaction process BRA or with hydrogenation reaction mistake The material of journey R10 or its precursor first deviate from the minimum that granularity is equal to the large-size particles catalyst BP for being easy to mechanically decoupled The particle of partial size obtains poor granule materials, and then poor granule materials enter floating bed hydrogenation modified-reaction process BRA or and plus hydrogen Reaction process R10.

The present invention can be set guide and take off solid particle step:

Take off solid particle step in guide, finally enter floating bed hydrogenation modified-reaction process BRA or with hydrogenation reaction mistake The material of journey R10 or its precursor first deviate from granularity and are less than the most granule for being easy to mechanically decoupled large-size particles catalyst BP The particle of diameter obtains poor granule materials, and then poor granule materials enter floating bed hydrogenation modified-reaction process BRA or and add hydrogen anti- Answer process R10.

The present invention can be set guide and take off solid particle step:

Take off solid particle step in guide, finally enter floating bed hydrogenation modified-reaction process BRA or with hydrogenation reaction mistake The material of journey R10 or its precursor first deviate from the minimum that granularity is equal to the large-size particles catalyst BP for being easy to mechanically decoupled The particle of 50% partial size of partial size obtains poor granule materials, and then poor granule materials enter floating bed hydrogenation modified-reaction process BRA or with hydrogenation process R10.

The present invention, (2) obtain hydrogen rich gas gas SRV in removal process SU10, returned logistics R10-ENDP, obtain containing often Advise the material containing distributed beaded catalyst R10C of liquid hydrocarbon；

At least part hydrogen rich gas gas SRV can enter floating bed hydrogenation modified-reaction process BRA or and hydrogenation reaction Process R10 is used as hydrogen rich gas SRV-RH bis- times；

The reaction effluent R10-ENDP of the hydrogenation process R10, with 1 tunnel or 2 tunnels or multichannel material R10-ENDP Form occur, the composition and phase of different R10-ENDP logistics be identical or different.

The present invention, (2) obtain hydrogen rich gas gas SRV in removal process SU10, returned logistics R10-ENDP, at least part Hydrogen rich gas gas SRV can enter floating bed hydrogenation modified-reaction process BRA or with hydrogenation process R10 as hydrogen rich gas SRV-RH bis- times uses；

The H of hydrogen rich gas gas SRV₂Volumetric concentration, a kind selected from following manner:

Option 1, the H of hydrogen rich gas gas SRV₂Volumetric concentration is greater than 75%；

Option 2, the H of hydrogen rich gas gas SRV₂Volumetric concentration is greater than 80%；

Option 3, the H of hydrogen rich gas gas SRV₂Volumetric concentration is greater than 85%.

The present invention, in general, thermal high separation process THPS is arranged in removal process SU10；

It obtains in thermal high separation process THPS, returned logistics R10-ENDP containing hydrogen, impurity hydrogenation products, conventional gas Body hydrocarbon and normal boiling point are lower than the hot high score gas THPS-V of 350 DEG C of conventional liquid hydrocarbon and containing dissolution hydrogen, normal boiling point The possibility of conventional liquid hydrocarbon higher than 350 DEG C contains the hot high score liquid THPS-L of solid particle；

In thermal high separation process THPS, for the heat isolated based on hydrogenation process R10 effluent R10-ENDP High score gas BASE-THPS-V can be set the liquid scrubbing settling section DWU66 that gas phase takes off solid, it is lower to obtain solid content Gas；

The liquid scrubbing settling section DWU66 of solid is taken off in gas phase, at least part cleaning solution that may be used is condensation base In the lime set that the logistics of hot high score gas THPS-V obtains.

The present invention, in general, the component materials BRAF of wax oil containing aryl of floating bed hydrogenation modified-reaction process BRA processing, is Material rich in aryl wax oil component.

The present invention, in general, in floating bed hydrogenation modified-reaction process BRA, hydro carbons in hydrogenation modification reaction product BRAP Hydrogen supply hydrocarbon total amount concentration improves DATA10 than the hydrogen supply hydrocarbon total amount concentration of hydro carbons in the component materials of wax oil containing aryl BRAF, can be with Selected from one of the following:

Selection 1 is greater than 5%；

Selection 2 is greater than 10%；

Selection 3 is greater than 15%；

Selection 4 is greater than 20%；

Selection 5 is greater than 25%；

Selection 6 is greater than 35%；

Selection 7 is greater than 45%；

Selection 8 is greater than 55%；

Normal boiling point in floating bed hydrogenation modified-reaction process BRA, hydrogenation modification reaction product BRAP is higher than 350 DEG C The hydrocarbon component heat from hydrogenation cracking weight conversion rate, one of the following can be selected from:

Selection 1, less than 5%；

Selection 2, less than 10%；

Selection 3, less than 15%；

Selection 4, less than 20%；

Selection 5, less than 25%；

Selection 6, less than 30%；

Selection 7, less than 35%；

Selection 8, less than 40%.

The present invention, normal boiling point in the process U100 of hydrocarbon-bearing material R10F, hydrocarbon-bearing material R10F is higher than 530 DEG C The heat from hydrogenation cracking weight conversion rate of the hydrocarbon component, can be selected from one of the following:

Selection 1 is greater than 25%；

Selection 2 is greater than 40%；

Selection 3 is greater than 55%；

Selection 4 is greater than 70%；

Selection 5 is greater than 85%；

Selection 6 is greater than 95%；

Selection 7 is greater than 96%；

Selection 8 is greater than 97%；

Selection 9 is greater than 98%；

Selection 10 is greater than 99%.

The present invention, (2) use hydrogen supply hydrocarbon material DSF and component containing high boiling hydrocarbon in floating bed hydrogenation reaction process R10 The material R10F of HAC or in which the working method of hydrogenation products contact, can be selected from one of the following or several:

Option 1, the weight concentration absolute value of hydrogen supply the hydrocarbon component DS is higher than component containing high boiling hydrocarbon in hydrogen supply hydrocarbon material DSF The weight concentration absolute value at least 10% of hydrogen supply the hydrocarbon component DS in the material R10F of HAC；

Option 2, hydrogen supply hydrocarbon material DSF are mainly that 250~530 DEG C of hydro carbons form by normal boiling point, part saturation virtue It is 0.35~0.70 that the weight content of hydrocarbon, which is greater than 15%, aromatic carbon rate,；

In option 3, the weight flow of hydrogen supply hydrocarbon material DSF and material R10F the weight flow of high boiling hydrocarbon component HAC it Than being 0.05~4.0；

Option 4, the weight concentration absolute value of hydrogen supply the hydrocarbon component DS is 10~65% in hydrogen supply hydrocarbon material DSF；

Option 5, hydrogen supply hydrocarbon material DSF are mainly made of the hydrocarbon component that normal boiling point is 250~350 DEG C；

Option 6, high boiling hydrocarbon component in the weight flow of hydrogen supply dissolvent component DS and material R10F in hydrogen supply hydrocarbon material DSF The ratio between weight flow of HAC is 0.05~2.0.

The present invention, (2) use hydrogen supply hydrocarbon material DSF and component containing high boiling hydrocarbon in floating bed hydrogenation reaction process R10 The material R10F of HAC or in which hydrogenation products contact；

Hydrogen supply hydrocarbon material DSF is the hydrocarbon material containing hydrogen supply based on stabilized hydrogenation reaction process MR product MRP；

Based on the hydrogen material of stabilized hydrogenation reaction process MR, hydrogenation process R10 can be entered and be used in series；

For producing the stabilized hydrogenation reaction process MR raw material MRF of hydrogen supply hydrocarbon material DSF, separation hydrogenation reaction may include Process R10 effluent R10-ENDP obtains hydrocarbon-bearing material.

In removal process SU10, thermal high separation process THPS is set；

Based on the hydrogen material of hot high score gas THPS-V, stabilized hydrogenation reaction process MR can be entered and be used in series；

The present invention, in general, (1) is in floating bed hydrogenation modified-reaction process BRA, the absolute value of the aromatic carbon rate of the dilution hydrocarbon The absolute value of aromatic carbon rate than the component materials of wax oil containing aryl BRAF is at least low by 0.1；

(2) in floating bed hydrogenation reaction process R10, aromatic carbon of the absolute value than material R10F of the aromatic carbon rate of the dilution hydrocarbon The absolute value of rate at least low 0.1.

The present invention, in general, dilution hydrocarbon WWF is mainly made of the hydrocarbon component that normal boiling point is 250~350 DEG C.

Hydrogen, hydrocarbonaceous oil material based on hot high score gas THPS-V can enter and add hydrogen upgrading reaction process HT66 It carries out plus HT66-R is reacted in hydrogen upgrading, be converted into and add hydrogen upgrading reaction product HT66-P；

Add hydrogen upgrading react HT66-R, including hydrogenated olefin saturated reaction, hydrodesulfurization reaction, hydrodenitrogeneration reaction, plus One or more of hydrogen aromatic hydrocarbons saturated reaction, hydrocracking reaction, hygrogenating isomerization reaction；

Add hydrogen upgrading reaction process HT66, can be capable of processing and be fractionated the distilled oil that hot high score liquid THPS-L is obtained；

Recycling plus hydrogen upgrading reaction product HT66-P.

The degassing hydrocarbonaceous oil material that hot high score gas THPS-V is obtained is condensed and separated, can enter and add hydrogen upgrading reaction process HT66 is carried out plus hydrogen upgrading reaction HT66-R, is converted into and adds hydrogen upgrading reaction product HT66-P；

Recycling plus hydrogen upgrading reaction product HT66-P.

Based on the hydrogen material for adding hydrogen upgrading reaction product HT66-P, it is used in series into hydrogenation process R10；

Recycling plus hydrogen upgrading reaction product HT66-P.

In separation fractional distillation process, at least part for the narrow fraction oil that heat of dissociation high score liquid THPS-L is obtained can be returned The starting position or middle position for returning the reaction process of hydrogenation process R10 carry out circulation plus hydrogen.

Separation fractional distillation process, heat of dissociation high score liquid THPS-L obtain mainly by wax oil component or with residue fraction group At narrow fraction hydrocarbon material at least part, the starting position or centre of the reaction process of hydrogenation process R10 can be returned to Position carries out circulation plus hydrogen.

The present invention, (2) add hydrogen anti-in floating bed hydrogenation reaction process R10, the son that may include 2 or multiple serial operations Area R10-1, R10-2 etc. are answered, at this point, the reaction effluent based on upper alien hydroconversion reaction zone includes the conventional liquid of at least part The logistics of state hydrocarbon enters the adjacent sub- hydroconversion reaction zone in downstream, and the first sub- hydroconversion reaction zone R10-1 obtains reaction effluent R10-1P, The logistics R10-1PX comprising at least part hydrogenated oil R10-1PO based on reaction effluent R10-1P enters the second son The reaction effluent of hydroconversion reaction zone R10-2, last sub- hydroconversion reaction zone are used as reaction effluent R10P；

Material R10F can be divided into the sub- hydroconversion reaction zone of difference that at least 2 tunnel branch raw materials enter serial operation.

The present invention, (2) in floating bed hydrogenation reaction process R10, existing dispersing type particle hydrogenation catalyst R10C's is first Beginning additive can be nanometer ultra-fine grain aqua oxidation iron catalyst, iron oxide, pyrite, bloodstone, molybdenum oxide, vulcanization One or more of molybdenum, ammonium molybdate, nickel sulfide.

The present invention, (2) in floating bed hydrogenation reaction process R10, using floating bed hydrogenation reactor, the hydrogenation catalyst that uses Agent R10C can be a kind of composite hydrogenation catalyst, include high-activity component and low activity component；The high-activity component gold Belonging to the weight ratio of low activity component metals is 1: 10 to 10: 1；The high-activity component be molybdenum water soluble salt compound or Its mixture；The low activity group is divided into ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, Catalyst R10C water content is lower than 2wt%；The powdered granule that R10C particle diameter is 1~100 μm；

The operating condition of hydrogenation process R10 can be with are as follows: temperature is 300~480 DEG C, pressure be 4.0~30.0MPa, It there are weight is the HAC of component containing high boiling hydrocarbon that hydrogen/feedstock oil volume ratio, which is 0.01: 1~4000: 1, hydrogenation catalyst R10C, Material R10F weight 0.001%~8.0%, volume space velocity be 0.1~10.0hr^-1；The material of the HAC of component containing high boiling hydrocarbon R10F weight chemistry hydrogen consumption is 0.05%~4.0%.

The present invention, (2) in floating bed hydrogenation reaction process R10, using floating bed hydrogenation reactor, the hydrogenation catalyst that uses Agent R10C, typically at least includes Mo element, and Mo is molybdenum disulfide MoS in the body of work form of hydrogenation process R10₂, add The powdered granule that hydrogen catalyst R10C is 0.0001~100 μm；

The operating condition of hydrogenation process R10 can be with are as follows: temperature is 360~460 DEG C, pressure be 6.0~22.0MPa, It there are weight is the HAC's of component containing high boiling hydrocarbon that hydrogen/feedstock oil volume ratio, which is 50: 1~2000: 1, hydrogenation catalyst R10C, Material R10F weight 0.001%~5.0%, volume space velocity be 0.2~5.0hr^-1；The material of the HAC of component containing high boiling hydrocarbon R10F weight chemistry hydrogen consumption is 0.25%~3.0%.

The operating condition of hydrogenation process R10 can be with are as follows: temperature is 360~460 DEG C, pressure be 8.0~16.0MPa, It there are weight is the HAC of component containing high boiling hydrocarbon that hydrogen/feedstock oil volume ratio, which is 200: 1~1200: 1, hydrogenation catalyst R10C, Material R10F weight 0.001%~20.0%, volume space velocity be 0.5~3.0hr^-1；The material of the HAC of component containing high boiling hydrocarbon R10F weight chemistry hydrogen consumption is 0.25%~2.5%.

Hot high score liquid THPS-L is separated and recovered, obtains being mainly what 250~530 DEG C of the hydrocarbon component formed by normal boiling point Distilled oil R10-P-ML, at least part distilled oil R10-P-ML can enter hydrogenation process R10A.

Hot high score liquid THPS-L is separated and recovered, obtains being mainly what 350~530 DEG C of the hydrocarbon component formed by normal boiling point Distilled oil R10-P-ML rich in aromatic hydrocarbons, at least part distilled oil R10-P-ML can enter floating bed hydrogenation modified-reaction mistake Journey BRA.

Hot high score liquid THPS-L is separated and recovered, obtains being mainly what 450~530 DEG C of the hydrocarbon component formed by normal boiling point Distilled oil R10-P-ML rich in aromatic hydrocarbons, at least part distilled oil R10-P-ML can enter floating bed hydrogenation modified-reaction mistake Journey BRA.

The present invention, in general, (1) includes large-size particles catalysis based on hydrogenation modification reaction product BRAP at least partially The flow B RAP-BP-X of agent BP participates in reaction by least part reaction compartment of floating bed hydrogenation reaction process R10, with The charging R10F of floating bed hydrogenation reaction process R10 or the contact of its hydro-conversion object；

Flow B RAP-BP-X, can be selected from the one or several of following logistics:

1. the hydrogenation modification reaction product BRAP of the BP of catalyst containing large-size particles is used as flow B RAP-BP-X；

2. the hydrogenation modification reaction product BRAP of the BP of catalyst containing large-size particles enters thermal high separation process BRAP- BP-X-HS is separated into the hot high score oil BRAP-BP-X-HSO and hot high score gas BRAP-BP-X- of the BP of catalyst containing large-size particles HSV, the hot high score oil BRAP-BP-X-HSO of at least part are used as flow B RAP-BP-X；

3. the hydrogenation modification reaction product BRAP of the BP of catalyst containing large-size particles enters thermal high separation process BRAP- BP-X-HS is separated into the hot high score oil BRAP-BP-X-HSO and hot high score gas BRAP-BP-X- of the BP of catalyst containing large-size particles HSV, gained contains greatly after the hot high score oil BRAP-BP-X-HSO decompression, degassing of the BP of catalyst containing large-size particles at least partially The liquid B RAP-BP-X-HSOA of particles catalyst BP is used as flow B RAP-BP-X；

4. separation hydrogenation modification reaction product BRAP obtains the hydrogenated oil BRAP- of the BP of catalyst containing large-size particles BP-XPO and hydrogen-rich gas；In hydrogenated oil BRAP-BP-XPO fractionating section, separates hydrogenated oil BRAP-BP-XPO and obtain To the logistics of the BP of catalyst containing large-size particles, the logistics rich in hydrogen supply the hydrocarbon component is used as flow B RAP-BP-X at least partially；

5. separation hydrogenation modification reaction product BRAP obtains the hydrogenated oil BRAP- of the BP of catalyst containing large-size particles BP-XPO and hydrogen-rich gas；In hydrogenated oil BRAP-BP-XPO fractionating section, separates hydrogenated oil BRAP-BP-XPO and obtain To the logistics rich in hydrogen supply the hydrocarbon component of the BP of catalyst containing large-size particles, the BP of catalyst containing large-size particles at least partially Logistics rich in hydrogen supply the hydrocarbon component is used as flow B RAP-BP-X；

6. separation hydrogenation modification reaction product BRAP obtains hydrogenated oil BRAP-BP-XPO and hydrogen-rich gas；Adding hydrogen Oil BRAP-BP-XPO fractionating section is generated, separation hydrogenated oil BRAP-BP-XPO obtains the BP's of catalyst containing large-size particles It is mainly that the logistics that hydrogen supply the hydrocarbon component forms of being rich in greater than 350 DEG C is used as flow B RAP-BP-X by normal boiling point.

Hot high score liquid THPS-L is separated and recovered, obtains mainly being added by what the hydrocarbon component that normal boiling point is higher than 530 DEG C formed Hydrogen tail oil R10-P-VS, typically at least a part of tail oil R10K-P-VS do not enter hydrogenation process.

The present invention is recycled back into suspension generally, based on the hydrocarbon material RKKC rich in catalyst that logistics R10-ENDP is obtained Bed hydroprocessing modified-reaction process BRA is mixed with the component materials BRAF of wax oil containing aryl or its hydrogenation products；

Hydrocarbon material RKKC containing catalyst, can be selected from one or more of following materials:

Option 1, a part are high in the heat that the thermal high separation process of hydrogenation process R10 effluent R10-ENDP obtains Divide oil, as the hydrocarbon material RKKC containing catalyst；

Option 2, destilling tower discharge of a part in the separation fractional distillation process of hydrogenation process R10 effluent R10-ENDP The hydrocarbon material containing catalyst, as the hydrocarbon material RKKC containing catalyst；

Option 3, destilling tower discharge of a part in the separation fractional distillation process of hydrogenation process R10 effluent R10-ENDP The distillation cold oil containing catalyst, as the hydrocarbon material RKKC containing catalyst；

Option 4, destilling tower discharge of a part in the separation fractional distillation process of hydrogenation process R10 effluent R10-ENDP The destilling tower base oil containing catalyst, as the hydrocarbon material RKKC containing catalyst；

Option 5, at least part separate the hydrocarbon for the bituminous component that hydrogenation process R10 effluent R10-ENDP is obtained Oil, the raw material VS-EF as solvent extraction and separation process VS-EU contain catalyst what solvent extraction and separation process VS-EU was obtained Hydrocarbon material, as the hydrocarbon material RKKC containing catalyst；

Option 6, at least part separate the hydrocarbon for the bituminous component that hydrogenation process R10 effluent R10-ENDP is obtained Oil, the raw material VS-EF as solvent extraction and separation process VS-EU contain catalyst what solvent extraction and separation process VS-EU was obtained Heavy asphalt hydrocarbon material, as the hydrocarbon material RKKC containing catalyst；

Option 7, at least part separate the hydrocarbon for the bituminous component that hydrogenation process R10 effluent R10-ENDP is obtained Oil, the raw material VS-EF as solvent extraction and separation process VS-EU contain catalyst what solvent extraction and separation process VS-EU was obtained Light asphalt hydrocarbon material, as the hydrocarbon material RKKC containing catalyst；

Option 8, at least part separate the hydrocarbon for the bituminous component that hydrogenation process R10 effluent R10-ENDP is obtained Oil, the raw material VS-EF as solvent extraction and separation process VS-EU contain catalyst what solvent extraction and separation process VS-EU was obtained Middle matter pitch hydrocarbon material, as the hydrocarbon material RKKC containing catalyst.

The present invention contains coal tar pitch component in general, the material R10F of the HAC of component containing high boiling hydrocarbon comes from high temperature coal-tar；

The extraction needle coke that the containing hydrogenated coal tar pitch material based on hydrogenation process R10 effluent R10-ENDP is arranged is former The solvent extraction and separation process VS-EU using solvent segregation of material；

Based on the hydrocarbon material RKKC rich in catalyst that hydrogenation process R10 effluent R10-ENDP is obtained, circulation is returned Hydrogenation process R10 is returned to mix with the raw material of hydrogenation process R10 or intermediate product or final product；

Option 1 is used as to contain and urge in the hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained at least partially The hydrocarbon material RKKC of agent；

Option 2, the heavy asphalt hydrocarbon material containing catalyst obtained at least partially in solvent extraction and separation process VS-EU As the hydrocarbon material RKKC containing catalyst；

Option 3, the light asphalt hydrocarbon material containing catalyst obtained at least partially in solvent extraction and separation process VS-EU As the hydrocarbon material RKKC containing catalyst；

Option 4, the middle matter pitch hydrocarbon material containing catalyst obtained at least partially in solvent extraction and separation process VS-EU As the hydrocarbon material RKKC containing catalyst；

The method that light liquid phase and heavy-fluid phase are isolated using the separation process of solvent segregation, a kind in following:

Option 1, solvent-sedimentation, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present；

Option 2, solvent-centrifugal process, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present；

Option 3, solvent-filtration method, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present；

Option 4, solvent-flocculence, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present；

Option 5, solvent-extraction process, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present；

Option 6, supercritical extraction, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present.

The present invention is raw in based on hydrogenation reaction effluent R10P plus hydrogen in the process U100 of hydrocarbon-bearing material R10F At the separation process of the material containing liquid material of oily R10P-OIL, obtain being higher than containing distributed metal compound particles, containing normal boiling point 450 DEG C of the hydrocarbon components containing colloid or with the hydrocarbon-bearing material S333 of asphalitine；

It can be isolated after being mixed with extractant in solvent extraction and separation process VS-EU-SPU60, material S333 containing extraction The liquid material VS-EU-SPU60-SL of the light phase containing agent for taking solvent, the hydrocarbon component containing relatively low molecular weight is isolated containing extractant, containing phase To the liquid material of heavy phase containing the agent VS-EU-SPU60-SH of high molecular weight the hydrocarbon component, the distributed beaded catalyst R10C of enrichment；

Solvent extraction and separation process VS-EU-SPU60, the extractant used are dissolution colloid or strong with asphalitine ability Organic low boiling point solvent；

The method that solvent extraction and separation process VS-EU-SPU60 isolates light liquid phase and heavy-fluid phase, can be in following 1 kind:

Option 6, supercritical extraction, including light liquid phase distillation process or with heavy-fluid phase distillation process that may be present；

In the fractional distillation process of the liquid material of light phase containing the agent VS-EU-SPU60-SL of distillation abjection extractant that may be present, contain Become light phase material VS-EU-SPU60-LP after agent light phase liquid material VS-EU-SPU60-SL distillation removing extractant；

In the fractional distillation process of the liquid material of heavy phase containing the agent VS-EU-SPU60-SH of distillation abjection extractant that may be present, contain Become heavy phase material VS-EU-SPU60-HP after agent heavy phase liquid material VS-EU-SPU60-SH distillation removing extractant；

The material of the distributed beaded catalyst R10C of richness of at least part based on heavy phase material VS-EU-SPU60-H, is used as Desiccation material VS-EU-SPU60-H-R10C-OUT is used；

Desiccation material VS-EU-SPU60-H-R10C-OUT, the raw material for possibly serving for recycling metal use.

The present invention, solvent extraction and separation process VS-EU-SPU60, the extractant used can be selected from one of the following Or it is several:

Option 1, the solvent containing benzene or toluene；

Option 2, the solvent containing tetrahydrofuran；

Option 3, the solvent containing carbon disulfide；

Option 4, the solvent containing quinoline；

Option 5, the solvent containing cyclohexanone；

Option 6, the solvent containing pyridine；

Option 7, the solvent containing N-Methyl pyrrolidone；

Option 8, the solvent containing dimethyl ether；

Option 9, the solvent containing dimethyl sulfoxide；

Option 10, the solvent containing dimethylformamide；

Option 11, the solvent containing ethylenediamine；

Option 12, the solvent containing acetone；

Option 13, the solvent containing phenolic groups；

The coal tar fraction or its either shallow hydrogenated oil of 14,120~300 DEG C of fraction sections of option；

The liquefied coal coil or its either shallow hydrogenated oil of 15,120~300 DEG C of fraction sections of option；

Option 16, the strong low boiling point richness aromatic solvent of other dissolution asphalitine abilities.

The present invention, in general, dispersing type metal compound particles contained by hydrocarbon-bearing material S333, including distributed beaded catalyst R10C。

The present invention, generally, dispersing type metal compound particles contained by hydrocarbon-bearing material S333, including molybdenum sulfide dispersing type particle Catalyst R10C.

The present invention, in general, at least part liquid material VS-EU-SPU60-SL of light phase containing agent, working method can be selected from following One or more of:

Option 1 is used as outer discharge and process U100 is discharged；

Option 2 returns to floating bed hydrogenation reaction process R10 by least part reaction compartment and participates in reaction.

The present invention, in general, the light phase material VS-EU-SPU60-LP after at least part distillation removing extractant, work side Formula can be selected from one of the following or several:

Option 1 is used as outer discharge and process U100 is discharged；

The present invention, in general, solvent extraction and separation process VS-EU-SPU60, can be used 1 grade of extraction separation process or 2 Grade extraction separation process or multitple extraction separation process.

The present invention, solvent extraction and separation process VS-EU-SPU60 obtain desiccation material VS-EU-SPU60-H-R10C-OUT；

Desiccation material VS-EU-SPU60-H-R10C-OUT containing metal molybdenum or with vanadium or and nickel, may be used as tamping coking technique Raw material, after mixing with coal, the high coke of production tenor produces stamp-charging coke.

Desiccation material VS-EU-SPU60-H-R10C-OUT containing metal molybdenum or with vanadium or and nickel, may be used as tamping coking technique Raw material, after being mixed with coal, the high coke of production tenor, in general, the step of production stamp-charging coke is as follows:

1. it is mixed, is crushed with coking with clean fine coal after desiccation material VS-EU-SPU60-H-R10C-OUT solidification, crushing, It makes cake of press firm by ramming, obtains briquette；

2. sending into coke oven in isolation heated under air and keeping the temperature briquette, then through cooling and screening process, obtain Coke.

Desiccation material VS-EU-SPU60-H-R10C-OUT containing metal molybdenum or with vanadium or and nickel, may be used as recycling metal original Material uses.

Desiccation material VS-EU-SPU60-H-R10C-OUT containing metal molybdenum or with vanadium or and nickel, with can make recycle metal original Material uses；

The working method for recycling metal, can be selected from one of the following or several:

Option 1 first burns the desiccation material VS-EU-SPU60-H-R10C-OUT of liquid condition or solid particle state, so Flue dust is handled to obtain ammonium molybdate with ammonia and ammonium carbonate afterwards；

Desiccation material VS-EU-SPU60-H-R10C-OUT progress coking is first obtained coke, then combustion of coke by option 2, Then flue dust is handled to obtain ammonium molybdate with ammonia and ammonium carbonate；

Option 3 is carried out in the presence of first alcohol and oxidizing agent using sulfuric acid and desiccation material VS-EU-SPU60-H-R10C-OUT Reaction, molybdenum are extracted into water phase and are recycled；Oxidant may be hydrogen peroxide；

Option 4, the high temperature high pressure process under molten, ammonia pressure using acid add inorganic acid, separate, be passed through hydrogen sulfide, divide From and etc. molybdenum be converted to molybdenum sulfide and recycle molybdenum；

Option 5, the first step will roast after desiccation material VS-EU-SPU60-H-R10C-OUT and solid base ground and mixed；The The solid obtained after roasting is carried out water logging by two steps, and obtained leaching liquid obtains molybdate by condensing crystallizing and crystallizes.

The present invention, the component materials BRAF of wax oil containing aryl can be mainly made of the hydrocarbon that normal boiling point is 350~570 DEG C And solid particle may be contained, it can be selected from one or more of following materials:

1. logistics containing oil product obtained by middle coalite tar or its distillate or its hot procedure；Hot procedure is selected from coke Change process or catalytic cracking process or catalytic pyrolysis process or hydrogenation process；

2. logistics containing oil product obtained by high temperature coal-tar or its distillate or its hot procedure；

3. logistics containing oil product obtained by direct hydrogenation liquefaction of coal liquefaction process, including using the coal hydrogenation of hydrogen supply dissolvent oil direct Liquefaction liquefaction process, coal refines process to oil altogether, coal faces hydrogen thermosol liquefaction process；

4. logistics containing oil product obtained by shale oil or its distillate or its hot procedure；

5. logistics containing oil product obtained by ethylene cracking tar or its distillate or its hot procedure；

6. logistics containing oil product obtained by petroleum based heavy fuel oils or its hot procedure；

7. logistics containing oil product obtained by tar sand base weight oil or its hot procedure；

8. other aromatic hydrocarbons weight contents are higher than the hydrocarbon ils that 40%, organic nitrogen weight content is higher than 0.10%.

The present invention, the component materials of wax oil containing aryl BRAF can be the high aromatic hydrocarbons wax oil containing solid particle, mainly by normal The hydrocarbon that boiling point is 350~570 DEG C is advised to form, it can be selected from one or more of following materials:

1. the wax slop of petroleum base viscous crude；

2. the heavy-oil catalytic heavy-cycle oil that heavy oil catalytic cracking reaction product fractionation process obtains；

3. the heavy-oil catalytic clarified oil that heavy oil catalytic cracking reaction product fractionation process obtains；

4. the coking wax slop that coking heavy oil reaction product fractional distillation process obtains；

5. the wax slop that heavy-oil hydrogenation heat cracking reaction product fractionation process obtains；

6. the wax slop that direct hydrogenation liquefaction of coal reaction product fractional distillation process obtains；

7. kerosene refines the wax slop that hydrogenation reaction product fractional distillation process obtains altogether.

The present invention, the component materials BRAF of wax oil containing aryl can be mainly made of the hydrocarbon that normal boiling point is 350~570 DEG C And contain solid particle.

The present invention separates the hydro carbons in hydrogenation modification reaction product BRAP, obtains rich in double ring arene or polycyclic aromatic hydrocarbon It is anti-by at least part that wax oil KKAA, at least part wax oil KKAA can return to floating bed hydrogenation modified-reaction process BRA It answers space to participate in reaction, is contacted with the charging richness aromatic hydrocarbons wax oil BRAF of floating bed hydrogenation reaction process R10 or its hydro-conversion object.

The present invention separates the hydro carbons in hydrogenation reaction product R10P, obtains the wax oil rich in double ring arene or polycyclic aromatic hydrocarbon KKBB, at least part wax oil KKBB can return to floating bed hydrogenation modified-reaction process BRA and react empty by least part Between participate in reaction, contacted with the charging richness aromatic hydrocarbons wax oil BRAF of floating bed hydrogenation reaction process R10 or its hydro-conversion object.

The present invention, the operating condition of floating bed hydrogenation modified-reaction process BRA can be with are as follows: reaction temperature is 390~445 DEG C, reactor pressure be 6~30MPa, vapor phase hydrogen volumetric concentration 50~95%, gas-liquid volume ratio be 100~2000 standards stand Square rice/ton, hydrogenation modification catalyst BRA-CAT additive amount are 0.001 matter of mass %~5 of the weight of high aromatic hydrocarbons wax oil BRF % is measured, co-catalyst additive amount is that sulphur in co-catalyst/catalyst activity metal molar ratio is 1.0~2.0, when reaction stops Between TRU be 5 minutes~120 minutes.

The present invention, the hydrogenation catalyst that floating bed hydrogenation modified-reaction process BRA is used, can be a kind of composite hydrogenation Catalyst includes high-activity component and low activity component；The weight ratio of the high-activity component metal and low activity component metals It is 1: 10 to 1000: 1；The high-activity component contains the oil-soluble salt compounds or water soluble salt compound or it is mixed of molybdenum Close object；The low activity component contains ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, urges Agent water content is lower than 2wt%.

The present invention, the hydrogenation catalyst that floating bed hydrogenation modified-reaction process BRA is used, may include a nanometer ultra-fine grain Aqua oxidation iron catalyst or with iron oxide or with pyrite or with bloodstone or with molybdenum oxide or with molybdenum sulfide or and ammonium molybdate Or and nickel sulfide.

The present invention, in general, floating bed hydrogenation modified-reaction process BRA, uses at least part hydrogen supply dissolvent BRA-DS；

Hydrogen supply dissolvent BRA-DS, it may be possible in gas phase obtained by the intermediate reaction product based on separation hydrogenation process A10 Contained the hydrocarbon component or its stabilized hydrogenation the hydrocarbon component；

Hydrogen supply dissolvent BRA-DS, it may be possible to hydrocarbon obtained by the final reacting product A10P based on separation hydrogenation process A10 Component or its stabilized hydrogenation the hydrocarbon component；

Hydrogen supply dissolvent BRA-DS, it may be possible to the hydrogen supply the hydrocarbon component generated based on high aromatic hydrocarbons wax oil BRAF in hydrogenation process BRA BRA-CDC；

Hydrogen supply dissolvent BRA-DS, it may be possible to external hydrogen supply hydrocarbon OUT-TO-BRA-DS.

It is routinely boiled in the weight flow rate BRA-DS-W of hydrogen supply dissolvent flow B RA-DS and the component materials of wax oil containing aryl BRAF The ratio that point is higher than the weight flow rate BRAF-D-W of 450 DEG C of the hydrocarbon components is oil ratio BK100=(BRA-DS-W)/(BRAF-D- W), BK100 is 0.1~10.0.

Hydrogen supply dissolvent BRA-DS is mainly that 250~530 DEG C of hydro carbons form by normal boiling point, the weight of part saturation aromatic hydrocarbons Measuring content to be greater than 15%, aromatic carbon rate is 0.35~0.70.

The present invention, generally, floating bed hydrogenation modified-reaction process BRA uses at least part hydrogen supply dissolvent BRA-DS；

Hydrogen supply dissolvent BRA-DS is mainly that 250~530 DEG C of hydro carbons form by normal boiling point, the weight of part saturation aromatic hydrocarbons Measuring content to be greater than 25%, aromatic carbon rate is 0.45~0.60.

The present invention, (1) the component materials of wax oil containing aryl BRAF floating bed hydrogenation modified-reaction process BRA, at least one It is based partially on the flow B RAP-BP-WX comprising large-size particles catalyst BP, the hydrocarbon containing hydrogen supply of product BRAP, it can be by adding At least part reaction compartment of the floating bed hydrogenation reaction process CR of material CRF of the work containing residue fraction participates in reaction, with object Expect CRF or the contact of its hydro-conversion object；

In floating bed hydrogenation reaction process CR, there are hydrogen, conventional liq, distributed large-size particles catalyst BP are same When there may be hydrogen supply hydrocarbon, there may be dilution hydrocarbon, there may be under conditions of distributed small size particle catalyst LP, at least A part carries out hydrogenation reaction R10R containing the material CRF that normal boiling point is higher than 530 DEG C of hydrocarbon and at least part removal of ccr by hydrotreating occurs Reaction is converted into hydrogenation reaction product CRP；

Flow B RAP-BP-W comprising large-size particles catalyst BP of at least part based on product CRP, passes through suspension At least part reaction compartment of bed hydroprocessing reaction process R10 participates in reaction, the charging with floating bed hydrogenation reaction process R10 R10F or the contact of its hydro-conversion object.

The present invention, in general, flow B RAP- comprising large-size particles catalyst BP of at least part based on product CRP BP-W participates in reaction by least part reaction compartment of floating bed hydrogenation reaction process R10, reacted with floating bed hydrogenation The charging R10F of journey R10 or the contact of its hydro-conversion object；

Flow B RAP-BP-W, can be selected from the one or several of following logistics:

1. the hydrogenation reaction product CRP of the BP of catalyst containing large-size particles is used as flow B RAP-BP-W；

2. the hydrogenation reaction product CRP of the BP of catalyst containing large-size particles enters thermal high separation process BRAP-BP-W-HS It is separated into the hot high score oil BRAP-BP-W-HSO and hot high score gas BRAP-BP-W-HSV of the BP of catalyst containing large-size particles, at least A part of hot high score oil BRAP-BP-W-HSO is used as flow B RAP-BP-W；

3. the hydrogenation reaction product CRP of the BP of catalyst containing large-size particles enters thermal high separation process BRAP-BP-W-HS It is separated into the hot high score oil BRAP-BP-W-HSO and hot high score gas BRAP-BP-W-HSV of the BP of catalyst containing large-size particles, at least The hot high score oil BRAP-BP-W-HSO of a part catalyst containing large-size particles BP is depressured, gained contains large-size particles after degassing The liquid B RAP-BP-W-HSOA of catalyst BP is used as flow B RAP-BP-W；

4. separation hydrogenation reaction product CRP obtains hydrogenated oil BRAP-BP-WPO and hydrogen-rich gas；In hydrogenated oil BRAP-BP-WPO fractionating section, separation hydrogenated oil BRAP-BP-WPO obtain the logistics of the BP of catalyst containing large-size particles, The logistics of at least part catalyst containing large-size particles BP is used as flow B RAP-BP-W；

5. separation hydrogenation reaction product CRP obtains hydrogenated oil BRAP-BP-WPO and hydrogen-rich gas；In hydrogenated oil BRAP-BP-WPO fractionating section, separation hydrogenated oil BRAP-BP-WPO obtain being rich in for the BP of catalyst containing large-size particles and supply The logistics of hydrogen the hydrocarbon component, the logistics rich in hydrogen supply the hydrocarbon component of the BP of catalyst containing large-size particles is used as logistics at least partially BRAP-BP-W；

6. separation hydrogenation reaction product CRP obtains hydrogenated oil BRAP-BP-WPO and hydrogen-rich gas；In hydrogenated oil BRAP-BP-WPO fractionating section, separation hydrogenated oil BRAP-BP-WPO obtain the BP of catalyst containing large-size particles mainly by Normal boiling point is that the logistics rich in hydrogen supply the hydrocarbon component composition greater than 350 DEG C is used as flow B RAP-BP-W.

The present invention separates the hydro carbons in hydrogenation reaction product CRP, obtains the wax oil rich in double ring arene or polycyclic aromatic hydrocarbon KK66, at least part wax oil KK66 can return to floating bed hydrogenation modified-reaction process BRA or react with floating bed hydrogenation Journey CR participates in reaction by least part reaction compartment.

The present invention separates the hydro carbons in hydrogenation reaction product R10P, obtains the wax oil rich in double ring arene or polycyclic aromatic hydrocarbon KK77, at least part wax oil KK77 can return to floating bed hydrogenation modified-reaction process BRA or react with floating bed hydrogenation Journey CR participates in reaction by least part reaction compartment with floating bed hydrogenation reaction process R10.

The present invention, separate hydrogenation reaction product CRP or with the hydro carbons in hydrogenation reaction product R10P, obtain rich in bicyclic virtue The wax oil KK77 of hydrocarbon or polycyclic aromatic hydrocarbon obtains mainly being rich in colloid, pitch by what the hydrocarbon component that normal boiling point is higher than 520 DEG C formed The possibility of matter contains the hydrocarbon stream KK255 of solid particle；

At least part wax oil KK77 can return to floating bed hydrogenation modified-reaction process BRA and be reacted by least part Space participates in reaction；

At least part wax oil KK255 can return to floating bed hydrogenation reaction process CR and pass through at least part reaction compartment Participate in reaction.

The present invention, hydrocarbon CRF inferior can be mainly by normal boiling point higher than 570 DEG C of the hydrocarbon component form rich in colloid, The possibility of asphalitine contains the hydrocarbon stream of solid particle, and carbon residue content is 20~65 weight %.

The present invention, hydrocarbon CRF inferior can be mainly by normal boiling point higher than 570 DEG C of the hydrocarbon component form rich in colloid, The possibility of asphalitine contains the hydrocarbon stream of solid particle, and carbon residue content is 30~45 weight %.

The present invention, hydrocarbon CRF inferior can be mainly by normal boiling point higher than 570 DEG C of the hydrocarbon component form rich in colloid, The high carbon residue hydrocarbon containing solid particle of asphalitine, the weight concentration of solid particle are 0.010 weight of weight %~40.0 %.

The present invention, hydrocarbon CRF inferior can be mainly by normal boiling point higher than 570 DEG C of the hydrocarbon component form rich in colloid, The high carbon residue hydrocarbon containing solid particle of asphalitine, the weight concentration of solid particle are 0.10 weight of weight %~20.0 %.

The present invention, hydrocarbon CRF inferior can be mainly by normal boiling point higher than 570 DEG C of the hydrocarbon component form rich in colloid, The high carbon residue hydrocarbon containing solid particle of asphalitine, the weight concentration of solid particle are 0.10 weight of weight %~5.0 %.

The present invention, in general, in hydrocarbon CRF floating bed hydrogenation reaction process CR inferior, the heat from hydrogenation cracking rate of hydrocarbon CRF inferior is 5~45%.

The present invention, in general, the operating condition of floating bed hydrogenation reaction process CR are as follows: reaction temperature is 390~445 DEG C, instead Answer device pressure be 6~30MPa, vapor phase hydrogen volumetric concentration 50~95%, gas-liquid volume ratio be 100~2000 standard cubic meters/ Ton, hydrogenation modification catalyst CRA-CAT additive amount are the 0.001 mass % of mass %~5 of the weight of hydrocarbon CRF inferior, co-catalysis Agent additive amount is that sulphur in co-catalyst/catalyst activity metal molar ratio is 1.0~2.0, and reaction time TRU is 5 points Clock~120 minute.

The present invention, the hydrogenation catalyst that floating bed hydrogenation reaction process CR is used can be a kind of composite hydrogenation catalysis Agent includes high-activity component and low activity component；The weight ratio of the high-activity component metal and low activity component metals is 1: 10 to 1000: 1；The high-activity component contain molybdenum oil-soluble salt compounds water soluble salt compound or its mixing Object；The low activity component contains ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, catalysis Agent water content is lower than 2wt%；The powdered granule that deliquescence accelerant particle diameter is 0~100 μm.

The present invention, in general, the hydrogenation catalyst that floating bed hydrogenation reaction process CR is used, may include a nanometer ultra-fine grain Aqua oxidation iron catalyst or with iron oxide or with pyrite or with bloodstone or with molybdenum oxide or with molybdenum sulfide or and ammonium molybdate Or and nickel sulfide.

The present invention, in general, using at least part hydrogen supply dissolvent CR- in hydrocarbon CRF floating bed hydrogenation reaction process CR inferior DS；

Hydrogen supply dissolvent CR-DS, it may be possible to institute in gas phase obtained by the intermediate reaction product based on separation hydrogenation process R10 The hydrocarbon component contained or its stabilized hydrogenation the hydrocarbon component；

Hydrogen supply dissolvent CR-DS, it may be possible to based on separation hydrogenation process R10 final reacting product obtained by the hydrocarbon component or its Stabilized hydrogenation the hydrocarbon component；

Hydrogen supply dissolvent CR-DS, it may be possible to institute in gas phase obtained by the intermediate product based on separation hydrogenation modification reaction process BRA The hydrocarbon component contained or its stabilized hydrogenation the hydrocarbon component；

Hydrogen supply dissolvent CR-DS, it may be possible to based on separation hydrogenation modification reaction process BRA final product obtained by the hydrocarbon component or its Stabilized hydrogenation the hydrocarbon component；

Hydrogen supply dissolvent CR-DS, it may be possible to hydrocarbon group contained in gas phase obtained by the intermediate product based on separation reaction process CR Point or its stabilized hydrogenation the hydrocarbon component；

Hydrogen supply dissolvent CR-DS, it may be possible to based on separation reaction process CR final product obtained by the hydrocarbon component or its add hydrogen steady Determine the hydrocarbon component；

Hydrogen supply dissolvent CR-DS, it may be possible to the hydrogen supply the hydrocarbon component generated based on hydrocarbon CRF floating bed hydrogenation reaction process CR inferior CR-CDC；

Hydrogen supply dissolvent CR-DS, it may be possible to external hydrogen supply hydrocarbon OUT-TO-CR-DS.

The ratio of the weight flow rate CRF-W of the weight flow rate CR-DS-W of hydrogen supply dissolvent flow C R-DS and hydrocarbon stream CRF inferior Value is oil ratio BK100=(CR-DS-W)/(CRF-W), and CK100 is 0.05~5.0.

The present invention generally in hydrocarbon CRF floating bed hydrogenation reaction process CR inferior, uses at least part hydrogen supply dissolvent CR- DS；

Normal boiling point is higher than 450 DEG C of the hydrocarbon components in the weight flow rate CR-DS-W and material CRF of hydrogen supply dissolvent flow C R-DS Weight flow rate CRF-H-W ratio be oil ratio BK100=(CR-DS-W)/(CRF-H-W), CK100 be 0.5~1.5.

Hydrogen supply dissolvent flow C R-DS is mainly that 250~530 DEG C of hydro carbons form by normal boiling point, part saturation aromatic hydrocarbons Weight content be greater than 15%, aromatic carbon rate be 0.35~0.70.

Hydrogen supply dissolvent flow C R-DS is mainly that 250~530 DEG C of hydro carbons form by normal boiling point, part saturation aromatic hydrocarbons Weight content be greater than 25%, aromatic carbon rate be 0.45~0.60.

The present invention, in general, the operation target of up flow type expanded bed hydrogenation modification reaction process CRA are as follows: hydrogen consumption is Gao Fang The 0.1 mass % of mass %~1.5 of chloroflo oil BRF weight, heat from hydrogenation cracking reaction conversion ratio are 20~35 mass %.

The present invention, generally, the operation target of up flow type expanded bed hydrogenation modification reaction process CRA are as follows: hydrogen consumption is Gao Fang The 0.1 mass % of mass %~1.5 of chloroflo oil BRF weight, heat from hydrogenation cracking reaction conversion ratio are 5~25 mass %.

Detailed description of the invention

Fig. 1 be a kind of content of wax oil plant add hydrogen, add containing oil of dreg hydrogen, catalyst circulation combined method principle flow chart.

Content of wax oil plant shown in FIG. 1 adds hydrogen, adds the combined method of hydrogen, catalyst circulation containing oil of dreg, includes rich aromatic hydrocarbons wax Up flow type floating bed hydrogenation modified-reaction process BRA, the up flow type floating bed hydrogenation thermal cracking reactor R10, reaction product of oil The high pressure hot separator THPS of R10P, heat low separate section TLPS, low point of oily prefractionator 1T of heat, the charging of vacuum fractionation tower Heating furnace 2T-INFU, the first reduced-pressure flash tank 2TFS1, the first vacuum flashing gas heating furnace 2T-FVFU, the second reduced-pressure flash tank 2TFS2, vacuum fractionation tower 2T, the rich catalyst material circulatory system.

As shown in Figure 1, in up flow type floating bed hydrogenation modified-reaction process BRA, along the circulation wax oil R- of the conveying of pipeline 001 VGO (solid particle catalyst may be contained), it is urged along other wax oil BRA9F of the conveying of pipeline 002, along containing for the conveying of pipeline 003 Agent BP material (precursor of solid particle catalyst BP can be generated containing solid particle catalyst BP or in reaction process), The hydrogen material BRAH for being rich in BP cycle stock XS10-KS, conveying along pipeline 005 conveyed along pipeline 209, is mixed into along pipeline The reaction feed BRATF of 008 conveying；Reaction feed BRATF enters reactor B RA from bottom, the mainstream material in reactor B RA It flows from bottom to top, the gas, liquid, solid phase reaction conveyed along pipeline 011 that reaction is converted into from top discharge reactor B RA produces Object BRAP, the reaction product BRAP comprising catalyst BP, hydrogen supply dissolvent enter reactor R10.

As shown in Figure 1, residual oil R10FL, edge in hydrogenation of residual oil suspended bed heat cracking reaction process, along the conveying of pipeline 101 (solid can be generated containing solid particle catalyst or in reaction process in the R10C containing catalyst feed that pipeline 102 conveys Grain catalyst) the mixture R10MF conveyed along pipeline 103 is mixed into mixed cell FMIXER；Mixture R10MF with along pipeline Hydrogen material R10H, the reaction product BRAP of 105 conveyings are mixed into the reaction feed R10TF conveyed along pipeline 108；React into Expect that R10TF from bottom enters reactor R10, the mainstream material in reactor R10 flows from bottom to top, reacts and is converted into from top The gas, liquid, solid phase reaction product R10P that discharge reactor R10 is conveyed along pipeline 111.

As shown in Figure 1, gas, liquid, solid phase reaction product R10P is separated into through pipeline 111 into high pressure hot separator THPS The hot high score gas THPS-V conveyed along pipeline 121, the hot high score oil THPS-L conveyed along pipeline 122, hot high score oil THPS-L warp Decompression, vaporization are realized after crossing the dropping valve being mounted in 122 system of G pipeline, are fed as thermal low-pressure separators TLPS and are entered heat Low pressure separate section TLPS, the hot low point of oil for being separated into the low point of gas TLPS-V of heat along the conveying of pipeline 131, being conveyed along pipeline 132 TLPS-L。

As shown in Figure 1, low point of oil TLPS-L of heat with may be mixed into and mix along the cold low point of oil LLPS-L that pipeline 201 conveys Expect that 1TTF enters prefractionator 1T along pipeline 135；Before mixture 1TTF enters prefractionator 1T along pipeline 135, it may pass through Prefractionator feeds the heating of heating furnace 1T-INFU (not shown), still, for simple flow, reduces investment outlay, does not set usually Set prefractionator charging heating furnace 1T-INFU.

As shown in Figure 1, mixture 1TTF through prefractionator 1T fractionate out along pipeline 151 convey narrow fraction oil 1TP1 (such as Normal boiling point lower than 150 DEG C of hydrocarbon composition hydrocarbon containing conventional gas, hydrogen sulfide, hydrogen prefractionator liquid of top of the tower), along pipeline 152 The narrow fraction oil 1TP2 (prefractionator first side line oil of such as normal boiling point between 130~200 DEG C of hydro carbons composition) of conveying, edge Narrow fraction oil 1TP3 (the prefractionator second side of such as normal boiling point between 180~260 DEG C of hydro carbons composition that pipeline 153 conveys Line oil), along pipeline 159 convey prefractionator tower bottom oil 1TP9 (such as by normal boiling point be higher than 250 DEG C hydrocarbon and solid form) Deng.

As shown in Figure 1, inside prefractionator 1T, it is that may be present in prefractionator the second side line oil 1TP3 in order to reduce The concentration of solid particle sets up washing section 1TWU between mixture 1TTF import and the second outlet port side line oil 1TP3, usually Using flowed down from tower internal upper part withdrawing fluid washing rise hydrocarbon vapours, can in a manner of arbitrary suitable wash, such as Spray head atomization mode of washing or setting tower tray washing section mode of washing or setting padding washing section mode of washing can be used, The solid particle that liquid contact ascending vapor is trapped usually enters prefractionator tower bottom oil with the washing oil that washing section is discharged In 1TP9.

As shown in Figure 1, prefractionator tower bottom oil 1TP9, absorbs heat by vacuum fractionation tower charging heating furnace 2T-INFU Afterwards to improve rate of gasification, the vacuum tower charging 2TF of discharge heating furnace 2T-INFU enters the first reduced-pressure flash tank along pipeline 161 2TFS1, the first vacuum flashing liquid for being separated into the first vacuum flashing gas 2TFS1V along the conveying of pipeline 171, being conveyed along pipeline 172 2TFS1L。

As shown in Figure 1, the first vacuum flashing liquid 2TFS1L, is that (normal boiling point is dense lower than the weight of 350 DEG C of hydro carbons for initial boiling point Degree is suitable for (viscosity is low, density is low, asphalitine good dispersion) containing distributed beaded catalyst lower than 15%) suitable physical property R10C, the XS10-F containing liquid phase material for being higher than 450 DEG C of the hydrocarbon components containing normal boiling point.Due to containing a large amount of heavy diesel fuel component, wax Oil ingredient, temperature is also higher (can control temperature and be in 280~430 DEG C of ranges), and the viscosity of the logistics is low, density is small, pitch Matter all dissolution dispersions are suitable for being applicable in cyclone hydraulic separators or sedimentation centrifuge or filter centrifugal work.

As shown in Figure 1, material XS10-F enters the mechanically decoupled process XS10 using cyclone hydraulic separators, it is separated into 2 road objects Material: rich catalyst feed XS10-KS, the poor catalyst liquid material XS10-F-LP that gas phase may be contained；

As shown in Figure 1, richness catalyst feed XS10-KS returns to up flow type floating bed hydrogenation modified-reaction mistake along pipeline 209 Journey BRA；

As shown in Figure 1, after material XS10-F-LP, the first vacuum flashing gas 2TFS1V mixing, along pipeline 174 by depressurizing To improve rate of gasification after fractionating column charging heating furnace 2T-FVFU absorption heat, the heat of heating furnace 2T-FVFU is discharged along pipeline 175 Material becomes 2TF66 along pipeline 177 and enters the second reduced-pressure flash tank 2TFS2, is separated into along pipe after mixing with possible mixed material The second vacuum flashing gas 2TF99, the second vacuum flashing liquid 2TFS2L conveyed along pipeline 178 that road 179 conveys.

As shown in Figure 1, the second vacuum flashing liquid 2TFS2L, is that (normal boiling point is dense lower than the weight of 530 DEG C of hydro carbons for initial boiling point Degree lower than 10%, the residue oil that mainly residual oil by normal boiling point higher than 530 DEG C and solid form)) be suitable for containing distributed The XS20-F containing liquid phase material of grain catalyst R10C.

In order to isolate the circulation hydro-conversion of the heavy hydrocarbon in XS20-F containing liquid phase material, while isolating catalyst particles Grain, other particulate matters will contain liquid phase material XS20-F and pressurizeing with extractant (the strong low boiling point solvent of dissolution asphalitine ability) Under the conditions of mixing disperse asphalitine, then under the conditions of 150~200 DEG C, carry out rotary filter press, be separated into extraction light phase, extraction Take heavy phase；After extracting light phase distillation abjection extractant, partially becomes outer discharge XS20-OUTL discharge system, partially become along pipe The material that road 339 conveys returns to hydrogenation process R10；Become the edge desiccation material S100 after extracting heavy phase distillation abjection extractant Pipeline 350 is discharged, and partially becomes outer discharge S101 discharge system and is used as metal recovery raw material, is partially used as recycling catalyst material edge Pipeline 352 returns to hydrogenation process R10；

As shown in Figure 1, vacuum tower feeds 2TF99, the narrow fraction oil conveyed along pipeline 181 is fractionated out through vacuum fractionation tower 2T 2TP1 (such as normal boiling point between 240~360 DEG C of distillate), narrow fraction oil 2TP2 (such as normal boiling point conveyed along pipeline 182 Vacuum fractionation tower the first side line oil formed between 350~450 DEG C of hydro carbons), the narrow fraction oil 2TP3 that is conveyed along pipeline 183 (vacuum fractionation tower second side line oil of such as normal boiling point between 440~520 DEG C of hydro carbons composition) containing along what pipeline 184 conveyed Solid particle narrow fraction oil 2TP4 (vacuum fractionation tower tower bottom oil that such as normal boiling point is formed between 515~540 DEG C of hydro carbons, Washing section discharge oil) etc..

As shown in Figure 1, inside vacuum fractionation tower 2T, in order to reduce solid that may be present in the second side line oil 2TP3 The concentration of grain feeds in vacuum tower and sets up washing section 2TWU between 2TF import and the second outlet port side line oil 2TP3, usually used The hydrocarbon vapours that the withdrawing fluid washing flowed down from tower internal upper part rises, can be in a manner of arbitrary suitable wash, such as can be with Mode of washing or setting tower tray washing section mode of washing or setting padding washing section mode of washing, liquid are atomized using spray head The solid particle that contact ascending vapor is trapped usually is collected as vacuum fractionation with the rich solid washing oil of washing section discharge Oil 2TP4 is discharged in tower washing section, and vacuum fractionation tower 2T is discharged along pipeline 184.

Oil 2TP3 (rich aromatic hydrocarbons heavy wax oil), 2TP4 is discharged (containing the rich virtue of solid particle in vacuum fractionation tower 2T as shown in Figure 1 Hydrocarbon heavy wax oil), return to up flow type floating bed hydrogenation modified-reaction process BRA circulation plus hydrogen.

Specific embodiment

The mechanically decoupled process of solid-liquid belongs to solid-liquid two-phase flow scope, and wherein solid particle is dispersed phase, the liquid of continuous state It is mutually decentralized medium, since they have different physical properties, it is possible to mechanically be isolated.Realize separation Bare bones are to make to generate relative motion between solid and liquid phase.Separation of solid and liquid is usually divided into two major classes, that is, is concentrated and filters, The two can be applied in combination, and constitute 2 grades or multistage separation of solid and liquid process.

About solid-liquid separation technique principle, isolation technics, sorting device and system, the information of Separation Indexes, record this kind of One document of data is shown in document A01: 1. publication title: " separation of solid and liquid "；2. retrieval is encoded with books: ISBN coding: 7- 5024-1945-4, Chinese depository library CIP data core word (96) the 18533rd；3. chief editor: Luo Qian；4. publishing house: metallurgy Industrial publishing house.

Table 1 lists some solid-liquid mechanical separation technologies, and applicable technology therein can be used in the present invention.

Cyclone hydraulic separators of the present invention belongs to centrifugal separation equipment, continuous feed and is continuously discharged during the separation process Clear liquid and concentrate, belong to hydrocyclone.

Cyclone hydraulic separators of the present invention, alternatively referred to as cyclone separator, hydrocyclone etc. are former using centrifugal sedimentation The equipment that solid particle is separated from suspension is managed, equipment body is made of cylinder and circular cone two parts.

When for solid-liquor separation, the basic functional principle of single-stage cyclone hydraulic separators is, suspension through feed pipe tangentially into Enter cylinder, make spiralling downwards, solid particle is thrown toward wall by centrifugal inertial force effect, is down to cone bottom with lower eddy flow Outlet is known as underflow by the enrichment liquid that bottom is discharged.Clear liquid or liquid containing subparticle then become the internal layer eddy flow of rising, It is discharged from the central tube at top, referred to as overflow.There is the air column for being in negative pressure at internal layer eddy flow center, the gas in air column be by It is released in slurry, or due to being drawn air into device when overflow nozzle is exposed in atmosphere.Cyclone separator The characteristics of be that drum diameter is small and tapered segment is long, the cylinder of minor diameter is conducive to increase centrifugal inertial force, to improve sedimentation speed Degree；Meanwhile conical section lengthening can increase liquid stream stroke, to extend residence time of the suspension in device.

When for Liquid liquid Separation, two-phase mixtures liquid to be separated is entered in device with certain pressure from tangential admission mouth, and Strong rotary motion is formed in device.Due to centrifugal sedimentation act on, most of light phase by overflow port discharge, and heavy phase then by Outside underflow opening jetting device at the vertex of a cone.

After solid phase particles enter hydrocyclone, depending on the relationship of movement velocity active force suffered by it.Particle is thinner Or solid-liquid two-phase density contrast is smaller, the motion profile and streamline of particle are closer, and such particle is difficult to divide from liquid phase It separates out and；Thicker particle then due to suffered centrifugal force is enough that it is made to carry out centrifugal sedimentation, then generates between liquid phase opposite It moves and is achieved two alternate separation.

Therefore, the density contrast for expanding grain density and liquid component density as far as possible is the effective way for improving separative efficiency Therefore diameter for the present invention, is changed very little within the scope of 0~400 DEG C and fluid density is at 0~400 DEG C using density of solid The very big feature of variation in range carries out rotary filter press under the condition of high temperature of fractionating column discharge material as far as possible, it might even be possible to will Fractionating column discharge material first pressurize heat up again after carry out rotary filter press, to improve separation accuracy.

Cyclone separator can be used for being separated by solid-liquid separation (enrichment), solid recycling, be used as more significant special when classifying equipoment uses Point.Also there is corresponding variation according to enrichment or the difference of classification purposes, the dimension scale of cyclone separator.

Table 1 is separated by solid-liquid separation classification chart

Cyclone separator diameter is greatly lowered i.e. for same charging rate in cyclone separator, including micro- cyclone separator Eddy flow field diameter is reduced, centrifugal acceleration can be increased considerably, shortens the distance that solid reaches cyclone separator wall, divides to improve From efficiency.Micro- rotation point of the present invention, can according to need reduces its eddy flow field diameter, allows to reach very high CENTRIFUGAL ACCELERATING Degree, for example can achieve the centrifugal acceleration of tens of to hundreds of G (acceleration of gravity).

In cyclone separator, solid particle will cause the serious abrasion of separator along quickly moving for wall surface, make to extend With the time limit, Ying Caiyong wear-resistant material manufactures or makees liner using wear-resistant material.

The advantages of cyclone hydraulic separators, is:

1. simple structure, non-activity part, in suspension by tangential admission pressure and rotate, performance can It leans on, is low in cost；

2. small in size, occupied area is also small；

3. production capacity is big, more rotary filter press unit collection can be used in a container；

4. isolated granulometric range is wider.

In general, rotary filter press process is used for high magnification thickened solid, recycled with the rate of recovery as high as possible without solid liquid material, Concentrated slurry as a small amount of as possible is obtained, due to being limited by distribution ratio is too small, point of spinning liquid separation process under normal condition It is lower from efficiency, can using what concatenated mode or with other separation equipment fit applications, to improve its separative efficiency.

Hydrocyclone no-rotary part, in suspension by tangential admission pressure and rotate.In waterpower In cyclone, there is the shear action formed because velocity gradient is very high in suspension, this will destroy issuable particle and gather Collective or floc sedimentation, it is desired in separation operation process that this effect, which should be said not, but for the liquid phase high for viscosity, It is then a kind of advantageous anti-deposition cleaning action.

Decompression residuum uses the solid particle in the product R10P of the floating bed hydrogenation reaction process R10 of solid particless catalyst, It can be catalyst granules, ash content, free carbon, organic metal hydroformylation product solution metal sulfide, according to specific technological operation Journey, equivalent diameter can be nanoscale or micron order, and density is determined by forming, the density of some common metal sulfide, Melting point data is shown in Table 2.

The density of some common metal sulfide in 2 decompression residuum floating bed hydrogenation reaction product R10P of table, fusing point number According to

The present invention described in detail below.

Pressure of the present invention, refers to absolute pressure.

Normal boiling point of the present invention refers to vapour of the substance under an atmospheric pressure, liquid equilibrium temperature.

Routine boiling range of the present invention refers to the normal boiling point range of fraction.

Specific gravity of the present invention, unless stated otherwise, refer to normal pressure, fluid density and normal pressure under the conditions of 15.6 DEG C, The ratio of water density under the conditions of 15.6 DEG C.

The composition or concentration or content or yield value of component of the present invention are unless stated otherwise weight basis Value.

Conventional gas hydrocarbon of the present invention refers under normal condition in gaseous hydro carbons, including methane, ethane, third Alkane, butane.

Conventional liq hydrocarbon of the present invention refers to the hydro carbons being in a liquid state under normal condition, including pentane and its boiling point Higher hydro carbons.

Impurity element of the present invention, refer to non-hydrogen in feedstock oil, non-carbon, nonmetallic ingredient for example oxygen, sulphur, nitrogen, Chlorine etc..

Impurity composition of the present invention refers to hydro-conversion object such as water, ammonia, the vulcanization of non-hydrocarbon component in feedstock oil Hydrogen, hydrogen chloride etc..

Light hydrocarbon of the present invention is naphtha component, refers to that normal boiling point is lower than 200 DEG C of conventional liq hydrocarbon.

Diesel component of the present invention refers to that normal boiling point is 200~350 DEG C of hydro carbons.

Wax oil component of the present invention refers to that normal boiling point is 350~530 DEG C of hydro carbons.

Middle matter hydrocarbon of the present invention refers to that normal boiling point is 230~400 DEG C of hydro carbons.

Heavy hydrocarbon of the present invention refers to that normal boiling point is higher than 350 DEG C of hydro carbons.

Polycyclic aromatic hydrocarbon mentioned herein, aromatic ring number >=3.

Hydrogen to oil volume ratio of the present invention refers to the normal of the standard state volume flow of hydrogen and specified oily logistics The ratio of pressure, 20 DEG C of volume flow.

High boiling hydrocarbon component HAC of the present invention refers to that normal boiling point is higher than 450 DEG C of the hydrocarbon component.

The material BRF of the HAC of component containing high boiling hydrocarbon of the present invention is the higher boiling for being higher than 450 DEG C comprising normal boiling point The material of the hydrocarbon component HAC component.

The hydrogenation process BR of the material BRF of the HAC of component containing high boiling hydrocarbon of the present invention, as needed, Ke Nengfa Raw hydrofining reaction or reacted with catalytic hydrocracking or with heat from hydrogenation cracking reaction or with thermal cracking free radical fragment plus The reaction process such as stabilized hydrogen reaction.

Heavy oil of the present invention refers to mainly being higher than by normal boiling point 350 DEG C of hydro carbons, preferably mainly by routine The weight that the heavy hydrocarbon oil that hydro carbons of the boiling point higher than 450 DEG C forms, the preferably mainly hydro carbons by normal boiling point higher than 530 DEG C form Matter hydrocarbon ils is particularly preferably the heavy rich in aromatic structure unit mainly low higher than 530 DEG C of hydrogen content by normal boiling point The inferior heavy oil of hydro carbons composition；For the hydrogenation process especially heat from hydrogenation cracking reaction process of inferior heavy oil, in order to add Fast hydrogen supply speed inhibits thermal condensation reaction, reduces heat of reaction, improves reaction operability, and efficient inferior heavy oil adds hydrogen anti- Process is answered to need using hydrogen supply dissolvent oil.

The hydrofining reaction of the hydrocarbon material, can be plus hydrogen removing impurities qualitative response such as hydrodemetallization reacts, adds hydrogen is de- to have The reaction of machine oxygen plus the reaction of hydrogen removal of organic sulfur plus hydrogen take off organic oxygen reaction plus hydrogen takes off organochlorine reaction plus hydrogen takes off Organic fluoride reaction, Can be unsaturated carbon-carbon bond adds hydrogen saturated reaction such as olefins hydrogenation reaction, alkynes to add hydrogen saturated reaction, aromatic hydrogenation Saturated reaction can be one or more of above-mentioned reaction.The heat from hydrogenation cracking reaction of the hydrocarbon material and thermal cracking free radical The stabilized hydrogenation of fragment reacts, and usually always occurs together, it is generally present in coal or the high-temperature hydrogenation hot tearing with heavy oil Change in reaction process, the hydrogenation process that refines altogether such as direct hydrogenation liquefaction of coal reaction process, kerosene, heavy-oil hydrogenation thermal cracking are anti- Answer process, in heavy-oil hydrogenation reaction process.

Therefore, hydrocarbon material hydrogenation process of the present invention can be the high-temperature hydrogenation reaction process of inferior heavy oil, even In can be extra heavy oil hydrodemetallization reaction process, hydrodesulfurization reaction process, hydrodenitrogeneration reaction process, can be super The front hydrofining reaction section of hydrocracking heavy oil reaction process such as hydrodemetallization conversion zone, hydrodesulfurization reaction section or and Hydrodenitrogeneration conversion zone.

2 of liquid material (including slurries) serial operation or the hydrocarbon material hydrogenation reaction system of multiple conversion zones composition is described below System.

A conversion zone of the present invention, refers to the gas-liquid comprising hydrocarbon material hydrogenation reaction step and the step gas-liquid product The technical process of separating step.

By taking decompression residuum floating bed hydrogenation heat cracking reaction process as an example, it belongs to the high hydrocarbon material depth of hydrogen consumption and adds Hydrogen reaction process, since always main body reaction is rapidly completed in the reaction zone in front to easy reactive component, also because of common process middle front part Always hydrogen purity is high, objectionable impurities gas concentration is minimum for reaction zone, the easy highest reaction zone of reactant concentration, therefore, from adding It is said in hydrogen reaction speed, reaction hydrogen-consuming volume, wait the reaction compartment of liquid reaction volumes, the amounts of hydrogen of front reaction zone consumption is long-range In the amounts of hydrogen of rear portion reaction zone consumption, and usually discharge a large amount of reaction heat；Key simultaneously between impurity element and carbon is strong It spends lower chemical bond and is prone to cleavage reaction, therefore, the foreign gas amount that front reaction zone generates, after being generally also much larger than The foreign gas amount that portion's reaction zone generates, is the main generation area of foreign gas；With the extension of the reaction mechanism mechanism of reaction, solid or with it is high boiling Point the hydrocarbon component is gradually converted into the hydro carbons of low boiling point, mid-boiling point, the average molecular weight of such liquid (including slurries) is smaller and smaller, Mean boiling point is lower and lower.Based on above-mentioned analysis, can usually be divided into the whole hydrogenation process on a macro scale: first adds Hydrogen reaction process, that is, hydrogen consumption is high, foreign gas yield is high, the front reaction process more than liquid material high boiling component, and second adds hydrogen The rear portion reaction process that reaction process, that is, hydrogen consumption is low, foreign gas low output, liquid material high boiling component are few.

Hydrocarbon material hydrogenation process described in detail below.

Hydrocarbon material hydrogenation reaction of the present invention, refer to hydrogen exist and pressurized conditions under, carbon containing, protium liquid Body or with solid such as oil or with coal occur hydrogenation reaction, for its feedstock oil of hydrocarbon oil hydrogenation process occur hydrofinishing or and plus Hydrogen heat cracking reaction generates the hydrocarbon products of at least part more low molecular weight or normal boiling point lower than 450 DEG C, straight for coal hydrogenation Connect its feed coal of liquefaction reaction process occur swollen thermosol, primary pyrolysis, the secondary thermal cracking of intermediate product, free radical stabilized hydrogenation, The reactions such as thermal condensation generate the hydrocarbon products that at least part normal boiling point is lower than 450 DEG C.

Hydrocarbon material hydrogenation process of the present invention, typical example are that high temperature coal-tar floating bed hydrogenation deep refining is anti- It answers process, middle coalite tar floating bed hydrogenation heat cracking reaction process, direct hydrogenation liquefaction of coal reaction process, kerosene to refine altogether to add Hydrogen reaction process, petroleum based heavy fuel oils suspension bed or boiling bed hydrogenation cracking reaction process, usually using hydrogen supply dissolvent oil or dilution Oil.

Hydrocarbon material hydrogenation reaction of the present invention, reaction product BASE-RU-P, at least gas-liquid two-phase logistics are most Situation belongs to gas, liquid, solid three-phase logistics.Hydrogenation reaction effluent RU-P-X of the present invention is for being discharged hydrogenation reaction product BASE-RU-P occurs in the form of 1 tunnel or 2 tunnels or multichannel material, is gas phase or liquid phase or gas-liquid mixed phase or gas-liquid-solid three-phase object Stream.

Hydrocarbon material heat from hydrogenation cracking reaction process of the present invention, including hydrocarbon material heat cracking reaction and thermal cracking free radical The stabilized hydrogenation of fragment reacts, and it is total to be present in direct hydrogenation liquefaction of coal reaction process, heavy-oil hydrogenation heat cracking reaction process, kerosene It processes in the reaction process such as heat from hydrogenation cracking reaction process.

Hydrocarbon material heat from hydrogenation cracking reaction process of the present invention, usually using up flow type expanded bed hydrogenator

Hydrogenation reaction space refers to the process fluid flowing space that the hydrogenation reaction occurs, can be empty in reaction Between such as empty barrel reactor area, air lift hydrogen mixed zone, liquid collection cups upper space region, can be the reactor external space such as Space in pipeline, space in valve, space in mixer, space etc. in pump.

Up flow type hydrogenator of the present invention, reaction compartment or the processing medium in hydrogenation catalyst bed Macroscopic view flowing dominant direction is from top to bottom.

Back-mixing stream expanded bed reaction zone of the present invention, refers to the reaction zone or main reaction region using expanded bed reactor Mode of operation there are liquid stream back-mixings there is circulation fluid in other words；Back-mixing stream or circulation fluid refer to the intermediate production at flow points K At least part liquid phase XK-L in object XK or final product XK as the upstream reaction zone circulating fluid XK-LR return logistics XK, The reaction product of circulating fluid XK-LR flows through K point and is present among XK.The mode of formation back-mixing stream can be any appropriate Mode, as built-in inner ring flow cartridge, built-in outer ring flow cartridge, built-in liquid collecting cup+diversion pipe+circulating pump, outer is arranged in reactor Set formula circulation pipe etc..Under above-mentioned working condition, due to the multiple circulate operation of liquid product or intermediate liquid product, make to bring about the desired sensation Hydrogen supply dissolvent oil in phase product is therefore remaining more with respect to experienced less thermal response for the hydrogen supply dissolvent oil in liquid phase Hydrogen supply capacity, be more suitable for using the present invention.

Liquid product recycle up flow type expanded bed hydrogenator system of the present invention, refers to reacting using expanded bed The reaction zone of device or the mode of operation of main reaction region return to the processing of upstream reaction space cycle there are product liquid and exist in other words Liquid product recycle；Liquid product recycle in hydrogenator refers to intermediate product XK or final product at flow points K At least part liquid phase XK-L in XK as the upstream reaction zone circulating fluid XK-LR return logistics XK, circulating fluid XK-LR's Reaction product flows through K point and is present among XK.The mode for forming Liquid product recycle can be any appropriate mode, still Gas-liquid separation zone must be set in the headspace in reactor, obtain circulation fluid and other products, that is, built-in liquid collecting is set Cup+diversion pipe+circularly-supercharged device, circularly-supercharged device are generally circulated pump, can be arranged in inside reactor or outside.

The liquid collecting cup or liquid trap being arranged in reactor of the present invention, refer to being arranged in reactor for collecting The container of liquid, usual top or upper side opening, bottom or lower side installation diversion pipe are for conveying or being discharged collection Liquid；The top liquid trap of expanded bed reactor is typically mounted on the de- liquid zone of gas-liquid material, obtains the liquid containing a small amount of bubble With gas-liquid mixed phase logistics or obtain liquids and gases, at least partly liquid product returns to reaction compartment after circulating pump pressurizes and follows Ring processing.Typical example is that heavy oil boiling bed hydrogenation reactor, the HTI direct hydrogenation liquefaction of coal that H-OIL technique uses react Device, Shenhua direct hydrogenation liquefaction of coal reactor.

Suspended-bed reactor of the present invention, structure type can be any one suitable form, can be empty cylinder Suspended-bed reactor can be using internal circulation guide shell to form piston flow or the back-mixing stream there are interior circulation to shape At circulation in inside or internal outside circulation, can be makes top reaction compartment liquid flow into lower part using its outer circulating tube reacts empty Between shaper outer circulation stream back-mixing flow pattern, can be and collected using top product separation, liquid and flow guide system is to passing through It recycles compression system and forms the back-mixing flow pattern for forcing inner recirculation flow.

Hot high score device of the present invention, refers to the gas-liquid separation for separating hydrogenation reaction intermediate product or final product Hydrogen air lift function can be set in equipment, reduces the content of the intracorporal low boiling component of liquid after separation.

Second level of the present invention or multistage method of hydrotreating refer to comprising two order of reactions or multiple order of reactions plus hydrogen side Method.

A hydrogenation reaction grade of the present invention refers to adding entering a hydrogenation process since hydrocarbon raw material to it Hydrogen product gas-liquid separation obtains at least one process section until generating the liquid product that oil forms by least part, comprising being somebody's turn to do The gas-liquid separation process of at least part hydrogenation reaction product of the hydrogenation process and this grade of hydrogenation reaction grade.Therefore, one Grade method of hydrotreating refers to that the process of initial hydrocarbon feedstock only includes that a hydrogenation reaction step and the hydrogenation reaction step produce The flow model of object gas-liquid separation process, a hydrogenation reaction step can be used 1 or 2 or more as needed The hydrogenator of platform serial operation, therefore number of reactors and form are not the foundation for determining order of reaction, one or some strings Connection reactor group at reaction step and its product separator common combination could form one complete meaning on hydrogenation reaction Grade.

Secondary hydrogenation method of the present invention refers to that the process of initial hydrocarbon feedstock includes liquid material processing flow For " by the gas-liquid separation process of two different hydrogenation reaction steps and corresponding hydrogenation reaction step products " group of serial operation At flow model, the logistics of wherein at least a part of level-one hydrogenated oil composition enters secondary hydrogenation reaction process.

Three-level method of hydrotreating of the present invention refers to that the process of initial hydrocarbon feedstock includes liquid material processing flow For " by the gas-liquid separation process of three different hydrogenation reaction steps and corresponding hydrogenation reaction step products " group of serial operation At flow model, the logistics of wherein at least a part of level-one hydrogenated oil composition enters secondary hydrogenation reaction process, at least The logistics that a part of secondary hydrogenation generates oil composition enters three-level hydrogenation process.The process knot of the method for hydrotreating of more series Structure is analogized according to mentioned above principle.Multistage method of hydrotreating refers to that the process of initial hydrocarbon feedstock includes liquid material processing flow For the process of serial operation formed " by three or more different hydrogenation processes and hydrogenation products gas-liquid separation process " Mode.

Three-level method of hydrotreating, it is serial operation that the process for referring to initial hydrocarbon feedstock, which includes liquid material processing flow, The process formed " by the gas-liquid separation process by three different hydrogenation reaction steps and corresponding hydrogenation reaction step products " Mode, according to this definition, it is evident that the gas-liquid separation process of the hydrogenation products not at the same level can be carried out independently, can also portion Divide or all joint carries out.

It is of the present invention like secondary hydrogenation method, the method for referring to being similar to secondary hydrogenation method, when rear class upper feeding When liquid phase flow ratio tends to infinity in the back-mixing liquid phase flow and upper feeding of back-mixing stream expanded bed reactor, it is considered as second level and adds Hydrogen methods.

Hydrogenator of the present invention, the basic element of character usually have:

1. reactor shell；

2. the opening (or being adapter tube) in reactor shell；

3. the up flow type being arranged in reactor enclosure body adds hydrogen main reaction space, usually using catalyst when working condition, Usually using charging distributed component for being uniformly distributed charging；

4. being arranged in the feed distributor of bottom in reactor enclosure body；

5. being arranged in the liquid collection cups LD and liquid conduits LK of upper section or middle upper section in reactor enclosure body；

6. reactor intermediate feed distributor (or distributor), the mixer of catalyst bed interlayer, such as cold hydrogen box；

7. rectification part is exported, such as collector, liquid phase discharge vortex-proof device, mixed phase product fairlead.

8. the measuring instrumentss that may be installed: testing the temperature-measuring part such as thermocouple of reaction bed temperature, measure reactor The pressure gauge of system specific location pressure measures liquid level instrument such as glass plate, floating drum, the double flange difference gauges, guided wave of liquid level Radar, ray level-sensing device etc.；

Reactor of the present invention, accessory be external insulation material, supporting element (skirt or trunnion), basis, ladder, Operating platform and fire-fighting accessory that may be present such as steam smothering ring.According to the conditions such as construction ground geology, meteorology, bonding apparatus weight The conditions such as amount, height, up-flow reactor of the present invention need to drive piles to control its basis under its basis as needed Sinking speed.

Up-flow reactor of the present invention, working method can choose:

1. floating bed hydrogenation reactor；

2. boiling bed hydrogenation reactor usually draws off the decreased catalysis of activity from bed bottom in an intermittent fashion Agent fills into fresh catalyst from bed top in an intermittent fashion and maintains bed catalyst reserve；

3. the combined type hydrogenator of suspension bed and ebullated bed

4. slight expanded-bed.

About the hydrogen addition technology of the material containing heavy hydrocarbon, use can be reasonably selected to prior art or is used cooperatively.

Solvent hydrocarbon ADSC described herein refers to hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor, in the up flow type hydrogenation process of heavy oil (hydrogenation modification reaction process, heat from hydrogenation cracking reaction process) serves as hydrogen supply hydrocarbon or hydrogen transmitting hydrocarbon or viscosity reduction degree hydrocarbon or diluent.

Hydrogen supply hydrocarbon described herein refers to that direct hydrogenation liquefaction of coal reaction process, heavy-oil hydrogenation reaction process, kerosene refine altogether In hydrogenation process with hydrogen supply function the hydrocarbon component, hydrogen supply hydrocarbon include the double ring arene of fractional saturation, fractional saturation it is more Cycloaromatics.Hydrogen supply hydrocarbon reduces reaction compartment thermal cracking certainly while discharging reactive hydrogen makes thermal cracking free radical stabilized hydrogenation By the concentration of base, to have the function of inhibiting thermal cracking, the hot tearing rate of heavy hydrocarbon can be reduced, for example, in heavy-oil hydrogenation hot tearing Change the front conversion zone R10A of a large amount of heat cracking reactions of generation of reaction process R10, the sufficient hydrogen supply hydrocarbon of usage quantity has suppression The function of heating condensation coking, has positive influences to production process；And at the rear portion that heat cracking reaction quantity is greatly reduced There is the superfluous hydrogen supply hydrocarbon in part in the hydrogen supply hydrocarbon of equivalent in conversion zone R10B, superfluous hydrogen supply hydrocarbon, which has, to be inhibited heavy hydrocarbon thermal cracking, reduces The negative effect of heavy hydrocarbon hot tearing rate.

Hydrogen supply hydrocarbon precursor described herein refers to that the hydrocarbon component of hydrogen supply agent can be changed into after adding hydrogen or hydrogen supply hydrocarbon loses Conversion product after the hydrogen of part.

Hydrogen described herein transmits hydrocarbon, refers to that direct hydrogenation liquefaction of coal reaction process, heavy-oil hydrogenation reaction process, kerosene are total Refine the hydrocarbon component in hydrogenation process with transmitting hydrogen function, such as polycyclic aromatic hydrocarbon.

Hydrogen supply hydrocarbon (or hydrogen supply the hydrocarbon component) DS is described below, hydrogen supply hydrocarbon precursor DS-BF, hydrogen supply dissolvent SHS, loses hydrogen hydrogen supply Solvent (or hydrogen supply hydrocarbon precursor or hydrogen supply hydrocarbon to be brought back to life) MFS, carry out lose hydrogen hydrogen supply dissolvent MFS or with hydrogen supply hydrocarbon precursor DS- The stabilized hydrogenation reaction process MR of the resurrection process of BF.

Hydrogen supply the hydrocarbon component DS described herein refers to facing (including the heavy-oil hydrogenation hot tearing of hydrogen hot-working reaction process in heavy oil Change reaction process), direct hydrogenation liquefaction of coal reaction process, kerosene refine hydrocarbon group in hydrogenation process with hydrogen supply function altogether Point, hydrogen supply hydrocarbon include the double ring arene of fractional saturation, fractional saturation polycyclic aromatic hydrocarbon (usually with tricyclic structure hydrocarbon, tetracyclic structure Hydrocarbon is advisable).In hydrogen supply hydrocarbon, the hydrogen supply speed of dihydro body is all larger than tetrahydro body, and the two of the dihydro body of thrcylic aromatic hydrocarbon and double ring arene Hydrogen body is compared, and it is low that hydrogen supply speed has height to have；Although test is it has been proved that polycyclic aromatic hydrocarbon has transmitting hydrogen without hydrogen supply capacity Ability.At 400 DEG C, the opposite hydrogen supply speed of following component is as follows:

For the hydrogen supply dissolvent SHS industrially used, usually containing hydrogen supply the hydrocarbon component DS or with hydrogen supply hydrocarbon predecessor The hydrocarbon mixture of object the hydrocarbon component DS-BF, the common source hydrogen supply dissolvent SHS have:

1. the hydrocarbon-fraction that the normal boiling point of coalite tar is 220~480 DEG C；

2. the hydrocarbon-fraction that the normal boiling point of medium temperature coal tar is 220~480 DEG C；

3. the hydrocarbon-fraction that the normal boiling point of high temperature coal-tar is 220~480 DEG C；

4. the hydrocarbon-fraction that the normal boiling point of pulverized coal pyrolysis tar is 220~480 DEG C；

5. 220~480 DEG C of hydrocarbon-fraction of ethylene bottom oil；

6. 220~480 DEG C of hydrocarbon-fraction obtained by petroleum based heavy fuel oils hot procedure, hot procedure is heavy oil catalytic cracking Process or heavy oil catalytic pyrolysis process；

7. 220~480 DEG C of hydrocarbon-fraction obtained by direct hydrogenation liquefaction of coal reaction process；

8. the hydrocarbon-fraction that normal boiling point is 450~570 DEG C；

9. other be rich in hydrogen supply the hydrocarbon component DS or the hydrocarbon mixture with hydrogen supply hydrocarbon precursor the hydrocarbon component DS-BF.

By taking heavy-oil hydrogenation heat cracking reaction process as an example, in hydrocarbon hydrogen heat cracking reaction process, thermal cracking of hydrocarbons from The stabilized hydrogenation process of reactive hydrogen is obtained by base, thermal cracking of hydrocarbons free radical belongs to hydrogen-abstracting agent, while the confession that hydrogen supply capacity is excellent Hydrogen the hydrocarbon component releases active hydrogen atom (referred to as mistake hydrogen) becomes the worse hydro carbons of the higher hydrogen supply capacity of aromatic carbon rate afterwards；Due to supplying Hydrogen hydrocarbon composition is special, and price is higher, outer in order to reduce for needing there are the occasion of a large amount of hydrogen supply hydrocarbon in order to reduce cost For the consumption of hydrogen supply hydrocarbon, it usually needs the hydrogen hydrogen supply hydrocarbon of recycling mistake in a certain way (or hydrogen supply hydrocarbon precursor or hydrogen supply to be brought back to life Hydrocarbon) DS-BF obtains losing hydrogen hydrogen supply dissolvent MFS, and restores the hydrogen supply of mistake hydrogen hydrogen supply dissolvent MFS by stabilized hydrogenation reaction process MR Then ability is recycled；It is obvious that usually lose hydrogen hydrogen supply dissolvent MFS be also hydrocarbon mixture, and would generally by with heavy-oil hydrogenation The same boiling product of process mixes, in this way if the same boiling product of heavy-oil hydrogenation process belongs to hydrogen supply the hydrocarbon component DS or and hydrogen supply Hydrocarbon precursor the hydrocarbon component DS-BF can then can increase hydrogen supply dissolvent quantity, in this way if the same boiling product of heavy-oil hydrogenation process not Belong to hydrogen supply the hydrocarbon component DS or can then reduce the concentration of hydrogen supply hydrocarbon in hydrogen supply dissolvent with hydrogen supply hydrocarbon precursor the hydrocarbon component DS-BF, it is right In there are the stable production systems that hydrogen supply dissolvent recycles, the basicly stable recycle stock of the hydrocarbon component will form.

Since hydrogen supply dissolvent can face in heavy oil, hydrogen hot-working aromatic hydrogenation saturated reaction process, that heavy oil faces hydrogen thermal cracking is anti- It answers process quickly to provide reactive hydrogen, quickly transmit reactive hydrogen and (for example pass out the reactive hydrogen of catalyst surface quickly to improve The utilization rate that catalyst generates active hydrogen efficiency, improves reactive hydrogen), therefore, in the cyclic process of a hydrogen supply dissolvent, if energy The enough work for crossing hydrogen supply the hydrocarbon component DS transmitting more with reasonable flow model (for example passing through more hydrocarbons hydrogenation reaction process) Property hydrogen, then can be improved the service efficiency of reactive hydrogen, to form the effective use method of reactive hydrogen.

Hydrogen supply the hydrocarbon component DS is mainly shown as in the beneficial effect of hydrocarbon hydrogen heat cracking reaction process:

1. under suitable conditions, being converted into the process for losing hydrogen solvent, molecular level is dispersed in entire reaction compartment, Reactive hydrogen is quickly provided to the free radical in liquid phase reactor space, there is hydrogen supply capacity, have the function of hydrogen supply agent, coking inhibitor, This is the distribution consistency degree that the smallest nm-class catalyst of current granularity also cannot achieve；

2. all processes for providing reactive hydrogen to hydro carbons belong to hydrogen migration between hydrocarbon molecule, reaction heat is not generated substantially, is had There is the function of reducing target hydrocarbon ils hydrogenation process reaction heat；

3. thermal cracking of hydrocarbons reaction temperature can be reduced, has the function of dynamics coking inhibitor；

4. can reduce the understanding energy of molecular hydrogen there are molecule inducing function, accelerate the rate of dissociation of molecular hydrogen；

5. quickly transmitting reactive hydrogen (for example quickly passes out the reactive hydrogen of catalyst surface and generates work to improve catalyst Property hydrogen efficiency, improve reactive hydrogen utilization rate)；

6., can be with multiple conversions " hydrogen supply hydrocarbon, hydrogen supply hydrocarbon precursor " under suitable conditions, under hydrogenation catalyst effect State, repeatedly plays the role of reactive hydrogen delivery agent, and the present invention also utilizes this feature.

1. heat cracking reaction can be induced, heat cracking reaction temperature is reduced, thermal condensation reacting dose is reduced, to improve operation Stability extends the operation cycle；

2. the reaction process time can be shortened, thermal condensation reacting dose is reduced, to improve operational stability, extend operation week Phase；

3. reaction overall temperature rise can be reduced；

4. the retention rate of pyrolysis molecule can be improved while reducing thermal condensation object such as coke yield, reducing gas yield, i.e., Light-end products yield is improved, saves to be separated by solid-liquid separation and consume energy；

5. operational stability can be improved, extend the operation cycle, catalyst efficiency is improved；

6. the overall thermal cracking conversion ratio of heavy oil can be improved.

The hydroconversion reaction zone MR described in detail below that target is prepared as with hydrogen supply hydrocarbon.

According to the present invention, the logistics SHS containing hydrogen supply hydrocarbon DS of recycling is from rich in double ring arene and/or polycyclic The hydrogen supply hydrocarbon precursor logistics SHSBF of aromatic hydrocarbons hydrogenation reaction obtained by the hydroconversion reaction zone MR conversion for being prepared as target with hydrogen supply hydrocarbon The logistics of effluent MRP or separating obtained logistics；It is prepared as the hydroconversion reaction zone MR of target with hydrogen supply hydrocarbon, can be suitble to any Under conditions of work.

Stabilized hydrogenation reaction process MR, can using beaded catalyst bed (down-flow fixed bed, it is upflow fixed bed, Up flow type slight expanded-bed) reactive mode, usually temperature is 280~440 DEG C, pressure is 6.0~20.0MPa, hydrogenation catalyst MR-CAT volume space velocity is 0.05~10.0hr^-1, hydrogen/feedstock oil volume ratio be 30: 1~3000: 1 reaction condition under grasp Make.

Stabilized hydrogenation reaction process MR, can be using the moving bed or boiling bed hydrogenation reaction side for using beaded catalyst Formula, usually temperature is 280~440 DEG C, pressure is 6.0~20.0MPa, hydrogenation catalyst MR-CAT volume space velocity be 0.05~ 10.0hr^-1, hydrogen/feedstock oil volume ratio be 100: 1~1200: 1 reaction condition under operate.

Stabilized hydrogenation reaction process MR, it might even be possible to use floating bed hydrogenation reactive mode, usually temperature be 280~ 440 DEG C, pressure be 6.0~20.0MPa, addition hydrogenation catalyst be preferably that the oil-soluble catalyst of high degree of dispersion or water solubility are urged It is operated under the reaction condition that agent, hydrogen/feedstock oil volume ratio are 100: 1~1200: 1.

The aromatic hydrogenation fractional saturation that the hydroconversion reaction zone MR of the present invention for being prepared as target with hydrogen supply hydrocarbon occurs is anti- It answers, refers to existing in hydrogen and suitable hydrogenation catalyst MR-CAT (catalyst with aromatic hydrogenation fractional saturation function) Under the conditions of the reaction process of consumption hydrogen that occurs of the hydrocarbon material SHSBF rich in double ring arene and/or polycyclic aromatic hydrocarbon, minimum reaction Depth should have the industrial significance of bottom line: complete to the hydrocarbon material SHSBF rich in double ring arene and/or polycyclic aromatic hydrocarbon pre- The aromatic hydrogenation fractional saturation of phase, the hydrogenation reaction depth should be according to aromatic component structure in SHSBF and expected aromatic moieties Degree of saturation determines, hydrogen supply hydrocarbon weight in the hydrocarbon-fraction that the normal boiling point in hydrogenation reaction effluent MRP is 250~530 DEG C The higher the better for concentration value SHN expectation, and SHN is the same as often greater than greater than 6 weight %, generally higher than 10 weight %.

The hydroconversion reaction zone MR that target is prepared as with hydrogen supply hydrocarbon, because (tenor, oxygen content contain feedstock property Amount, olefin(e) centent, sulfur content, nitrogen content, arene content, boiling range, specific gravity) difference and hydrogenation reaction (hydrogenation deoxidation plus hydrogen are de- Sulphur, hydrodenitrogeneration, plus hydrogen partial saturation) depth difference, the variation range of operating condition is very wide, should be according to specific process Condition determines.

For beaded catalyst bed (down-flow fixed bed, upflow fixed bed, up flow type slight expanded-bed) reactive mode, The hydroconversion reaction zone MR that target is prepared as with hydrogen supply hydrocarbon, the hydrogenation catalyst MR-CAT used can be it is one or two kinds of or It the tandem compound of a variety of Hydrobon catalysts and loads in mixture, can be the special-purpose catalyst for specific raw material, be also possible to close What the unifining process of suitable petroleum refining heavy diesel fuel type or wax oil type used has hydrodemetallization or hydrogenation deoxidation or adds Hydrogen desulfurization or hydrodenitrogeneration add the Hydrobon catalysts of functions and combinations thereof such as hydrogen saturation.Coal liquefaction crude oil produces coal liquefaction Aromatic hydrogenation fractional saturation reaction process catalyst, the coal tar light fraction deep hydrofinishing catalyst of solvent naphtha be usually It can be used.

The hydroconversion reaction zone MR that target is prepared as with hydrogen supply hydrocarbon, the hydrogenation catalyst MR-CAT used are included at least Hydrocatalyst for saturating arylhydrocarbon includes also usually Hydrodemetalation catalyst, (workflow position is usual for olefins hydrogenation catalyst Before hydrocatalyst for saturating arylhydrocarbon bed).

Any supplement sulphur can be added to the hydroconversion reaction zone MR that target is prepared as with hydrogen supply hydrocarbon as needed, to guarantee Reactive moieties necessary minimum concentration of hydrogen sulfide such as 500PPm (v) or 1000PPm (v), to guarantee the necessary vulcanization of catalyst Hydrogen partial pressure is not less than minimum must value.The supplement sulphur can be sulfide hydrogen or can be converted into hydrogen sulfide to adding hydrogen Material of the conversion process without ill-effect, such as hydrogen sulfide containing gas or oil product, or vulcanization is generated after contacting with high-temperature hydrogen The carbon disulfide of hydrogen or dimethyl disulfide etc..

Hydrogen supply dissolvent is used in the up flow type hydrogenation process of the material containing coal tar pitch, can quickly eliminate free radical, energy Hot cracked product hydrogen content is enough improved, but also therefore heat cracking reaction can be inhibited to reduce thermal cracking conversion ratio；And it is dripped containing coal The raising of the residual oil quality of the up flow type hydrogenation process of green material allows its further heat from hydrogenation cracking (for example to recycle Heat from hydrogenation cracking) to improve overall thermal cracking conversion ratio.Just thermal cracking of the material containing coal tar pitch and the object containing coal tar pitch For the general effect for expecting the thermal cracking again of a thermal cracking tail oil, overall heat from hydrogenation can effectively improve using hydrogen supply dissolvent Cracking conversion rate is effectively reduced and gets rid of the yield containing solid tail oil outside.

For the purpose of the present invention, the main purpose of the up flow type hydrogenation process of the material containing coal tar pitch can be progress The thermal cracking desulfurization of Suitable depth or and hydrodesulfurization, while carrying out a degree of hydrodemetallization reaction, while carrying out one That determines the high boiling hydrocarbon component of degree adds hydrogen aromatic moiety saturated reaction, heat from hydrogenation cracking reaction, heat cracking reaction and thermal cracking The stabilized hydrogenation of free radical reacts, and produces low sulfur content, low-metal content, the more floating bed hydrogenations of needle coke Suitable ingredients Then product is separated into once coal tar pitch after obtain plus hydrogen accordingly, it may be desirable to which floating bed hydrogenation product is fractionated first Hydrofining pitch and primary hydrogenation heavy asphalt, then will once hydrogenate heavy asphalt return floating bed hydrogenation upgrading processes into Row secondary operation, to improve beneficial overall thermal cracking conversion ratio.It is primary with regard to heat from hydrogenation cracking of coal tar pitch and coal tar pitch For the general effect of the cracking of heat from hydrogenation again of heat from hydrogenation cracking tail oil, overall plus hydrogen can effectively improve using hydrogen supply dissolvent Thermal cracking conversion ratio is effectively reduced and gets rid of the yield containing solid tail oil outside, to improve the economy of process.

Middle coalite tar of the present invention refers to producing from pyrolysis of coal or coal generating gas or the coal tar of other processes Product can be the medium temperature of coalite tar or medium temperature process of coking from semicoke process (pyrolysis temperature is lower than 700 DEG C) Coal tar (pyrolysis temperature is between 700~950 DEG C) or their miscella, usually contain coal tar heavy duty oil ingredient.Due to raw coal Property and coking or gas-making process condition change in a certain range, and the property of middle coalite tar also becomes in a certain range Change.The property specific gravity of middle coalite tar of the present invention is usually 0.89~1.15, usual tenor be 5~200PPm, Sulfur content is 0.1%~0.7%, nitrogen content is 0.6%~1.6%.Middle coalite tar of the present invention, inorganic water contains sometimes Amount is 0.2%~5.0%, sometimes organic oxygen content be usually 2.5%~11%, in particular 3.5%~10%, more particularly It is 5%~10%.

High temperature coal-tar of the present invention refers to the high temperature coal-tar of coal high-temperature coking process dust, due to naphthalene component Price is high, and high temperature coal-tar enters before hydrogenation plant, usually recycles naphthalene therein.

The present invention, can combine processing component is suitable for, property is suitable medium temperature coal tar fraction or with medium temperature coal tar coal Pitch, such as the coal tar pitch of medium temperature coal tar that jet coal fluid bed fast pyrolysis process generates, its composition and property and high Composition and the property difference of warm coal tar are smaller.

The hydrocarbon hydro-upgrading reaction process R10 inferior of hydrocarbon inferior is described below.

Up flow type hydro-upgrading the reaction process R10, reaction product BASE- of the R10F of hydrocarbon ils containing coal tar pitch of the present invention R10P, at least gas-liquid two-phase logistics, most cases belong to gas, liquid, solid three-phase logistics.Hydrogenation reaction effluent of the present invention R10P occurs in the form of 1 tunnel or 2 tunnels or multichannel material for hydrogenation reaction product BASE-R10P to be discharged, and is gas phase or liquid phase Or gas-liquid mixed phase or gas-liquid-solid three-phase logistics.

The appropriate catalysts of the up flow type hydro-upgrading reaction process R10 of the R10F of hydrocarbon ils containing coal tar pitch described in detail below Essential attribute.

As previously mentioned, the main purpose of the up flow type hydro-upgrading reaction process R10 of the R10F of hydrocarbon ils containing coal tar pitch, can be Be carry out Suitable depth thermal cracking desulfurization or and hydrodesulfurization, while carrying out a degree of hydrodemetallization reaction, simultaneously Carry out a degree of high boiling hydrocarbon component plus hydrogen aromatic moiety saturated reaction, heat from hydrogenation cracking reaction, heat cracking reaction and The stabilized hydrogenation of thermal cracking free radical reacts, and produces low sulfur content, low-metal content, needle coke Suitable ingredients and more suspends Therefore bed hydroprocessing product proposes catalyst claimed below naturally:

1. using high activated catalyst, reduce using proportion；To reduce the carrying amount in refined bitumen；

2. high degree of dispersion, i.e. granularity are small, the external surface area of Unit Weight catalyst is improved, is reduced using proportion；To drop Carrying amount in low refined bitumen；

3. catalyst surface coking yield is low, try not to be deposited in coke；

4. catalyst specific gravity and coal tar pitch specific gravity difference, will be enough to ensure that sedimentation separation；

5. promoting the function of heat cracking reaction small as far as possible.

Heavy hydrocarbon CRF up flow type heat from hydrogenation cracking reaction process CR, heavy hydrocarbon CRF inferior inferior of the invention described in detail below It can be coal tar pitch component heat from hydrogenation crackate decompression residuum THC-VR.

Heavy hydrocarbon CRF up flow type heat from hydrogenation cracking reaction process CR inferior generally comprises the hot tearing for generating thermal cracking free radical Change reaction, the stabilized hydrogenation reaction of thermal cracking free radical, generally also comprising hydrofining reaction as added hydrogen saturated reaction or aromatic hydrocarbons Partial hydrogenation saturated reaction.

Heavy hydrocarbon CRF up flow type hydrogenation modification reaction process CR inferior of the invention described in detail below, hydrogenation modification reaction It is meant that, in overall hydrogenation reaction, the partial hydrogenation saturated reaction of aromatic hydrocarbons is desired leading reaction.

Poor quality heavy hydrocarbon CRF of the present invention, usually heavy hydrocarbon inferior, common to be meant that: not use hydrogen supply dissolvent item Under part, in other operating conditions (reaction pressure, reaction temperature, catalyst composition and additive amount and amount, residence time, hydrogen Oil volume ratio, way of operation) under the same conditions, coking of the heavy hydrocarbon CRF inferior during heat from hydrogenation cracking reaction Tendency, coking tendency of the fraction more identical than boiling range in the R10F of hydrocarbon ils containing coal tar pitch during heat from hydrogenation cracking reaction are tighter Weight, i.e., coking yield is higher or lower with heat from hydrogenation cracking conversion rate；In general, the normal boiling point in heavy hydrocarbon CRF inferior is higher than 530 DEG C The carbon residue of hydro carbons is higher than the carbon residue that the normal boiling point in the R10F of hydrocarbon ils containing coal tar pitch is higher than 530 DEG C of hydro carbons.

The up flow type hydrogenation modification reaction process CR of poor quality heavy hydrocarbon CRF of the present invention, main target are, with routine Heat from hydrogenation cracking reaction process is compared, and under catalyst and hydrogen supply dissolvent existence condition that may be present, sends out heavy hydrocarbon CRF inferior Raw more plus hydrogen saturated reaction and the reaction of sufficient thermal cracking free radical stabilized hydrogenation, are effectively reduced the residual of heavy hydrocarbon CRF inferior Charcoal value makes hydro carbons of the normal boiling point therein higher than 530 DEG C become the heat from hydrogenation cracking reaction process of appropriate heat from hydrogenation cracking severity Raw material.

In group technology of the invention, the up flow type hydrogenation modification reaction process CR of poor quality heavy hydrocarbon CRF of the present invention The first reaction task be carry out heavy hydrocarbon inferior removal of ccr by hydrotreating reaction i.e. heavy arene or colloid, asphalitine plus hydrogen be saturated Reaction, certainly, while can occur hydrofining reaction (including demetalization plus hydrogen hydrogenolysis, olefins hydrogenation reaction plus Hydrogen removing impurities matter (oxygen, sulphur, nitrogen) reaction plus hydrogen aromatic hydrocarbons are satisfied or are reacted with fractional saturation reaction, removal of ccr by hydrotreating) or and be hydrocracked Reaction.The typical feedstock of the up flow type hydrogenation modification reaction process CR of heavy hydrocarbon CRF inferior is exactly the upper of the R10F of hydrocarbon ils containing coal tar pitch Product residual oil in streaming hydro-upgrading reaction process R10, in general, it is enriched in the tower of vacuum fractionation tower in product fractionation process In bottom ash oil, this residual oil THC-VR usually contains catalyst conversion product such as molybdenum sulfide of addition etc., from hydrocarbon ils containing coal tar pitch The R10 product metal sulfide of R10FL, the coke that may be accumulated.

When heavy hydrocarbon CRF inferior includes the up flow type hydro-upgrading reaction process R10 product from the R10F of hydrocarbon ils containing coal tar pitch When normal boiling point in R10P is higher than 530 DEG C of hydro carbons R10-VR, the carbon residue content of part heavy oil R10-VR is usually above original Expect the carbon residue content of the identical fraction of boiling range in R10F, in other words the liquid phase in hydrocarbon material up flow type hydro-upgrading reaction process R10 Be adapted as the colloid of the heat from hydrogenation cracking reaction process of heavy hydrocarbon CRF inferior, asphalitine, liquid phase coke dispersion solution, because This, the present invention, which introduces the heavy hydrocarbon in the up flow type hydrogenation modification reaction process CR reaction product of heavy hydrocarbon CRF inferior, contains coal tar pitch The second half section of the up flow type hydro-upgrading reaction process R10 of hydrocarbon ils R10F carries out appropriate heat from hydrogenation cracking reaction, can same time control The thermal cracking depth of hydro carbons poor quality heavy hydrocarbon CRF processed, prevents excessively high hot tearing rate from leading to the yield of thermal condensation object such as asphalitine Lead to the generation of second liquid phase (pitch phase) more than limitation.

In the up flow type hydrogenation modification reaction process CR of heavy hydrocarbon CRF inferior, when reactive hydrogen is supplied not in time, glue Matter, asphalitine thermal cracking free radical will occur condensation reaction, production molecular weight bigger molecule or structure group, repeatedly The final result of dehydrogenation and condensation reaction is to generate coke, and certainly, this is the negative reaction for needing inhibition or reduction.

The reactor types of the up flow type hydrogenation modification reaction process CR of poor quality heavy hydrocarbon CRF of the present invention, can be and appoint It anticipates suitable form, can be one or more of combination cot reactor of suspended-bed reactor, ebullated bed and suspension bed Combination.

The up flow type hydrogenation modification reaction process CR of poor quality heavy hydrocarbon CRF of the present invention, the reactor used can be 1 Or 2 or more, reactor working method can be any suitable form, usually up flow type expanded bed reactor or carrying liqs The up flow type expanded bed reactor of product circulation, the W-response area of separate unit up flow type expanded bed reactor can artificially be drawn It is divided into 2 or multiple reaction zones.The control mode of the inlet temperature of any reaction zone of up flow type expanded bed reactor of the present invention, Can be adjust hydrogen temperature or and flow, can be adjust oil product temperature or and flow.

The up flow type hydrogenation modification reaction process CR of heavy hydrocarbon CRF inferior, the reactor used, liquid phase in reaction compartment, The volume ratio of gas phase (or vapour phase), can be with liquid phase be it is main the case where, define reaction compartment in " liquid phase actual volume/ (liquid phase actual volume+gas phase actual volume) " is reaction compartment liquid phase fraction KL, and a point rate KL is typically larger than 0.5, is generally higher than 0.65, it is even greater than 0.80, actual reinforcing liquid-phase hydrogenatin mode is formed, in order to keep reaction compartment hydrogen partial pressure enough It is high, it may be necessary to the different height of reactor position 2 times or repeatedly add hydrogen.

It, can be former by a part of liquid in order to adjust reaction feed property, or in order to control reaction process property of liquid phase Expect that R10F introduces the up flow type hydrogenation modification reaction process CR of heavy hydrocarbon CRF inferior.

The R10F of hydrocarbon ils containing coal tar pitch of the present invention, refers to the hydrocarbon ils material containing coal tar pitch HDS；The coal tar pitch 370 DEG C of the usual > of the normal boiling point of its hydro carbons of HDS, 400 DEG C of general >, particularly 450 DEG C of >, and contain normal boiling point > 530 DEG C of the hydrocarbon component such as colloid, asphalitine, possible solid particle.

The up flow type hydro-upgrading reaction process R10 of the R10F of hydrocarbon ils containing coal tar pitch of the present invention, refers to that up flow type is swollen Swollen bed hydroprocessing heat cracking reaction process, such as floating bed hydrogenation heat cracking reaction process, suspension bed and ebullated bed combined type heat from hydrogenation Cracking reaction process etc..

The up flow type expanded bed heat from hydrogenation cracking reaction process R10 of the R10F of hydrocarbon ils containing coal tar pitch of the present invention occurs extremely The hydrodesulfurization reaction of few part of coal asphalt component HDS, heat from hydrogenation cracking reaction, the reaction of thermal cracking free radical stabilized hydrogenation, Generate that at least part sulfur content is lower, the lower hydrocarbon product of boiling point；The up flow type hydro-upgrading of the R10F of hydrocarbon ils containing coal tar pitch Reaction process R10 can usually need to realize that one way reacts whole lightings, and usually its rationally high conversion per pass is usual It is 15%~55%, there are a certain number of unconverted coal tar pitch components such as 45% in such hydro-upgrading reaction product R10P ~85% unconverted coal tar pitch component, and form heat from hydrogenation crackate residual oil THC-VR.

If big in heat from hydrogenation crackate residual oil THC-VR inherently coal tar pitch component from the point of view of component structure The residue or conversion product of the non-lighting of molecule or the concentrate of thermal condensation object macromolecular are dripped with its heat from hydrogenation cracking precursor coal Green component HDS compared with boiling fraction, in general, gum level therein, asphalt content, carbon residue content should not be increased significantly For example elevation amplitude is limited in 5%~20% or less；In fact, it would be desirable to heat from hydrogenation crackate residual oil THC-VR inherently coal The residue or conversion product of the non-lighting of macromolecular or the concentrate of thermal condensation object macromolecular, split with its heat from hydrogenation in asphalt component Change precursor coal tar pitch component HDS compared with boiling fraction, in general, gum level therein, asphalt content, carbon residue content It decreases, for example reduces at least 10%~25%.According to experimental study, such result limits coal tar pitch component HDS's Heat from hydrogenation cracking conversion rate is usually 5%~55%, generally 15%~45%, preferably 20%~35%.

In order to improve the comprehensive process efficiency of device, heat from hydrogenation cracking reaction process R10 preferably optimizes hydrocarbon ils containing coal tar pitch The conversion per pass of coal tar pitch component HDS in R10F；And the one way of the coal tar pitch component HDS in the R10F of hydrocarbon ils containing coal tar pitch turns The excessive raising of rate, necessarily increases the thermal condensation reaction of the supramolecular in coal tar pitch component HDS, while increasing thermal condensation object Colloid, asphalitine, liquid phase coke quantity, while increasing gas yield, while increasing adding for hydro carbons of the normal boiling point lower than 370 DEG C Hydrogen saturation depth makes the low aromaticity hydro carbons low to coal tar pitch dissolution dispersibility and extraction, which occurs, drips coal Blueness concentration, this " increase of colloid, asphalitine, the quantity of liquid phase coke " with " colloid, asphalitine, liquid phase coke are suitable for molten The reduction of agent oil quantity " develops to over-saturation degree or critical degree of saturation, will lead to colloid, asphalitine, liquid phase coke from steady It is second liquid phase that being precipitated in fixed colloidal solution system, which becomes over-saturation pitch mutually, leads to quick coking in the containers such as reactor, Device is forced to be stopped work.

In fact, the present invention can be using high-output qulified needle-shape coke raw material oil as target, at this point, the R10F of hydrocarbon ils containing coal tar pitch In conversion per pass excessively high of coal tar pitch component HDS will increase light fraction oil yield, reduce target asphalt component quantity.

In fact, the present invention program can be using high-output qulified needle-shape coke raw material oil as target, and therefore, hydrocarbon containing coal tar pitch Under conversion per pass the same terms of coal tar pitch component HDS in oily R10F, it is also desirable in desulfurization degree, the identical item of hot tearing rate Under part, add hydrogen amplitude more lower better, on the one hand can reduce hydrogen consumption cost in this way, on the other hand can also reduce the production in later period The dehydrogenation task of the delayed coking heat cracking reaction process of needle coke, therefore, typically, up flow type expanded bed heat from hydrogenation cracking The higher the better for the selectivity of the desulphurization reaction of reaction process R10, and desulphurization reaction catalyst highly selective in this way is just at important Optimize the condition of operation.Present invention preferably uses catalyst with base of molybdenum, especially nanoscale catalyst with base of molybdenum.

Diluent KWS of the present invention refers to make totally instead into up flow type hydro-upgrading reaction process R10 Liquid phase is answered to reduce viscosity or reduce pitch concentration or improve hydrogen supply capacity (inhibiting coking) or reduce the hydro carbons of reaction temperature rising, and The introducing of best diluent KWS does not bring adverse effect to needle-shape coke raw material fraction or does not have an impact, therefore, diluent KWS Preferably normal boiling point is lower than 320 DEG C and is rendered as the hydrocarbon of liquid as far as possible in up flow type hydro-upgrading reaction process R10 Class, that is to say, that diluent KWS is preferably the hydro carbons that normal boiling point is 250~320 DEG C.

Diluent KWS of the present invention, can be outer for logistics, can be separation up flow type hydro-upgrading reaction process The hydro carbons that the suitable hydro carbons of boiling range such as normal boiling point is 250~320 DEG C obtained by R10 reaction product R10P, can be rich in confession The hydro carbons of hydrogen hydrocarbon.

The coal that the up flow type hydro-upgrading reaction process R10 of the R10F of hydrocarbon ils containing coal tar pitch of the invention can be carried out is described below Pitch hydrogenation reaction.

At least part occurs for the up flow type hydro-upgrading reaction process R10 of the R10F of hydrocarbon ils containing coal tar pitch of the present invention Desulphurization reaction or hydrodesulfurization reaction, heat cracking reaction, the thermal cracking free radical stabilized hydrogenation of the R10FL of hydrocarbon ils containing coal tar pitch is anti- It answers, generates the lower hydrocarbon product of at least part sulfur content, the lower hydrocarbon product of boiling point；The R10F's of hydrocarbon ils containing coal tar pitch is upper Streaming hydro-upgrading reaction process R10 generally can not also be not intended to realize that one way reacts whole lightings, i.e., usually there are one Its reasonable high thermal cracking conversion per pass, there are a certain number of unconverted coals to drip in such hydro-upgrading reaction product R10P It is green；Unconverted coal tar pitch is partially separated in pitch purification to be used as refined bitumen (light asphalt) and heavy asphalt, heavy asphalt Tail oil；And in order to reduce outlet tail oil quantity, it may be necessary to which the heat from hydrogenation cracking reaction process that tail oil is arranged has produced low boiling point Product, and in order to simplify overall procedure, reduce investment and energy consumption, the heat from hydrogenation cracking reaction process of tail oil can be dripped with containing coal The up flow type hydro-upgrading reaction process R10 of green hydrocarbon ils R10F forms group technology, i.e., all merges or part merging carries out.

Although the up flow type hydro-upgrading reaction process R10 of the R10F of hydrocarbon ils containing coal tar pitch is with the desulphurization reaction of macromolecule hydrocarbon Or the reaction of hydrodesulfurization reaction, heat cracking reaction, thermal cracking free radical stabilized hydrogenation is goal response, but due to containing coal tar pitch The hydrogenation catalyst itself that the up flow type hydro-upgrading reaction process R10 of hydrocarbon ils R10F is usually used has the function of hydrofinishing, And existing reactive hydrogen also can induce hydrocarbon molecule and hydrofining reaction occur, therefore, at the upstream of the R10F of hydrocarbon ils containing coal tar pitch In formula hydro-upgrading reaction process R10, some hydrofining reactions also necessarily occur, and (hydrodemetallization reaction, hydrogenation deoxidation are anti- It answers, hydrodenitrogeneration reaction plus hydrogen aromatic moiety saturated reaction, olefins hydrogenation are reacted).

In the up flow type hydro-upgrading reaction process R10 of the R10F of hydrocarbon ils containing coal tar pitch, when reactive hydrogen is supplied not in time Wait, colloid, asphalitine thermal cracking free radical will occur condensation reaction, production molecular weight bigger molecule or structure group, Repeatedly the final result of dehydrogenation and condensation reaction is to generate coke, and certainly, this is the negative reaction for needing inhibition or reduction.

Main application of the invention is the up flow type hydro-upgrading reaction process R10 of the R10F of hydrocarbon ils containing coal tar pitch, is made Reactor can be 1 or 2 or more, and usually used reactor is 2~4；The R10F's of hydrocarbon ils containing coal tar pitch is upper The reactor working method of streaming hydro-upgrading reaction process R10 can be any suitable form, usually up flow type expanded bed The up flow type expanded bed reactor of reactor or carrying liqs product circulation, the W-response of separate unit up flow type expanded bed reactor Area can be artificially divided into 2 or multiple reaction zones.The entrance of any reaction zone of up flow type expanded bed reactor of the present invention The control mode of temperature, can be adjust hydrogen temperature or and flow, can be adjust oil product temperature or and flow, certainly Also heat exchanger brief introduction heat exchange cooling can be used.

The up flow type hydro-upgrading reaction process R10 of the R10F of hydrocarbon ils containing coal tar pitch, the reactor used, in reaction compartment The volume ratio of liquid phase, gas phase (or vapour phase) can be with liquid phase the case where being main, define in reaction compartment " liquid phase is practical Volume/(liquid phase actual volume+gas phase actual volume) " is reaction compartment liquid phase fraction KL, and a point rate KL is typically larger than 0.45, is general Greater than 0.55, even greater than 0.70, actual reinforcing liquid-phase hydrogenatin mode is formed, in order to keep reaction compartment hydrogen partial pressure sufficient Enough height, it may be necessary to the different height of reactor position 2 times or repeatedly add hydrogen.

When the second half reaction process R10B joint of the up flow type hydro-upgrading reaction process R10 of the R10F of hydrocarbon ils containing coal tar pitch When processing the heavy oil component CRPVR in the reaction product CRP of the up flow type hydrogenation modification reaction process CR of heavy hydrocarbon CRF inferior, after The residence time of half way reaction process R10B usually meets the requirement of the heat from hydrogenation cracking rate of control heavy oil component CRPVR first, Usually the heat from hydrogenation cracking rate upper limit of setting heavy oil component CRPVR is to prevent conversion per pass excessively high.

The reactor types of the up flow type hydro-upgrading reaction process R10 of the R10F of hydrocarbon ils containing coal tar pitch of the present invention, can To be any appropriate form, there are many known forms, such as upflow fixed bed reactor, up flow type slight expanded-bed to react Device, up flow type moving-burden bed reactor, up flow type replace bed reactor, fluidized bed reactor, suspended-bed reactor, ebullated bed online With the combination cot reactor of suspension bed and its combination of particular form, and it is most of have industrial application case, form more Fixed technical characterstic.

Gluey pitch shape component contained by petroleum base residual oil is usually to analyze data with dispersed phase existing for supramolecular structure Show that gluey pitch shape group dispersed phase therein is that molecular weight is up to thousands of to tens of thousands of or even hundreds of thousands rock-steady structure group, when These right groups contain a large amount of condensed-nuclei aromatics units and containing elements, the main tasks of lighting process such as metal, sulphur, nitrogen These macromoleculars are disassociated plus hydrogen saturation, cracking are ten times few compared with its original object charcoal number, hundred times even thousand times small molecules, very Obviously, the thermal cracking task of process is occupied an leading position, this can not rely solely on hydrodemetallization, hydrodesulfurization, hydrodenitrogeneration, Add hydrogen aromatic hydrocarbons saturation to realize, hydrodemetallization, hydrodesulfurization, hydrodenitrogeneration plus hydrogen aromatic hydrocarbons saturation of petroleum base residual oil etc. are pre- Hydrogenation process is substantially the unifining process for being subsequent hydrocracking reaction preparation feedstock oil, otherwise conventional downflow system Hydrocracking catalyst activated centre in fixed bed reactors by rapid Cover is caused to operate because of metal deposit and quick coking Period is too short, is unable to maintain that the minimum economic cycle of operation of course of industrialization requirement；Even with conventional downflow system The processes such as hydrodemetallization, hydrodesulfurization, hydrodenitrogeneration in fixed bed reactors plus hydrogen aromatic hydrocarbons are full, are also unable to reach higher Conversion ratio because being difficult the rapid, high volume coking problem for overcoming high temperature thermal cracking process to necessarily lead to, this is the heating power of process Learn what property was determined；In order to overcome the defect of above-mentioned fixed bed reactor system, up flow type, which occur, in reactor types to be fixed Bed, up flow type slight expanded-bed, up flow type replace the strong expanded bed of bed, up flow type i.e. ebullated bed, up flow type limiting equation expanded bed online I.e. suspension bed boiling, downflow system replace the diversified forms such as bed online.

In the hydrocracking process of petroleum base residual oil, it is normal boiling point less than 530 that normal boiling point, which is greater than 530 DEG C of fraction crackings, The conversion ratio of DEG C fraction is usually 40%~80% even higher, in order to reach so high cracking rate and improve reaction speed, Hot conditions necessary to the inevitable stronger thermal cracking of usage degree, the quick coking of catalyst active center is inevitable , in order to by reactor bed because metal deposit, coking remove the catalyst of active rapid decrease and replacement, technology people Member develops the biggish up flow type expanded bed reactor of both catalyst bed expansion ratios of ebullated bed, suspension bed, and will be subsequent High pressure hot separator and reactor merge into a unit equipment, by high viscosity, easily foaming, easily the residual oil that solidifies equipment it Between movement system (between reactor and hot high score) greatly simplify, reliability, safety, the thermal insulation of system can be improved, The uniformity for improving temperature of charge in reactor, saves occupied area；It is said in terms of advantageous, the cracking of residual oil boiling bed hydrogenation, The high conversion of floating bed hydrocracking is that fixed bed reactors are unable to reach, by the cracking reaction of heat absorption and exothermic plus hydrogen Reaction mixing carries out utilization conducive to reaction heat, is conducive to reduce reaction temperature rising, be recycled a large amount of hot reaction generation it is oily or Intermediate reaction generation oil, which directly heats feedstock oil, can reduce fuel oil preheating temperature；It is said in terms of unfavorable, catalyst bed is swollen It is swollen bigger, compared with fixed bed reactors, the complexity of system is increased, the stationarity of operation is reduced, increases considerably Construction investment；Because increasing the abrasion and collision of catalyst, the loss of reason other than the coking of catalyst is increased；Because of bed For layer there are the violent back-mixing of catalyst and liquid phase, the product quality containing the low conversion degree product of part fresh feed is necessarily poor.

Residual oil boiling bed hydrogenation cracking industrialization technology has H-OIL technique, LC-FINING technique, in order to optimize and stablize The fluidized state for controlling catalyst, is provided with recycle oil circulating pump system, the collector of recycle oil is placed in catalyst in reactor On bed, be equivalent to one for circulating pump provide the high-temperature high-pressure separator that must be placed in high elevation location of recycle oil with Fluidized bed reactor group, which merges, simplifies the structure of high-temperature high-pressure separator, but in order to not influence the fluidized state of ebullated bed, Position, size and the form of the collector of recycle oil all must be carefully designed；Usually by the collector arrangements of recycle oil In the underface of reactor upper spherical end socket, the collector catheter of recycle oil is mounted in reactor, the catheter There is certain rectified action to the gas, liquid, solid Multiphase Flow of suspension bed or ebullated bed bed, solve the heat preservation companion of catheter Heat problem, the stabilization of equipment performance bring adverse effect for weakening or eliminating the flowing of water conservancy diversion tube fluid to reactor；Residual oil boiling Rise bed hydroprocessing reaction system, it is necessary to catalyst interval discharge system, catalyst interval charging system are set, because system complex, Invest big, trivial operations；Residual oil boiling bed hydrogenation reaction system has another disadvantage that portion of product belongs to height plus hydrogen saturation Hydro carbons, therefore product liquid phase dissolved residue colloid, the ability of asphalitine are poor, and therefore, conversion ratio is lower, tail oil yield compared with Greatly, this limits the economy of the technique to a certain extent；Residual oil boiling bed hydrogenation reaction system has another disadvantage that not The poor-quality heavy residuum that carbon residue content is excessively high, tenor is excessively high can be handled, because tenor is excessively high so that catalyst for demetalation Consumption cause catalyst cost too big greatly very much, the excessively high conversion ratio for making reaction process of carbon residue content is too low or quick coking Cause quickly to stop work, which has limited the application ranges of the technique.

Up flow type boiling bed hydrogenation technology, be characterized in that makes to urge with the uplink flowing of reaction mass (mainly liquid phase) Agent bed generates violent expansion, and expansion rate is typically in the range of 25%~45%, to lose part fixed bed hydrogenation catalyst " high activity, high interception rate, material hydro-conversion depth are uniform " the advantages of be cost, formed " destroy catalyst agglomeration energy Power " and " the wide area channel of little particle impurity being freely discharged ", so as to process, tenor is higher, residual carbon content is higher Heavy oil, product quality have declined too much compared with bed technology, but its quality is preferably far beyond suspension bed；Due to ebullated bed Expansion power is mainly derived from the carrying of liquid phase material, and process should not usually prevent the liquid of reactor using a large amount of hydrogen Phase volume efficiency is too low, and therefore, the exothermic effect for also limiting reaction process cannot be excessively high, and usual boiling bed hydrogenation technology is more It is suitable for processing paraffinic base or paraffin intermediate crude base weight oil, the caloric receptivity and free radical of heat scission reaction adds the thermal discharge of hydrogen Macroscopical fuel factor after counteracting is smaller, and reactor overall temperature rise is lower, and the Unit Weight hydrogen of feedstock oil consumption is usually 1.4%~ 2.3%.But even so, the deactivation rate of catalyst is still too high, for this purpose, passing through low old of regular discharge part activity Then catalyst fills into amount of activated high raw catelyst to maintain the average activity of catalyst, therefore form expensive height The consuming cost of active hydrofining catalyst, in fact, less economic when processing petroleum base poor residuum.Meanwhile thermal response Feature hydrogenation tail oil poor quality when leading to high conversion, vaporize raw material, therefore, boiling bed hydrogenation after fuel oil can only be made Raw material lighting conversion ratio is usually 60%~75%, i.e. conversion ratio is low.Since the graininess that boiling bed hydrogenation technology uses is urged Agent is same as conventional fixed bed graininess (preferably spherical) Hydrobon catalyst substantially, still fall within rich in a large amount of inner ducts, The high activity of high internal surface area, pellet type catalyst are unable to satisfy diffusion and the hydro-conversion of poor residuum macromolecular, conventional to boil The heavy end or the hole is made to the formation aperture blocking of catalyst duct that point is huge higher than 530 DEG C of molecular dimension, polarity is strong Road loses activity or Long-Term Sorption is in inner wall activated centre generation shadowing effect, under conditions of lacking reactive hydrogen, because being difficult to Add hydrogen to be difficult to solve adsorption desorption admittedly, thermal condensation leading reaction occurs, is formed in the road of duct and blocked.Too fast catalyst inactivation speed, Form unaffordable hydrogenation catalyst consuming cost, and more importantly the aromatic hydrocarbons saturation hydrogen consumption of flood tide released it is huge Quantitative response heat makes boiling bed hydrogenation technology not have safety, the quick coking of the gum asphalt of high-temperature induction, also anti- It answers the bottom distribution plate of device, center liquid circulation pipe to form a large amount of cokings, device is forced quickly to be stopped work.If selecting up flow type boiling Rise the poor residuum that bed hydroprocessing technology processing tenor is high, carbon residue content is high, result is necessarily largely given birth in reactor device It is burnt, the cycle of operation is too short, reaction temperature is unable to control that i.e. dangerous, catalyst inactivation cost is odd high, these effects have been examination The Industrial Operation of the inferior heavy oil boiling bed hydrogenation device of production is confirmed.

The development of residue slurry-bed hydrocracking technology is the direct hydrogenation liquefaction of coal technology hair based on the 1940s What exhibition was got up, it is under conditions of facing hydrogen and fully dispersed catalyst or coexisting with additive, and leading reaction makes in height The process of warm elevated pressure raw thermal cracking residue reaction and the reaction of thermal cracking free radical stabilized hydrogenation.Floating bed hydrocracking is anti- Answer process, the catalyst of dispersion used or and additive, be fine grain powder, be suspended in reactant, can be effectively suppressed Coke generates.Hydrogenation of residual oil suspended bed technology to the content of impurities of raw material almost without limitation, can be with formed asphalt and oil Sand.

Typically there is the residue slurry-bed hydrocracking technology of industrialization operating achievement, there is Canadian CANMET residual oil to suspend Bed hydroprocessing thermocracking process, Italian eni company EST hydrogenation of residual oil suspended bed thermocracking process.It is other it is dreg-oil suspension bed plus Hydrogen cracking technology has the BPVCC technology path of British Petroleum Company, there is BPVCC technology, the state, Venezuela of British Petroleum Company HDHPLUS technology, the Uniflex technology of Uop Inc., the U.S., the VRSH technology of U.S. Chevron of family oil company (PDVSA) Etc..

The shortcomings that in order to overcome beaded catalyst hydrogen addition technology, floating bed hydrogenation technology has casted off once and for all " is urged using particle The flood tide inner surface of agent is as hydrogenation reaction place " mode, be characterized in that " using high degree of dispersion particle catalyst Outer surface is as hydrogenation reaction place ", so that the diffusion path for completely eliminating gum asphalt arrival hydrogenation reaction place is asked Topic, can handle that tenor is higher, the higher inferior heavy oil of carbon residue content, and certainly, tenor is high, carbon residue content The most handy coking process of high inferior heavy oil such as delay coking process is handled；The reaction compartment of floating bed hydrogenation reactor, Bed expansion rate has reached maximum, and solid catalyst additional amount is usually less than 10% (with feedstock oil poidometer), forms " having the advantages that coking material bearer capabilities " and " the discharge clear passage of suspended particulate impurity ".However in fact, suspension bed adds Hydrogen reactor do not have bed concept, reaction compartment thoroughly lose fixed bed hydrogenation catalyst " high activity, high interception rate, Material hydro-conversion depth is uniform " the advantages of, then the double characteristic of " backmixing of liquid phase " with height and " liquid phase short circuit ", because This, product quality had declined compared with bed technology it is extremely more, so floating bed hydrogenation technology can only be used as poor oil pre- place Reason process, and high quality of products can not be produced.

The reaction efficiency of the catalyst surface of floating bed hydrogenation reactor depends strongly on the renewal frequency of catalyst surface The stable replacement rate with reaction compartment, therefore, the more new tool and catalyst replacement means of catalyst surface are one important The reactor of the technological means for the raising catalyst efficiency that can not be lacked, the heavy oil floating bed hydrogenation device of some industrialization at present is adopted Circulating pump is not provided with bubbling bed, this is a huge technological deficiency, as a result, interior back-mixing amount of liquid phase is uncontrollable, interior When back-mixing catalytic amount (catalyst deposit amount) is uncontrollable, catalyst appropriate particle size range is too narrow and uncontrollable, liquid phase stops Between it is uncontrollable, and its uncontrollability is stronger with the expansion of reactor diameter, these effects have been the poor quality of test manufacture The Industrial Operation of heavy oil floating bed hydrogenation device is confirmed.The suspension bed that the present invention is recommended to use carrying liqs product circulation is anti- Device is answered, to realize the stable replacement rate of the renewal frequency and reaction compartment of expected catalyst surface.

The reaction efficiency of the catalyst surface of floating bed hydrogenation reactor, also by the polar impurity in gas phase in reactor The influence that occupies of absorption, coal tar hydrogenating process, tar and coal refine process altogether and generate a large amount of polar impurity such as H₂O、NH₃、 CO、CO₂Catalyst surface can be strongly adsorbed in and form shadowing effect, therefore international well-known oil product technology suppliers CHEVRON Company is arranged the scheme of the timely impurity removal gas of gas-liquid separator and in subsequent floating bed hydrogenation between proposing in the reactor The lower part of reactor introduces high-purity hydrogen, but big independent gas-liquid separator investment, Liquid level difficulty, operation danger is arranged It is dangerous big；For this purpose, this project recommends that " gas short route " technology can be used, it, will under conditions of not increasing gas-liquid separator The space that gas-liquid mixed phase material containing gas introduces at the top of suspended-bed reactor carries out gas-liquid separation, and gas phase is expelled directly out, and liquid The major part of phase enters liquid phase reactor space by circulation pipe, in the lower part of subsequent floating bed hydrogenation reactor, introduces high-purity Hydrogen gas stream forms the gaseous environment of extremely low impurity, has been formed simultaneously the highly concentrated condition of hydrogen volume, to give full play to catalysis Agent activity creates condition, and is conducive to reduce device stagnation pressure, improves conversion per pass, reduce thermal cracking gas making reaction, reduce pyrocondensation Close reaction；The scheme of above-mentioned timely impurity removal gas also has and low boiling hydrocarbon component is discharged in time, reduces its thermal cracking rate Advantage is conducive to improve liquid receipts, reduces hydrogen consumption.

The typical heavy oil lighting reaction that the floating bed hydrogenation inside reactor of inferior heavy oil occurs, is substantially one The double-bond hydrogenation of the liquid phase macromolecular carried out in the liquid phase is cracked into the string of free radical, free radical stabilized hydrogenation at singly-bound, singly-bound Connection process, high thermal cracking temperature (400~480 DEG C) generate a large amount of free radicals and relatively uniform point in entire state of aggregation liquid phase It is distributed in entire liquid Space, in order to prevent thermal condensation that prestissimo is needed to make free radical stabilized hydrogenation, it is evident that rely on catalyst The reactive hydrogen on surface is unable to reach purpose (because the probability of the liquid phase hydrocarbon molecule of catalyst contact is too low, reactive hydrogen moving process Also can group be combined into inactive hydrogen molecule), preferably reactive hydrogen and free radical uniformly adjacent presence, and same when free radical generates Step release, to realize efficiently for reactive hydrogen.The hydrogen supply agent that boiling point is suitable for is added in due course and can just cross and meets this requirement, prevents heat Condensation improves light product retention rate, these effects have been the Shenhua direct hydrogenation liquefaction of coal dress using hydrogen supply agent for running 8 years The successful longtime running result set is confirmed.The heavy that normal boiling point is huge higher than 530 DEG C of molecular dimension, polarity is strong is evaporated Point, if reactive hydrogen cannot be provided in due course, a large amount of colloids, asphalitine thermal cracking free radical will be condensed more compared with its cracking precursor Big condensation product is to reduce heat from hydrogenation cracked distillate oil (normal boiling point is lower than 530 DEG C of hydro carbons) yield, or even generates and exceed Thermal condensation the object such as coke or precursors of coke that reaction process liquid phase can dissolve, carry cause device quickly to be stopped work, these effects It should be confirmed by abundant experimental results.The present invention uses the operation mode of enough hydrogen supply agents, it is therefore intended that by mentioning in due course For the enough inhibition cokings of reactive hydrogen, the thermal cracking conversion ratio or the more stringent feed residue of working properties of residual oil are provided, is expanded The scope of application of technique, operational stability, the economy for improving process.

The possibility of thermal high separation process of the invention described in detail below or warm high pressure separation process uses air lift process XHBM。

Air lift process XHBM of the present invention, liquid hydrocarbon W material separate number with the counter current contacting of air lift hydrogen XBH: one As for 1~8 time, be usually 2~4 times；The quantity of air lift hydrogen XBH separates the needs of target according to air lift process XHBM component It determines；The operating pressure of air lift process XHBM, the typically slightly lower than operating pressure of its charging；The operation temperature of air lift process XHBM Degree, according to air lift process XHBM component separate target it needs to be determined that, usually 180~480 DEG C, generally 250~440 DEG C.

Reaction Separation section of the present invention, refer to comprising the R10F of hydrocarbon ils containing coal tar pitch hydro-upgrading reaction process (or Referred to as conversion zone) and the separation process of heavy oil the hydrocarbon component and lower boiling the hydrocarbon component in hydro-upgrading reaction product (or be Segregation section) process；The separation process of heavy oil the hydrocarbon component and lower boiling the hydrocarbon component can be the separation of residual oil Yu wax oil component Process (generally comprises vacuum fractionation process), is also possible to wax slop component and the separation process of light wax oil component (generally comprises Vacuum fractionation process) process, the separation process for being also possible to diesel oil and wax oil component (may include or not include decompression point Evaporate process).

Reaction Separation throttling journey of the present invention, the first hydro-upgrading comprising the R10F of hydrocarbon ils containing coal tar pitch reacted First separation process of the heavy oil the hydrocarbon component of journey and the first hydro-upgrading reaction product and lower boiling the hydrocarbon component, can be in process Unconverted residual oil or its modified oil including the first separation process (generally comprising vacuum fractionation process) discharge are recycled back into first Hydro-upgrading reaction process carries out the circulation process of circulation hydro-upgrading.

There are many modifications of the floating bed hydrogenation of existing heavy oil or residual oil or heat from hydrogenation cracking reaction separation method, and majority belongs to In a Reaction Separation throttling journey, add wherein there is the dreg-oil suspension bed hydrogenation cracking reaction separation method of industrialization operating achievement to have CANMET hydrogenation of residual oil suspended bed thermocracking process (being integrated into the Uniflex technology of Uop Inc., the U.S. later), the meaning of putting on airs are big The EST hydrogenation of residual oil suspended bed thermocracking process of sharp eni company.Other dreg-oil suspension bed hydrogenation cracking reaction separation methods, have The BPVCC technology of British Petroleum Company, the HDHPLUS technology of Petroleos de Venezuela SA (PDVSA), U.S. Chevron VRSH technology etc..

It may need for floating bed hydrogenation product to be fractionated first, a hydrogen then is separated into coal tar pitch after obtain plus hydrogen Change refined bitumen and primary hydrogenation heavy asphalt, then will once hydrogenate heavy asphalt return floating bed hydrogenation upgrading processes and carry out Secondary operation, to improve beneficial overall thermal cracking conversion ratio.Heat from hydrogenation cracking of coal tar pitch and coal tar pitch are once added For the general effect of the cracking of heat from hydrogenation again of hydrogen thermal cracking tail oil, overall heat from hydrogenation can effectively improve using hydrogen supply dissolvent Cracking conversion rate is effectively reduced and gets rid of the yield containing solid tail oil outside, to improve the economy of process.

The present invention, can be by each conversion zone of variation or the Process flow of segregation section, can be other suitable by joint processing In the hydrocarbon-bearing material of joint processing, a variety of groups can be formed by the downstream processing methods of hydrocarbon ils in a variety of hot high score gas of joint Close technique.

Flux oil or hydrogen supply dissolvent can be used in the present invention, each conversion zone.

The present invention supplements oil product obtained by hydrogenation process BRK, and may include naphtha, (60~180 DEG C of conventional boiling range evaporates Point) BRK-P-Y-N01, the first light diesel fuel (180~220 DEG C of fractions of conventional boiling range) BRK-P-Y-N02, the second light diesel fuel (routine 220~265 DEG C of fractions of boiling range) BRK-P-Y-N03, heavy diesel fuel (265~350 DEG C of fractions of conventional boiling range) BRK-P-Y-N04, light wax Oil (350~480 DEG C of fractions of conventional boiling range) BRK-P-Y-N05, wax slop (480~530 DEG C of fractions of conventional boiling range) BRK-P-Y- N06, residual oil (normal boiling point is higher than 530 DEG C of hydro carbons) BRK-P-Y-N07, above-mentioned title is a kind of address, is referred to as Light oil (60~180 DEG C of fractions of conventional boiling range) BRK-P-Y-N01, the first washing oil (180~220 DEG C of fractions of conventional boiling range) BRK-P- Y-N02, the second washing oil (220~265 DEG C of fractions of conventional boiling range) BRK-P-Y-N03, (265~350 DEG C of conventional boiling range evaporates carbolineum Point) BRK-P-Y-N04, light asphalt (350~480 DEG C of fractions of conventional boiling range) BRK-P-Y-N05, middle matter pitch (conventional boiling range 480~530 DEG C of fractions) BRK-P-Y-N06, heavy asphalt (normal boiling point is higher than 530 DEG C of hydro carbons) BRK-P-Y-N07.

Naphtha (60~180 DEG C of fractions of conventional boiling range) BRK-P-Y-N01 in products therefrom of the present invention, as needed, Deep hydrofinishing such as desulfurization, denitrogenation can be carried out to it, it is usually desirable to which generation benzene ring hydrogenation saturated reaction as few as possible adds Naphtha (60~180 DEG C of fractions of conventional boiling range) after hydrogen purification may be used as catalytic reforming raw material and prepare aromatic hydrocarbons.

The first light diesel fuel (180~220 DEG C of fractions of conventional boiling range) BRK-P-Y-N02 in products therefrom of the present invention or its add Stabilized hydrogen oil, be often unsuitable for enter up flow type hydro-upgrading reaction process R10 or and BRK be easy to vaporize because boiling point is too low It is difficult to serve as liquid phase solvent component；If into up flow type hydro-upgrading reaction process R10 or and BRK, further thermal cracking it is anti- The product answered is exactly to generate bulk gas and uneconomical；Therefore, unless carburet hydrogen Huge value, the first light diesel fuel (conventional boiling range 180~220 DEG C of fractions) BRK-P-Y-N02 usually should not enter up flow type hydro-upgrading reaction process R10 or with BRK or dedicated Heat from hydrogenation cracking process or hydrocracking process or other thermal cracking processes are processed, and hydrofining reaction can be usually entered Process carries out desulfurization, denitrogenation, production cleaning light diesel fuel.

The second light diesel fuel (220~265 DEG C of conventional boiling range in group technology direct hydrogenation liquefaction of coal products therefrom of the present invention Fraction) BRK-P-Y-N03, stabilized hydrogenation oil product is up flow type hydro-upgrading reaction process R10 or the boiling point with BRK needs Properly, the excellent hydrogen supply dissolvent oil of hydrogen supply capacity, in addition for up flow type hydro-upgrading reaction process R10 or and BRK, second is light Diesel oil or its stabilized hydrogenation oil, play liquid phase in up flow type hydro-upgrading reaction process R10 or front reaction process with BRK The effect of basic solvent composition, but the big portion in up flow type hydro-upgrading reaction process R10 or rear portion reaction process with BRK It point has vaporized, and usually up flow type hydro-upgrading reaction process R10 or there are the resource of surplus therefore has belonged to upstream with BRK Formula hydro-upgrading reaction process R10 or the product with BRK, therefore, the second light diesel fuel (220~265 DEG C of fractions of conventional boiling range) BRK-P-Y-N03 or its stabilized hydrogenation oil, usually part are used as lightweight hydrogen supply dissolvent oil and reacted for up flow type hydro-upgrading Journey R10 or and BRK, partially be used as plus hydrogen upgraded material for plus hydrogen upgrading reaction process produce final products.

(265~350 DEG C of conventional boiling range evaporates heavy diesel fuel in group technology direct hydrogenation liquefaction of coal products therefrom of the present invention Point) BRK-P-Y-N04, stabilized hydrogenation oil product, be up flow type hydro-upgrading reaction process R10 or with the most desirable boiling point of BRK Properly, hydrogen supply capacity it is excellent hydrogen supply dissolvent oil, in addition for up flow type hydro-upgrading reaction process R10 or and BRK, heavy diesel fuel Or its stabilized hydrogenation oil, the basic solvent group of liquid phase is played in up flow type hydro-upgrading reaction process R10 or whole process with BRK Point effect, and usually up flow type hydro-upgrading reaction process R10 or there are the resource of surplus therefore belong to up flow type with BRK Hydro-upgrading reaction process R10 or major product with BRK, therefore, heavy diesel fuel (265~350 DEG C of fractions of conventional boiling range) BRK- P-Y-N04 or its stabilized hydrogenation oil, usually part are used as heavy hydrogen supply dissolvent oil and are used for up flow type hydro-upgrading reaction process R10 Or and BRK, partially be used as plus hydrogen upgraded material for plus hydrogen upgrading reaction process produce final products.

Light wax oil (350~480 DEG C of fractions of conventional boiling range) BRK-P-Y-N05 in products therefrom of the present invention, as long as its is miscellaneous Matter content meets the needs as needle-shape coke raw material, and should not usually return is up flow type hydro-upgrading reaction process R10 or and BRK Secondary plus hydrogen.(350~480 DEG C of conventional boiling range evaporates light wax oil in group technology direct hydrogenation liquefaction of coal products therefrom of the present invention Point) BRK-P-Y-N05 or its stabilized hydrogenation oil product, it is up flow type hydro-upgrading reaction process R10 that liquid as needed, which can return, Or add hydrogen with BRK bis- times.

Wax slop (480~530 DEG C of fractions of conventional boiling range) BRK-P-Y-N06 in products therefrom of the present invention, as long as its is miscellaneous Matter content meets needs as needle-shape coke raw material, should not usually return up flow type hydro-upgrading reaction process R10 or with BRK bis- Secondary plus hydrogen.Light wax oil (350~480 DEG C of fractions of conventional boiling range) in group technology direct hydrogenation liquefaction of coal products therefrom of the present invention BRK-P-Y-N05 or its stabilized hydrogenation oil product, liquid as needed can return be up flow type hydro-upgrading reaction process R10 or and BRK bis- times plus hydrogen.In general, wax slop (480~530 DEG C of fractions of conventional boiling range) BRK-P-Y-N06 can carry a small amount of solid particle, And the high material of the carbon residue content for belonging to serious scarce hydrogen, excessive thermal cracking even form coke for thermal condensation object is generated.

Due to normal boiling point residual oil in products therefrom of the present invention (normal boiling point is higher than 530 DEG C of hydro carbons) BRK-P-Y-N07, It is typically found in vacuum tower tower bottom heavy bitumen logistics, usual discharge system no longer cyclic process certainly as needed can portion Divide and is recycled back into up flow type hydro-upgrading reaction process R10 or and BRK.

As previously mentioned, it is a principal object of the present invention to produce the hydro-upgrading drip for being suitable as needle-shape coke raw material light asphalt Green component, therefore, in the separation fractional distillation process of the product BRK-P of up flow type hydro-upgrading reaction process BRK, normal boiling point is higher than The cutting scheme of 350 DEG C of different fractions can according to need adjustment, for example can be and be separated into 350~400 DEG C of conventional boiling range Light fraction and the main tower bottom oil by normal boiling point higher than 400 DEG C of remaining fractional composition, can be and be separated into conventional boiling The tower bottom oil of the light fraction that 350~450 DEG C of journey and the mainly remaining fractional composition by normal boiling point higher than 450 DEG C, can be It is separated into the light fraction and the main tower by normal boiling point higher than 500 DEG C of remaining fractional composition of 350~500 DEG C of conventional boiling range Base oil, naturally it is also possible to it is to directly obtain the mainly tower bottom oil by normal boiling point higher than 350 DEG C of remaining fractional composition, above-mentioned point The relevant technologies such as the feasibility and stability, the mobility of tower bottom oil that need to consider to extract needle-shape coke raw material operating process from scheme Problem.

The air lift of the thermal high separation process S10 of second hydrogenation reaction effluent BRK-P of the invention described in detail below Process 1HBM.

Air lift process 1HBM of the present invention, liquid hydrocarbon BRK-P-L separate number with the counter current contacting of air lift hydrogen 1BH: Generally 1~8 time, usually 2~4 times；The quantity of air lift hydrogen 1BH separates the need of target according to air lift process 1HBM component It determines；The operating pressure of air lift process 1HBM slightly less than supplements the operating pressure of hydrogenation process BRK；Air lift process The operation temperature of 1HBM, according to air lift process 1HBM component separate target it needs to be determined that, usually 220~400 DEG C, generally 280~380 DEG C.

It is described in detail below it is of the invention using fixed bed hydrogenation reactor plus hydrogen upgrading reaction process HT66.

Add hydrogen upgrading reaction process HT66, the fixed bed reactors used can be 1 or 2 or more；Add hydrogen upgrading Reaction process HT66 catalyst bed working method, can be any suitable form, it is different types of to can be two or more The combination of reactor, can be down-type fixed-bed reactor, be also possible to upflow fixed bed reactor, it might even be possible on being Streaming slight expanded-bed, catalyst bed working method are usually down-flow fixed bed.Use adding for fixed bed hydrogenation reactor Hydrogen upgrading reaction process can be 1,2 or multiple beds using fixed bed catalyst bed, second and its subsequent urge The control mode of the inlet temperature of agent bed can be and use cold hydrogen or and cold oil.

Using fixed bed hydrogenation reactor plus hydrogen upgrading reaction process HT66, use plus hydrogen upgrading catalyst can be with It is the tandem compound use of 1,2 or multiple kinds plus hydrogen upgrading catalyst, along the flow direction of reaction stream, downstream Add the hydrogenation activity of hydrogen upgrading catalyst, generally equal to or higher than the upstream hydrogenation activity that adds hydrogen upgrading catalyst.

Add hydrogen upgrading reaction process HT66, the reactor used, catalyst bed using fixed bed hydrogenation reactor The volume ratio of middle liquid phase, gas phase (or vapour phase), can be with liquid phase be it is main the case where, definition plus hydrogen upgrading catalyst bed in " liquid phase actual volume/(liquid phase actual volume+gas phase actual volume) " is bed liquid phase fraction KL, and a point rate KL can be greater than 0.75, it is even greater than 0.95, forms actual liquid-phase hydrogenatin mode, in order to keep adding the hydrogen in hydrogen upgrading catalyst bed It divides sufficiently high, it may be necessary to add hydrogen in the entrance of each upgrading catalyst bed.

The present invention relates to the separation and recovery Utilizing question of decompression residuum floating bed hydrogenation hot cracked product residue, the decompressions Hydrogenation of residual oil suspended bed hot tearing product residue HVS refers to separation fractionation decompression residuum floating bed hydrogenation heat cracking reaction outflow What object R10P was obtained mainly contains catalyst granules, containing other solid higher than what 530 DEG C of Vacuum Residue Fractions formed by normal boiling point The vacuum tower base oil of body particle (organic metal in feedstock oil plus hydrogen hydroformylation product solution metal sulfide), in particle of the invention Under conditions of catalyst circulation accumulation, under conditions of very low catalyst matrix object additive amount, reaction process liquid phase can be with shape At high beaded catalyst concentration, so as to improve the overall conversion of decompression residuum, such decompression residuum suspension bed adds The yield of hydrogen hot tearing product residue HVS is very low, wherein the catalyst granules (such as molybdenum sulfide, magnetic iron ore phase Fe1-XS that carry Grain), the concentration containing other solid particles (organic metal vanadium, nickel, iron in feedstock oil plus hydrogen hydroformylation product solution metal sulfide) It is very high, such as iron content 100ppm, nickel content 200ppm, the content of vanadium 300ppm of heat from hydrogenation cracked stock decompression residuum R10F, Fresh catalyst with base of molybdenum is 200ppm with the additional amount that molybdenum measures, if decompression residuum floating bed hydrogenation hot tearing product residue HVS Weight yield only 2%, then the weight metal ratio therein from raw material decompression residuum R10F is about: iron content 0.005: 1, nickel Content 0.010: 1, content of vanadium 0.015: 1, molybdenum content 0.010: 1 are equivalent to the liquid enrichment for foring high value metals in this way Mineral reserve.

At this moment, to decompression residuum floating bed hydrogenation hot tearing product residue HVS, have with the high light solvent of aromaticity or polarity Solvent carries out extraction and separation, and the available extraction light phase being mainly made of light asphalt matter and more light hydrocarbon component obtains The extraction heavy phase being mainly made of solids such as heavy asphalt matter, free carbon, metal sulfides；If extraction light phase yield accounts for product The 50~80% of residue HVS, then taking for metallic particles in residue HVS will be concentrated by extracting the carrying ratio of metallic particles in heavy phase 2 to 5 times with ratio, weight metal carries ratio about are as follows: iron content 0.010~0.025: 1, nickel content 0.020~0.050: 1, content of vanadium 0.030~0.075: 1, molybdenum content 0.020~0.050: 1, the economic value of metal recovery process is bigger, because Metal concentration is very high.

Therefore, solvent extraction and separation process VS-EU-SPU60 can be set, extract product residue HVS, the steps include:

1. material S333 (i.e. product residue HVS) is mixed with extractant in solvent extraction and separation process VS-EU-SPU60 The liquid material VS-EU-SPU60-SL of the light phase containing agent containing extractant, the hydrocarbon component containing relatively low molecular weight is isolated afterwards, is isolated and is contained Extractant, the hydrocarbon component containing relatively high molecular weight, the liquid material of heavy phase containing the agent VS-EU- for being enriched with distributed beaded catalyst R10C SPU60-SH；

2. the fractional distillation process of the liquid material of light phase containing the agent VS-EU-SPU60-SL in distillation abjection extractant that may be present, Become light phase material VS-EU-SPU60-LP after the liquid material VS-EU-SPU60-SL of light phase containing agent distillation removing extractant；

3. the fractional distillation process of the liquid material of heavy phase containing the agent VS-EU-SPU60-SH in distillation abjection extractant that may be present, Become heavy phase material VS-EU-SPU60-HP after the liquid material VS-EU-SPU60-SH of heavy phase containing agent distillation removing extractant；

4. the material of the distributed beaded catalyst R10C of richness of at least part based on heavy phase material VS-EU-SPU60-H, is used Make desiccation material VS-EU-SPU60-H-R10C-OUT use.

Desiccation material VS-EU-SPU60-H-R10C-OUT containing metal molybdenum or with vanadium or and nickel, may be used as tamping coking technique Raw material, after mixing with coal, the high coke of production tenor makes gold for such as ironmaking, steelmaking process of metal smelt process Belong to molybdenum or is recycled with vanadium or with nickel.

If desiccation material VS-EU-SPU60-H-R10C-OUT is used as fuel combustion, a large amount of solid dusts, meeting can be discharged Increase environmental protection investments and expense.

Desiccation material VS-EU-SPU60-H-R10C-OUT containing metal molybdenum or with vanadium or and nickel, produce stamp-charging coke the step of such as Under:

1., by desiccation material VS-EU-SPU60-H-R10C-OUT solidification, crush after, mixed with coking with clean fine coal, crush, It makes cake of press firm by ramming, obtains briquette；

2., briquette sent into coke oven heated under air and kept the temperature in isolation, then through cooling and screening process, obtain Coke.

Can also directly recycle metal molybdenum contained by desiccation material VS-EU-SPU60-H-R10C-OUT or with vanadium or and nickel, production High-purity molybdenum compound etc., at least following 5 kinds of recovery methods:

1. method one first fires the desiccation material VS-EU-SPU60-H-R10C-OUT of liquid condition or solid particle state It burns, then flue dust is handled to obtain ammonium molybdate with ammonia and ammonium carbonate；Can refer to the method for United States Patent (USP) US6153155 into Row；

2. desiccation material VS-EU-SPU60-H-R10C-OUT progress coking is first obtained coke by method two, then burning is burnt Then charcoal is handled to obtain ammonium molybdate flue dust with ammonia and ammonium carbonate；Can refer to the method for United States Patent (USP) US6153155 into Row；

3. method three utilizes sulfuric acid and desiccation material VS-EU-SPU60-H- in the presence of first alcohol and oxidizing agent such as hydrogen peroxide R10C-OUT is reacted, and molybdenum is extracted into water phase and is recycled；Can refer to the method for United States Patent (USP) US4417972 into Row；

4. method four adds inorganic acid, separates, is passed through vulcanization then using high temperature high pressure process under sour molten, ammonia pressure Hydrogen, separation and etc. molybdenum is converted to molybdenum sulfide and recycles molybdenum；The method that can refer to Chinese patent CN102361994A It carries out；

5. method five, the first step will roast after desiccation material VS-EU-SPU60-H-R10C-OUT and solid base ground and mixed； The solid obtained after roasting is carried out water logging by second step, and obtained leaching liquid obtains molybdate by condensing crystallizing and crystallizes；It can join It is carried out according to the method for recycling molybdenum in a kind of coal liquefaction extraction residue of Chinese patent 201610952723.0.

The method that Chinese patent 201080012843.3 recycles metal from the coal liquefaction residues containing dead catalyst, is related to A method of recycling metal from metalliferous material, which comprises so that at least the one of the metalliferous material Partial granularity decline；The metalliferous material is blended in acid solution to be formed containing at least alkaline earth metal compound First slurry；At least alkaline earth metal compound is isolated from first slurry to form the first filtrate and metalliferous Material；Metal is leached from the metalliferous material to form the pressure leaching solution containing transition metal；Add from described It is precipitated in pressure infusion solution and recycles transition metal.In another aspect, the present invention relates to the coal liquefactions from de-oiling and drying The coal liquefaction residues of the method that metal is recycled in residue, the de-oiling and drying contain urges from group vib metal sulfide The dead catalyst of agent.

The method that molybdenum is recycled in a kind of coal liquefaction extraction residue of Chinese patent 201610952723.0, discloses a kind of coal liquid Change the method that molybdenum is recycled in extraction residue.Method includes the following steps: S1, coal liquefaction extraction residue and solid base is ground mixed It is roasted after conjunction；The solid obtained after roasting is carried out water logging by S2, and obtained leaching liquid obtains molybdate knot by condensing crystallizing It is brilliant.It applies the technical scheme of the present invention, coal liquefaction extraction residue is handled using wet type alkali extraction method, then water logging, dense Sheepshank is brilliant, recycles micro molybdenum element therein.The recovery method process route is simple, at low cost, environmental-friendly, extraction efficiency Height, obtained molybdenum element compound purity is high, business recovery value with higher.

The present invention, can be with shape by using for reference the above-mentioned method for recycling metal from the coal liquefaction residues containing dead catalyst At the metal recovery processes of desiccation material VS-EU-SPU60-H-R10C-OUT of the invention, because metal concentration is higher and impurity Ash content, the content of solid carbon are much lower, so the economic value of metal recovery process is bigger.

Enter the non-targeted catalyst bulky grain solid particle carried in the material of hydrogenation process R10 in order to prevent to exist It is easy to accumulate in the circulation loop of mechanically decoupled large-size particles BP, guide can be set and take off solid particle step, and need It wants regular intermittent discharge circulating particle or needs continuous and quantitative discharge cycle particulate matter.

The present invention finally enters the material of hydrogenation process R10, first deviates from general, taking off solid particle step in guide The particle that granularity is equal to the minimum grain size for the large-size particles BP for being easy to mechanically decoupled obtains poor granule materials, or first deviates from The particle that granularity is less than the minimum grain size for being easy to mechanically decoupled large-size particles BP obtains poor granule materials, or first deviates from grain The particle that degree is equal to 50% partial size of the minimum grain size for the large-size particles BP for being easy to mechanically decoupled obtains poor granule materials, so Poor granule materials enter hydrogenation process R10 afterwards.

The high aromatic hydrocarbons wax slop BRAF-AVGO of heat from hydrogenation cracked reaction product described in detail below is in heat from hydrogenation cracking reaction Reaction in journey tends to.

The high aromatic hydrocarbons wax slop BRAF-AVGO of heat from hydrogenation cracked reaction product of the present invention, from the point of view of component characteristic, It is the hydrocarbon-fraction for the enrichment polycyclic aromatic hydrocarbon that heat from hydrogenation cracking reaction difficulty is only second to heat from hydrogenation crackate decompression residuum THC-VR, Carbon residue with higher, thermal condensation sensibility, during heat from hydrogenation cracking reaction, hydrogenation reaction reacts parallel with thermal condensation In the presence of that is, there is parallel to add hydrogen lighting reaction and the reaction of dehydrogenative condensation heaviness, both the Direction of Reaction are:

1. plus hydrogen lighting reaction i.e. inhibit coking reaction, direction be " condensed-nuclei aromatics → polycyclic aromatic hydrocarbon → fractional saturation Multiring structure aromatic hydrocarbons → higher hydro carbons of hydrogen content "；

2. dehydrogenation reaction, that is, coking reaction, direction are " coke ← Carbonaceous mesophase ← asphalitine component ← colloid ← condensed ring Aromatic hydrocarbons ← polycyclic aromatic hydrocarbon ".

For high aromatic hydrocarbons wax slop BRAF-AVGO, in order to improve the adjoint heat from hydrogenation of Unionfining heat cracking reaction process The reaction environment of cracking material heavy oil serves as the dispersion solvent oil of gum asphalt in the high aromatic hydrocarbons wax slop BRAF-AVGO of expectation While, it just must try to inhibit polycyclic aromatic hydrocarbon therein that undesirable thermal condensation reaction occurs, to realize heavy-oil hydrogenation hot tearing Addition reaction process does not increase the first purpose of colloid, asphalitine, the yield of coke other than change process, and preferably realizing reduces heavy oil Colloid, asphalitine, the second purpose of the yield of even coke of heat from hydrogenation cracking process, to guarantee necessarily long to continuously run week Therefore phase, necessary low outlet residual oil ratio arrange high aromatic hydrocarbons wax slop BRAF-AVGO to first pass through an increase hydrogen content, drop Hydrogenation modification (or modification) reaction process BRA of low carbon residue just becomes inevitable, this is required in floating bed hydrogenation modified-reaction process BRA carries out the partial hydrogenation saturated reaction process of polycyclic aromatic hydrocarbon or adds hydrogen saturated reaction process, since the part of polycyclic aromatic hydrocarbon adds Hydrogen saturated reaction process product section saturation multiring structure aromatic hydrocarbons have the function of multi-solvents (coking inhibitor, catalyst carrier, The dispersion solvent of hydrogen supply agent, gluey asphaltic substances), also just become a kind of preferred operation scheme, is also conducive to remain necessary big Gum asphalt dispersion solvent oil internal circulating load (recycle ratio), prevent the conversion per pass of these recycled solvent oils is excessively high from leading Cause the internal circulating load of the dispersion solvent oil of gum asphalt too low.

The hydrogenation modification reaction process BRA of high aromatic hydrocarbons wax slop BRAF-AVGO described in detail below, usually with to greatest extent Preparing hydrogen supply hydrocarbon is selected objective target.

The hydrogenation modification of high aromatic hydrocarbons wax slop BRAF-AVGO such as heat from hydrogenation crackate wax slop of the present invention reacted Journey BRA, main target are, compared with conventional heat from hydrogenation cracking reaction process, in catalyst and hydrogen supply dissolvent existence condition Under, make that more plus hydrogen saturated reaction occurs first for high aromatic hydrocarbons wax slop BRAF-AVGO and sufficient thermal cracking free radical adds hydrogen Stablize reaction, so that the carbon residue of high aromatic hydrocarbons wax slop BRAF-AVGO be effectively reduced, makes normal boiling point that may be present therein Higher than 530 DEG C ground hydro carbons become the original of the heat from hydrogenation cracking reaction process of appropriate heat from hydrogenation cracking severity (usually reducing it as far as possible) Material.

In group technology of the invention, the hydrogenation process BRA of high aromatic hydrocarbons wax slop BRAF-AVGO of the present invention The first reaction task be the partial hydrogenation saturated reaction for carrying out the i.e. heavy arene of removal of ccr by hydrotreating reaction, certainly, while can be with Generation hydrofining reaction (including demetalization plus hydrogen hydrogenolysis, olefins hydrogenation reaction plus hydrogen removing impurities matter (oxygen, sulphur, nitrogen) Reaction plus hydrogen aromatic hydrocarbons saturated reaction, removal of ccr by hydrotreating reaction) or and hydrocracking reaction.Heat from hydrogenation cracking wax slop BRAF- AVGO, the product of the up flow type heat from hydrogenation cracking reaction process R10 as heavy oil R10F, in the vacuum fractionation step of fractional distillation process In be evaporated and with residue fraction completion separate, usually in the recycling step of vacuum flashing vapour or the fractionating step of vacuum flashing vapour It is condensed into as " heat from hydrogenation cracking wax slop BRAF-AVGO fraction or logistics ", since it is and heat from hydrogenation cracked vacuum residue THC-VR adjacent fractionation fraction, it usually contains catalyst conversion product such as molybdenum sulfide of addition etc., the R10 from heavy oil R10F Product metal sulfide, may accumulation coke, entrainment resin and asphalt；If from heat from hydrogenation cracking wax slop BRAF- Above-mentioned solid and high carbon residue component are strictly isolated in AVGO fraction, then increase considerably separating energy consumption and increase residual oil production Rate；And heat from hydrogenation cracking wax slop BRAF-AVGO fraction is introduced into up flow type hydrogenation modification reaction process BRA or heavy-oil hydrogenation heat Cracking reaction process R10 does not need then strictly to isolate above-mentioned solid and high carbon residue component, thus can be greatly lowered point From energy consumption and yield of bottoms can be reduced.

When heat from hydrogenation cracking wax slop BRAF-AVGO be enrichment polycyclic aromatic hydrocarbon and carry secretly a certain amount of catalyst solid and High carbon residue group timesharing, hydrogenation modification reaction process BRA usually preferably select up flow type expanded bed hydrogenator system.

In the up flow type hydrogenation process BRA of heat from hydrogenation cracking wax slop BRAF-AVGO, when reactive hydrogen is supplied not in time When, polycyclic aromatic hydrocarbon, colloid, asphalitine thermal cracking free radical will occur condensation reaction, bigger point of production molecular weight Son or structure group, repeatedly the final result of dehydrogenation and condensation reaction is to generate colloid, asphalitine even coke, certainly, this It is the negative reaction for needing inhibition or reduction, may be needed in this way using the smaller such as normal boiling point of molecular weight to be usually 230~450 DEG C, generally 230~380 DEG C of hydrogen supply dissolvent.

The reactor types of the hydrogenation modification reaction process BRA of high aromatic hydrocarbons wax slop BRAF-AVGO of the present invention, can be with It is any appropriate form, can be one of combination cot reactor of suspended-bed reactor, ebullated bed and suspension bed or several The combination of kind.

The hydrogenation process BRA of high aromatic hydrocarbons wax slop BRAF-AVGO of the present invention, the hydrogenation catalyst used can To be the combination of a kind or 2 kinds or a variety of, any suitable form can be.

According to specific oil property, hydrogenation process BRA, which can be, is applied in combination boiling bed hydrogenation reaction process, combination Use boiling bed hydrogenation catalyst.

In general, hydrogenation process BRA is floating bed hydrogenation reaction process according to specific oil property, reaction process is deposited Hydrogenation modification catalyst be distributed particle hydrogenation catalyst, precursor is granular material or solution shape material.

The hydrogenation process BRA of heat from hydrogenation cracking wax slop BRAF-AVGO of the present invention, the reactor used can be with 1 or 2 or more, reactor working method can be any suitable form, can be up flow type suspended-bed reactor or The up flow type suspended-bed reactor or adverse current suspended-bed reactor of carrying liqs product circulation, separate unit up flow type suspended-bed reactor W-response area may be considered that and be divided into 2 or multiple reaction zones.Any reaction of hydrogenation process reactor of the present invention The control mode of the inlet temperature in area, can be adjust hydrogen temperature or and flow, can be adjust oil product temperature or and Flow.

The hydrogenation process BRA of heat from hydrogenation cracking wax slop BRAF-AVGO, the reactor used, in reaction compartment The volume ratio of liquid phase, gas phase (or vapour phase) can be with liquid phase the case where being main, define in reaction compartment " liquid phase is practical Volume/(liquid phase actual volume+gas phase actual volume) " is reaction compartment liquid phase fraction KL, and a point rate KL is typically larger than 0.5, is general Greater than 0.65, even greater than 0.80, actual reinforcing liquid-phase hydrogenatin mode is formed, in order to keep reaction compartment hydrogen partial pressure sufficient Enough height, it may be necessary to the different height of reactor position 2 times or repeatedly add hydrogen.

It, can be former by a part of liquid in order to adjust reaction feed property, or in order to control reaction process property of liquid phase Expect that R10F introduces the up flow type hydrogenation process BRA of heat from hydrogenation cracking wax slop BRAF-AVGO.

In order to reuse the consolidating with the effect of heat from hydrogenation Cracking catalyst in heat from hydrogenation cracked vacuum residue THC-VR Body object can add a part of heat from hydrogenation cracked vacuum residue THC-VR up flow type for introducing high aromatic hydrocarbons wax slop BRAF-AVGO In hydrogen reaction process BRA.

Hydrogen supply dissolvent component in the reaction product BRAP of hydrogenation modification reaction process BRA of the invention described in detail below, The whereabouts of heavy oil component, hydrogen component.

The crucial purpose of of the invention one is to transform high aromatic hydrocarbons wax slop BRAF-AVGO as hydrogen supply dissolvent BRA-CDS, And hydrogen supply dissolvent BRA-CDS is introduced into the up flow type hydrogenation process R10 of decompression residuum and uses or be recycled, Huo Zheyin Enter the up flow type hydrogenation process CR comprising heat from hydrogenation cracked vacuum residue THC-VR, heavy oil up flow type heat from hydrogenation cracking reaction The series connection process of process R10 is repeatedly used in series or circulating series use, and the heavy oil component in reaction product BRAP is made to exist Subsequent up flow type heat from hydrogenation cracking reaction process carries out Unionfining thermal cracking, and working method can be any suitable form, The present invention lists some common schemes.

Another free-revving engine of the invention is, by the hydrogen in the reaction product BRAP of hydrogenation modification reaction process BRA, Heavy oil up flow type heat from hydrogenation is introduced into the up flow type hydrogenation process CR of heat from hydrogenation cracked vacuum residue THC-VR or introduces to split Change secondary use or recycling in reaction process R10, or introduces the upstream comprising heat from hydrogenation cracked vacuum residue THC-VR Formula hydrogenation process CR, heavy oil up flow type heat from hydrogenation cracking reaction process R10 series connection process it is secondary be used in series or It is recycled, while simplifying material transferring process.

Another free-revving engine of the invention is, by the dispersion in the reaction product BRAP of hydrogenation modification reaction process BRA Shape hydrogenation catalyst is introduced into the up flow type hydrogenation process CR of heat from hydrogenation cracked vacuum residue THC-VR or introduces on heavy oil Secondary use or recycling in streaming heat from hydrogenation cracking reaction process R10, or introducing includes heat from hydrogenation cracked vacuum residue The series connection process two of the up flow type hydrogenation process CR of THC-VR, heavy oil up flow type heat from hydrogenation cracking reaction process R10 It is secondary to be used in series or be recycled, while simplifying material transferring process.

Hydrocarbon CRF up flow type hydrogenation process CR inferior of the invention described in detail below, hydrocarbon CRF inferior can be plus hydrogen Thermal cracking decompression residuum THC-VR.

Poor quality hydrocarbon CRF of the present invention, usually heavy hydrocarbon inferior, common to be meant that: not use hydrogen supply dissolvent condition Under, in other operating conditions (reaction pressure, reaction temperature, catalyst composition and additive amount and amount, residence time, hydrogen oil Volume ratio, way of operation) under the same conditions, coking tendency of the hydrocarbon CRF inferior during heat from hydrogenation cracking reaction, More serious than coking tendency of heavy oil R10F during heat from hydrogenation cracking reaction, i.e., coking yield is higher or turns with heat from hydrogenation cracking Rate is lower；In general, the normal boiling point in hydrocarbon CRF inferior is higher than the carbon residue of 530 DEG C of hydro carbons than the normal boiling point in heavy oil ARF Carbon residue higher than 530 DEG C of hydro carbons is higher.

The up flow type hydrogenation process CR of poor quality hydrocarbon CRF of the present invention, main target are, with conventional heat from hydrogenation Cracking reaction process is compared, and under catalyst and hydrogen supply dissolvent existence condition, makes hydrocarbon CRF inferior that more plus hydrogen occur first full With reaction and the reaction of sufficient thermal cracking free radical stabilized hydrogenation, so that the carbon residue of hydrocarbon CRF inferior be effectively reduced, make therein Normal boiling point higher than 530 DEG C hydro carbons become appropriate heat from hydrogenation cracking severity heat from hydrogenation cracking reaction process raw material.

In group technology of the invention, the first of the up flow type hydrogenation process CR of poor quality hydrocarbon CRF of the present invention Reaction task is that the removal of ccr by hydrotreating reaction i.e. heavy arene for carrying out heavy hydrocarbon inferior or colloid, asphalitine add hydrogen saturated reaction, Certainly, while hydrofining reaction can occur (including demetalization plus hydrogen hydrogenolysis, olefins hydrogenation reaction plus hydrogen is de- Impurity (oxygen, sulphur, nitrogen) reaction plus hydrogen aromatic hydrocarbons are satisfied or are reacted with fractional saturation reaction, removal of ccr by hydrotreating) or and be hydrocracked anti- It answers.The typical feedstock of the up flow type hydrogenation process CR of hydrocarbon CRF inferior is exactly that the up flow type heat from hydrogenation cracking of heavy oil R10F is anti- The residue fraction in process R10 product is answered, in general, in the tower bottom residual oil that it is enriched in vacuum fractionation tower in product fractionation process, This residual oil THC-VR usually contains catalyst conversion product such as molybdenum sulfide of addition etc., the hydrogenation products metal from heavy oil R10F Sulfide, the coke that may be accumulated.

When hydrocarbon CRF inferior includes the conventional boiling in the up flow type heat from hydrogenation cracked reaction product people R10P from heavy oil R10F When point is higher than 530 DEG C of hydro carbons R10-VR, the carbon residue content of part heavy oil R10-VR is usually above heavy oil R10F, in other words carbon Liquid phase in hydrogen material up flow type heat from hydrogenation cracking reaction process R10 is adapted as the heat from hydrogenation cracking reaction of hydrocarbon CRF inferior The colloid of journey, asphalitine, liquid phase coke dispersion solution, therefore, the present invention is by the up flow type hydrogenation process of hydrocarbon CRF inferior The second half section that heavy hydrocarbon in CR reaction product introduces the up flow type heat from hydrogenation cracking reaction process AR of heavy oil R10F carries out appropriateness and adds Hydrogen heat cracking reaction can control the thermal cracking depth of hydro carbons poor quality hydrocarbon CRF simultaneously, prevent excessively high hot tearing rate from leading to pyrocondensation The yield for closing object such as asphalitine is more than the generation for limiting the quantity and causing second liquid phase (pitch phase).

In the up flow type hydrogenation process CR of hydrocarbon CRF inferior, when reactive hydrogen is supplied not in time, colloid, pitch Condensation reaction will occur for the thermal cracking free radical of matter, production molecular weight bigger molecule or structure group, repeatedly dehydrogenation with The final result of condensation reaction is to generate coke, and certainly, this is the negative reaction for needing inhibition or reduction.

The reactor types of the up flow type hydrogenation process CR of poor quality hydrocarbon CRF of the present invention, can be any appropriate Form, can be the combination of one or more of combination cot reactor of suspended-bed reactor, ebullated bed and suspension bed.

The up flow type hydrogenation process CR of poor quality hydrocarbon CRF of the present invention, the reactor used can be 1 or 2 Or more, reactor working method can be any suitable form, can be up flow type suspended-bed reactor or carrying liqs product The up flow type suspended-bed reactor or adverse current suspended-bed reactor of circulation, the W-response of separate unit up flow type suspended-bed reactor Area may be considered that and be divided into 2 or multiple reaction zones.The entrance of any reaction zone of hydrogenation process reactor of the present invention The control mode of temperature, can be adjust hydrogen temperature or and flow, can be adjust oil product temperature or and flow.

The up flow type hydrogenation process CR of hydrocarbon CRF inferior, the reactor used, liquid phase in reaction compartment, gas phase (or Vapour phase) volume ratio, can be with liquid phase the case where being main, define " the liquid phase actual volume/(liquid phase is real in reaction compartment Border volume+gas phase actual volume) " be reaction compartment liquid phase fraction KL, a point rate KL is typically larger than 0.5, generally higher than 0.65, even Greater than 0.80, actual reinforcing liquid-phase hydrogenatin mode is formed, in order to keep reaction compartment hydrogen partial pressure sufficiently high, it may be necessary to The different height of reactor position 2 times or repeatedly add hydrogen.

It, can be former by a part of liquid in order to adjust reaction feed property, or in order to control reaction process property of liquid phase Expect that R10F introduces the up flow type hydrogenation process CR of hydrocarbon CRF inferior.

It, can be by the upper of heavy oil R10F in order to adjust reaction feed property, or in order to control reaction process property of liquid phase A part of product liquid or final liquid of the intermediate liquid product such as front conversion zone of streaming heat from hydrogenation cracking reaction process R10 A part of product liquid of body product such as rear portion conversion zone, is introduced directly into the up flow type of hydrocarbon CRF inferior under high-temperature high-pressure state Hydrogenation process CR, especially when the heavy oil component in the up flow type hydrogenation process CR reaction product CRP of hydrocarbon CRF inferior It is introduced directly into the rear portion conversion zone R10B of the up flow type heat from hydrogenation cracking reaction process R10 of heavy oil R10F and is reacted without front When section R10A is processed.

The residue fraction in up flow type heat from hydrogenation cracked reaction product R10P in order to shorten heavy oil R10F enters hydrocarbon inferior The path of the up flow type hydrogenation process CR of CRF, when (normal boiling point is lower than the distillate that the liquid phase of reaction product R10P contains 530 DEG C of hydro carbons) when being rich in hydrogen supply agent or precursor of hydrogen donor, directly the liquid phase of part reaction product R10P can be introduced bad The up flow type hydrogenation process CR of matter hydrocarbon CRF, at this point, foring the short circulation loop of tail oil high pressure；When reaction product R10P's When the distillate (normal boiling point is lower than 530 DEG C of hydro carbons) that liquid phase contains only contains a small amount of hydrogen supply agent or precursor of hydrogen donor, lead to It often needs to obtain the miscella of residual oil or residual oil and wax slop as bad in the oily separation and recovery system of the generation of reaction product R10P Matter heavy hydrocarbon introduces up flow type hydrogenation process CR, at this point, foring conventional tail oil long circulating circuit.

It is supplied in the up flow type hydrogenation process CRA reaction product CRAP of hydrocarbon CRF inferior of the invention described in detail below The whereabouts of hydrogen solvent composition, heavy oil component, working method can be any suitable form, and the present invention lists some common sides Case.The crucial purpose of of the invention one is that as needed, (circulation makes hydrogen supply dissolvent component in reuse reaction product CRP With, be used in series, series circulation use), the heavy oil component in reaction product CRAP can be made to add in the up flow type of heavy oil R10F Hydrogen heat cracking reaction process R10 (rear portion conversion zone) carries out Unionfining thermal cracking.

Hydrocarbon catalytic heat cracking reaction process of the present invention, refers to the raw material hydrocarbon under hot cracking catalyst existence condition What is occurred is broken heat cracking reaction process as the main purpose with carbon-carbon bond, including the usually catalytic cracking reaction process or urges Change cracking reaction process, the body material oil usually processed is wax oil, reduced crude, records a document T001 of this kind of technology It is: 1. publication title: " catalytic cracking process and engineering "；2. retrieval is encoded with books: ISBN coding: 7-80043-537-7； Chinese depository library CIP data core word: (2004) No. 131193；3. chief editor: Chen Junwu；4. publishing house: Sinopec goes out Version society.Pages 459 to page 488 of document " catalytic cracking process and engineering " describe typical catalytic cracking light diesel fuel (light circulation Oil), catalytic cracking recycle oil (heavy-cycle oil), catalytic cracking clarified oil physical data.According to the operating condition of specific device With the difference of product separation scheme, catalytic cracking light diesel fuel (light cycle oil), catalytic cracking recycle oil (heavy-cycle oil), catalysis are split The boiling point range for changing clarified oil fluctuates in a certain range, and based on the present invention, catalytic thermal cracking reaction can be improved and generate oil Heavy wax oil yield, then go up flow type hydrogenation modification process carry out hydrogenation reaction.

Coking heavy oil reaction process of the present invention is referred to the mink cell focus of poor hydrogen (such as decompression residuum, cracked residue Deng) it is raw material, under the conditions of high temperature and long reaction time, carry out the hot procedure of depth thermal cracking and condensation reaction, raw material It is converted into gas, naphtha, gasoline, diesel oil, heavy distillate (coking light wax oil, coking wax slop) and coke.Coking Technology type include autoclave coking, open hearth coking, delayed coking, contact coking, fluid coking, flexicoking.Modern heavy The techniques such as oily coking, including delayed coking, contact coking, fluid coking, flexicoking.Record a text of this kind of technology Offering is: 1. publication title: " delay coking process and engineering "；2. retrieval is encoded with books: ISBN coding: 978-7-80229- 456-1；Chinese depository library CIP data core word: (2007) No. 168082；3. chief editor: Qu Guohua；4. publishing house: China Petrochemical industry publishing house.Pages 188 to page 254 of document T002 " delay coking process and engineering ", describe typical delayed coking wax The physical data of oil.According to the difference of the operating condition of specific device and product separation scheme, the boiling point range of wax tailings exists Fluctuation in a certain range, and based on the present invention, the yield that coking generates the heavy wax oil of oil can be improved, up flow type is then gone to add Hydrogen modifying process carries out hydrogenation reaction.

Due to catalytic cracking recycle oil (heavy-cycle oil), catalytic cracking clarified oil, wax tailings poor quality, it is difficult to directly Catalytic cracking or fixed bed hydrogenation cracking, and it is then real to use the present invention to enter high aromatic hydrocarbons wax slop hydrogenation modification reaction process BRA Optimization processing is showed.

Characteristic of the invention is described below.

Recycle the material of machinery separation process XSX0 discharge；

Select 1, LP-K100 0.000500: 1~0.002000: 1；

Select 2, LP-K100 0.002000: 1~0.005000: 1；

Select 3, LP-K100 0.005000: 1~0.020000: 1.

Select 1, BP-K100 0.000500: 1~0.002000: 1；

Select 2, BP-K100 0.002000: 1~0.005000: 1；

Select 3, BP-K100 0.005000: 1~0.020000: 1；

Select 4, BP-K100 0.020000: 1~0.200000: 1.

Select 1, LP-K100 0.000500: 1~0.002000: 1；

Select 2, LP-K100 0.002000: 1~0.005000: 1；

Select 3, LP-K100 0.005000: 1~0.020000: 1；

Select 1, BP-K100 0.000500: 1~0.002000: 1；

Select 2, BP-K100 0.002000: 1~0.005000: 1；

Select 3, BP-K100 0.005000: 1~0.020000: 1；

Select 4, BP-K100 0.020000: 1~0.200000: 1.

Select 1,100-LP-K100 0.000200: 1~0.000500: 1；

Select 2,100-LP-K100 0.000100: 1~0.000200: 1；

Select 3,100-LP-K100 0.000050: 1~0.000100: 1；

Select 4,100-LP-K100 0.000010: 1~0.000050: 1.

Select 1,200-BP-K100 0.000200: 1~0.000500: 1；

Select 2,200-BP-K100 0.000100: 1~0.000200: 1；

Select 3,200-BP-K100 0.000050: 1~0.000100: 1；

Select 4,200-BP-K100 0.000010: 1~0.000050: 1.

Select 1,100-LP-K100 0.000200: 1~0.000500: 1；

Select 2,100-LP-K100 0.000100: 1~0.000200: 1；

Select 3,100-LP-K100 0.000050: 1~0.000100: 1；

Select 4,100-LP-K100 0.000010: 1~0.000050: 1；

Select 1,200-BP-K100 0.000200: 1~0.000500: 1；

Select 2,200-BP-K100 0.000100: 1~0.000200: 1；

Select 3,200-BP-K100 0.000050: 1~0.000100: 1；

Select 4,200-BP-K100 0.000010: 1~0.000050: 1.

Selection 1, settling methods use settlement separation tank；

Selection 1, uses granular membrane；

Selection 2, uses key joint web filter；

Selection 3, centrifugal filtration process uses centrifugal filter；

Selection 4, filter press technique uses pressure filter；

Selection 5, vacuum filtration process uses vacuum filter.

1. 120~200 DEG C；

2. 200~250 DEG C；

3. 250~300 DEG C；

4. 300~350 DEG C；

5. 350~400 DEG C；

6. 400~450 DEG C.

1. the sulfide of molybdenum；

2. the sulfide of iron；

3. the sulfide of nickel；

4. the sulfide of vanadium；

5. the sulfide of tungsten.

At least part heavy phase material VS-EU-H is used as material XSX0-F；

At least part mixture QQ77 is used as material XSX0-F.

Selection 3, centrifugal filtration process uses centrifugal filter；

1. level-one partition method；

1. being horizontally mounted；

2. right angle setting；

Option 1, the high hydrocarbon ils of gluey pitch shape constituent content；

Option 2, the high hydrocarbon ils of content of ashes；

Option 3, the high hydrocarbon ils of easy coking constituent content；

Option 5, the hydrocarbon ils of high aromatic carbon rate.

Option 8, the hydrogenation process of ethylene cracking tar；

The present invention can be set guide and take off solid particle step:

Selection 1 is greater than 5%；

Selection 2 is greater than 10%；

Selection 3 is greater than 15%；

Selection 4 is greater than 20%；

Selection 5 is greater than 25%；

Selection 6 is greater than 35%；

Selection 7 is greater than 45%；

Selection 8 is greater than 55%；

Selection 1, less than 5%；

Selection 2, less than 10%；

Selection 3, less than 15%；

Selection 4, less than 20%；

Selection 5, less than 25%；

Selection 6, less than 30%；

Selection 7, less than 35%；

Selection 8, less than 40%.

Selection 1 is greater than 25%；

Selection 2 is greater than 40%；

Selection 3 is greater than 55%；

Selection 4 is greater than 70%；

Selection 5 is greater than 85%；

Selection 6 is greater than 95%；

Selection 7 is greater than 96%；

Selection 8 is greater than 97%；

Selection 9 is greater than 98%；

Selection 10 is greater than 99%.

In removal process SU10, thermal high separation process THPS is set；

Recycling plus hydrogen upgrading reaction product HT66-P.

Hydrocarbon material RKKC containing catalyst, can be selected from one or more of following materials；

Option 1, the solvent containing benzene or toluene；

Option 2, the solvent containing tetrahydrofuran；

Option 3, the solvent containing carbon disulfide；

Option 4, the solvent containing quinoline；

Option 5, the solvent containing cyclohexanone；

Option 6, the solvent containing pyridine；

Option 7, the solvent containing N-Methyl pyrrolidone；

Option 8, the solvent containing dimethyl ether；

Option 9, the solvent containing dimethyl sulfoxide；

Option 10, the solvent containing dimethylformamide；

Option 11, the solvent containing ethylenediamine；

Option 12, the solvent containing acetone；

Option 13, the solvent containing phenolic groups；

Option 1 is used as outer discharge and process U100 is discharged；

1. the wax slop of petroleum base viscous crude；

The general control principle of the gas-phase presulfiding hydrogen concentration of hydrogenation process of the invention described in detail below.

As needed, any supplement sulphur can be added to the hydrogenation process for requiring supplementation with sulphur, but be usually to be added To most upstream hydrogenation process entrance to be used in series sulphur, to guarantee that the necessary minimum hydrogen sulfide of hydrogenation process is dense Such as 500PPm (volume) or 1000PPm (volume) or 3000PPm (volume) are spent, to guarantee the necessary hydrogen sulfide sectional pressure of catalyst Not less than minimum must value.The supplement sulphur can be sulfide hydrogen or can be converted into hydrogen sulfide to hydro-conversion mistake Material of the journey without ill-effect, such as hydrogen sulfide containing gas or oil product, or the two of hydrogen sulfide is generated after contacting with high-temperature hydrogen Nitric sulfid or dimethyl disulfide or sulphur (such as molten sulfur) etc..When the hydrogen sulfide number in the gas phase of hydrogenation process BRK, R70 When amount satisfaction needs, sulfur supplementary agent can not used.

The rule of the high pressure separation process of hydrogenation reaction effluent of the invention described in detail below.

The high pressure separation process of hydrogenation reaction effluent generally comprises cold high pressure separator, when hydrocarbon in hydrogenation reaction effluent When oil density big (such as close with water density) or viscosity are difficult to separate greatly or with water emulsification, it is also necessary to which it is usual that operation temperature is set For 150~450 DEG C of high pressure hot separator, hydrogenation reaction effluent enters high pressure hot separator and is separated into one in volume at this time On the hot high score gas gas that is mainly made of hydrogen and one be mainly made of conventional liq hydrocarbon and solid that may be present Hot high score oil liquid body, hot high score gas enter the cold high pressure separator that operation temperature is usually 20~80 DEG C be separated into cold high score oil and Cold high score gas realizes following target since a large amount of high boiling components enter in hot high score oil liquid body: cold high score oil density becomes smaller Or viscosity becomes smaller or is easily isolated with water.High pressure hot separator is arranged in the high pressure separation process of hydrogenation reaction effluent, is also equipped with The advantages of reducing thermal loss because hot high score oil liquid body can be undergone to avoid hot high score gas using air cooler or water cooler Cool process.Meanwhile the hydrogenation process that the hot high score oil liquid body in part can be returned to upstream is recycled, to improve The overall raw material property of the hydrogenation process of the recycle oil is received, or circulation plus hydrogen are carried out to the recycle oil.

Hydrogenation reaction effluent or hot high score gas enter before cold anticyclone separate section, usually first reduce temperature (usually Feed and exchange heat with reactive moieties) (temperature should be higher than that in the hydrogenation reaction effluent gas phase that sulphur hydrogenates ammonia to about 220~100 DEG C Crystallization temperature), then usually injection washing water forms water filling back end hydrogenation reaction effluent thereto, washing water for absorbing ammonia and Issuable other impurity such as hydrogen chloride etc., and the aqueous solution after absorbing ammonia necessarily absorbs hydrogen sulfide.In cold anticyclone separation unit Point, the water filling back end hydrogenation reaction effluent separates are as follows: one be mainly made of hydrogen in volume cold high score gas, a master Will by cold high score that conventional liq hydrocarbon and dissolved hydrogen form oil, one it is being mainly made of water and dissolved with ammonia, hydrogen sulfide it is cold High score water.The cold high score water, wherein the content of ammonia is generally 0.5%~15% (w), preferably 1%~8% (w).Note washing One purpose of water is the ammonia and hydrogen sulfide absorbed in hydrogenation reaction effluent, prevents from forming sulphur hydrogenation ammonia or the crystallization of more sulphur ammonia is stifled Heat exchanger channel is filled in, system pressure drop is increased.The injection rate of the washing water should be determined according to following principles: on the one hand, washing It is divided into vapour phase water and liquid phase water after water injection hydrogenation reaction effluent, liquid phase water has to be larger than zero, preferably washing water inventory 30% or more；In another aspect, washing water is used to absorb the ammonia in hydrogenation reaction effluent, the ammonia density of high score gas is prevented too Height reduces catalyst activity, and the lower the ammonia volumetric concentration of usual high score gas the better, generally no greater than 200PPm (v), preferably less In 50PPm (v).The cold high pressure separator operating pressure is that hydrogenation reaction partial pressure subtracts actual pressure drop, cold anticyclone The difference of separate section operating pressure and hydrogenation reaction pressure, it is unsuitable too low or excessively high, generally 0.35~3.2MPa, be usually 0.5~1.5MPa.The hydrogen volume concentration value of the cold high score gas, should not too low (cause device operating pressure rise), one As should not less than 70% (v), preferably be not less than 80% (v), be preferably not below 85% (v).As previously described at least partially, usually 85%~100% cold high score gas is returned to be recycled in hydrogenation reaction part, to provide hydrogenation reaction part necessary hydrogen Amount and hydrogen concentration；In order to improve plant investment efficiency, it is necessary to assure circulation hydrogen concentration is not less than lower limit value above-mentioned, for this purpose, root According to specific feedstock property, reaction condition, product distribution, a part of cold high score gas can be excluded to exclude reaction generation Methane, ethane.It, can be using conventional membrane separation process or pressure swing adsorption technique or oil wash technique for the cold high score gas of discharge It realizes hydrogen and the separation of non-hydrogen gas component, and the hydrogen of recycling is used as new hydrogen.

New hydrogen enters plus hydrogen partial is to supplement the hydrogen that hydrogenation process consumes, and the higher the better for new hydrogen hydrogen concentration, generally Not preferably less than 95% (v), preferably not below 99% (v).All new hydrogen can be introduced any hydrogenation reaction part.

Claims

1. content of wax oil plant adds hydrogen, adds the combined method of hydrogen, catalyst circulation containing oil of dreg, it is characterised in that comprise the steps of:

(1) in the floating bed hydrogenation modified-reaction process BRA of the component materials of wax oil containing aryl BRAF, there are hydrogen, conventional liquid Body hydrocarbon, dispersing type large-size particles catalyst BP simultaneously there may be hydrogen supply hydrocarbon, there may be dilution hydrocarbon, there may be dispersing type Under conditions of small size particle catalyst LP, the wax containing aryl of solid particle is contained containing double ring arene or with the possibility of polycyclic aromatic hydrocarbon Oil ingredient material BRAF carries out hydrogenation reaction BRR in hydrogenation modification reaction process BRA and at least part aromatic hydrogenation part occurs Saturated reaction is converted into the hydrogenation modification reaction product BRAP rich in hydrogen supply the hydrocarbon component BRA-DSC；

Flow B RAP-BP-X comprising distributed large-size particles catalyst BP of at least part based on product BRAP, passes through At least part reaction compartment of floating bed hydrogenation reaction process R10 participates in reaction, with floating bed hydrogenation reaction process R10 into Expect R10F or the contact of its hydro-conversion object；

(2) in floating bed hydrogenation reaction process R10, there are hydrogen, conventional liq, distributed large-size particles catalyst BP are same When there may be hydrogen supply hydrocarbon, there may be dilution hydrocarbon, there may be under conditions of distributed small size particle catalyst LP, at least A part occurs at least part heavy hydrocarbon containing the material R10F progress hydrogenation reaction R10R that normal boiling point is higher than 530 DEG C of hydrocarbon and adds hydrogen anti- Hydrogenation reaction product R10P should be converted into；

(3) hydrogen rich gas gas SRV is obtained in removal process SU10, returned logistics R10P-X, obtains distributed large-size particles and urges The material that agent BP may contain distributed small size particle catalyst LP, may contain conventional liquid hydrocarbon simultaneously；

It is obtained in the reaction effluent R10-ENDP of the thermal high separation process THPS that may be arranged, recycling hydrogenation process R10 To the hot high score gas of the conventional liquid hydrocarbon containing hydrogen, impurity hydrogenation products, conventional gas hydrocarbon and normal boiling point lower than 350 DEG C THPS-V, obtain being higher than containing dissolution hydrogen, normal boiling point 350 DEG C of conventional liquid hydrocarbon contains distributed beaded catalyst The hot high score liquid THPS-L of R10C；

In the separation fractional distillation process DU10 that may be arranged, the R10C containing catalyst based on hot high score liquid THPS-L, boiling containing routine The hydrogenation reaction that point is higher than 450 DEG C of the hydrocarbon components generates oil R10P-Y, and isolating at least one includes normal boiling point higher than 450 DEG C The narrow fraction DU10-HL of the hydrocarbon component, at least one include narrow fraction DU10-LL of the normal boiling point lower than 450 DEG C of the hydrocarbon component, obtain It is higher than the material DU10-SHL of 450 DEG C of the hydrocarbon components at least one R10C containing catalyst, containing normal boiling point；In point that may be arranged From fractional distillation process DU10, solvent extraction may be used；

It is higher than the material of 450 DEG C of the hydrocarbon components there may be at least part catalyst containing small size particle LP, containing normal boiling point DU10-SHL returns to hydrogenation process R10 circular response；

(3) distributed beaded catalyst may be contained simultaneously in mechanically decoupled process XSX0, distributed large-size particles catalyst BP LP, the XSX0-F containing liquid phase material for being higher than 450 DEG C of the hydrocarbon components containing normal boiling point, are separated at least 2 road materials: rich catalyst feed KSX, the poor catalyst liquid material XSX0-F-LP that gas phase may be contained；

The poor catalyst liquid material XSX0-F-LP that gas phase may be contained is rich in small size particle catalyst LP that may be present；

Recycle the material of machinery separation process XSX0 discharge；

Recycling may contain the poor catalyst liquid material XSX0-F-LP of gas phase, may recycle solid component therein or with non-solid group Point；

Selection 1, the material containing distributed large-size particles catalyst BP based on material KSX, is used as recycle at least partially Expect KSX-TOBRA, by return course KSX-LOOP, returns to floating bed hydrogenation modified-reaction process BRA and pass through at least part Reaction compartment participates in reaction, connects with the charging richness aromatic hydrocarbons wax oil BRAF of floating bed hydrogenation reaction process R10 or its hydro-conversion object Touching；

2 are selected, at least partially the material containing distributed large-size particles catalyst BP based on material KSX, as downstream The XSY0-F containing liquid phase material of concentration and separation process XSY0 containing catalyst material；

Selection 3, the material containing distributed large-size particles catalyst BP based on material KSX at least partially, be used as again to Concentration material KSX2-TOSOLID takes off liquid process SPU10 into solid, deviates from least part hydrocarbon material SPU10-HC, consolidate Bulk concentration higher desiccation material VR-R10C-OUT, at least part desiccation material VR-R10C-OUT are used as distributed large-size particles The outlet material of catalyst BP；

2 that may be present or multiple mechanically decoupled processes XSX0, XSY0 containing catalyst material, it is therefore possible to use serial flow operation；

Selection 6, what the separation hydrogenated oil R10P-OIL that may be present based on hydrogenation reaction effluent R10P was obtained contains liquid Material material is used as material XSX0-F；

Selection 7, what the fractionation hydrogenated oil R10P-OIL that may be present based on hydrogenation reaction effluent R10P was obtained contains liquid Material material is used as material XSX0-F；

Selection 8, in the material containing liquid material of the hydrogenated oil R10P-OIL that may be present based on hydrogenation reaction effluent R10P Separation process, obtain being higher than containing distributed beaded catalyst R10C, containing normal boiling point 450 DEG C of the hydrocarbon components containing colloid or and drip The hydrocarbon-bearing material S888 of green matter, in the solvent extraction and separation process VS-EU using solvent segregation, what is obtained contains distributed particle Catalyst R10C, the material containing liquid material for being higher than 450 DEG C of the hydrocarbon components containing normal boiling point, are used as material XSX0-F；

Selection 9, in the material containing liquid material of the hydrogenated oil R10P-OIL that may be present based on hydrogenation reaction effluent R10P The fractional distillation process using fractionating column, what is obtained is higher than 450 DEG C of the hydrocarbon components containing distributed beaded catalyst R10C, containing normal boiling point Containing colloid or with the hydrocarbon-bearing material S888 of asphalitine, using solvent segregation solvent extraction and separation process VS-EU, obtain The material containing liquid material for being higher than 450 DEG C of the hydrocarbon components containing distributed beaded catalyst R10C, containing normal boiling point, as material XSX0- F；

Selection 2, realizes the filtering of large-size particles catalyst BP, and the large-size particles catalyst BP being collected by filtration is present in richness and urges In agent material KSX.

2. method according to claim 1, it is characterised in that:

(1) in floating bed hydrogenation modified-reaction process BRA, existing dispersing type particle hydrogenation catalyst, including it is easy to mechanical point From large-size particles catalyst BP and that may be present be difficult to mechanically decoupled small size particle catalyst LP；

In floating bed hydrogenation modified-reaction process BRA, there is that when being difficult to mechanically decoupled small size particle catalyst LP, BP is average Partial size is higher than 5 times of LP average grain diameter.

3. method according to claim 1, it is characterised in that:

In floating bed hydrogenation modified-reaction process BRA, exist when being difficult to mechanically decoupled small size particle catalyst LP, small particle The size distribution of beaded catalyst LP is selected from one of the following or several:

The size distribution of large-size particles catalyst BP is selected from one of the following or several:

4. method according to claim 1, it is characterised in that:

In floating bed hydrogenation modified-reaction process BRA, exist when being difficult to mechanically decoupled small size particle catalyst LP, suspension bed In the liquid phase of hydrogenation modification reaction process BRA small size particle catalyst LP there are weight LP-W and liquid phase state hydrocarbon weight Ratio LP-K100, LP-K100=(LP-W)/(YXT-W) of YXT-W is selected from one of the following:

Select 1, LP-K100 0.000500: 1~0.002000: 1；

Select 2, LP-K100 0.002000: 1~0.005000: 1；

Select 3, LP-K100 0.005000: 1~0.020000: 1.

5. method according to claim 1, it is characterised in that:

In the liquid phase of floating bed hydrogenation modified-reaction process BRA large-size particles catalyst BP there are weight BP-W and liquid phase shape Ratio BP-K100, BP-K100=(BP-W)/(YXT-W) of state hydrocarbon weight YXT-W is selected from one of the following:

Select 1, BP-K100 0.000500: 1~0.002000: 1；

Select 2, BP-K100 0.002000: 1~0.005000: 1；

Select 3, BP-K100 0.005000: 1~0.020000: 1；

Select 4, BP-K100 0.020000: 1~0.200000: 1.

6. method according to claim 1, it is characterised in that:

Select 1, LP-K100 0.000500: 1~0.002000: 1；

Select 2, LP-K100 0.002000: 1~0.005000: 1；

Select 3, LP-K100 0.005000: 1~0.020000: 1；

Select 1, BP-K100 0.000500: 1~0.002000: 1；

Select 2, BP-K100 0.002000: 1~0.005000: 1；

Select 3, BP-K100 0.005000: 1~0.020000: 1；

Select 4, BP-K100 0.020000: 1~0.200000: 1.

7. method according to claim 1, it is characterised in that:

In floating bed hydrogenation modified-reaction process BRA, exist when being difficult to mechanically decoupled small size particle catalyst LP, addition The catalyst substrate 100-LP for forming small size particle catalyst LP, using active metal as mete-wand, catalyst substrate 100- Normal boiling point is higher than the weight R10F-KC-W's of 350 DEG C of the hydrocarbon components in the addition weight 100-LP-W and hydrocarbon-bearing material R10F of LP Ratio 100-LP-K100,100-LP-K100=(100-LP-W)/(R10F-KC-W) are selected from one of the following:

Select 1,100-LP-K100 0.000200: 1~0.000500: 1；

Select 2,100-LP-K100 0.000100: 1~0.000200: 1；

Select 3,100-LP-K100 0.000050: 1~0.000100: 1；

Select 4,100-LP-K100 0.000010: 1~0.000050: 1.

8. method according to claim 1, it is characterised in that:

The catalyst substrate 200-BP of the formation large-size particles catalyst BP of addition, using active metal as mete-wand, catalysis Normal boiling point is higher than the weight of 350 DEG C of the hydrocarbon components in the addition weight 200-BP-W and hydrocarbon-bearing material R10F of agent substrate 200-BP Ratio 200-BP-K100,200-BP-K100=(200-BP-W)/(R10F-KC-W) of R10F-KC-W, one in following Kind:

Select 1,200-BP-K100 0.000200: 1~0.000500: 1；

Select 2,200-BP-K100 0.000100: 1~0.000200: 1；

Select 3,200-BP-K100 0.000050: 1~0.000100: 1；

Select 4,200-BP-K100 0.000010: 1~0.000050: 1.

9. method according to claim 1, it is characterised in that:

Select 1,100-LP-K100 0.000200: 1~0.000500: 1；

Select 2,100-LP-K100 0.000100: 1~0.000200: 1；

Select 3,100-LP-K100 0.000050: 1~0.000100: 1；

Select 4,100-LP-K100 0.000010: 1~0.000050: 1；

Select 1,200-BP-K100 0.000200: 1~0.000500: 1；

Select 2,200-BP-K100 0.000100: 1~0.000200: 1；

Select 3,200-BP-K100 0.000050: 1~0.000100: 1；

Select 4,200-BP-K100 0.000010: 1~0.000050: 1.

10. method according to claim 1, it is characterised in that:

11. method according to claim 1, it is characterised in that:

Small size particle catalyst LP that may be present includes at least magnetic iron ore phase Fe1-xS particle；

Large-size particles catalyst BP includes at least magnetic iron ore phase Fe1-xS particle.

12. method according to claim 1, it is characterised in that:

(3) in mechanically decoupled process XSX0, separating effect is to realize dispersing type beaded catalyst R10C in rich catalyst feed KSX In concentration, enriching service method be selected from one of the following or several:

Selection 1, settling methods use settlement separation tank；

13. method according to claim 1, it is characterised in that:

(3) in mechanically decoupled process XSX0, separating effect is the filtering for realizing large-size particles catalyst BP, and what is be collected by filtration is big Particles catalyst BP is present in rich catalyst feed KSX, and filtration method is selected from one of the following or several:

Selection 1, uses granular membrane；

Selection 2, uses key joint web filter；

Selection 3, centrifugal filtration process uses centrifugal filter；

Selection 4, filter press technique uses pressure filter；

Selection 5, vacuum filtration process uses vacuum filter.

14. method according to claim 1, it is characterised in that:

(3) in mechanically decoupled process XSX0, the BP of catalyst containing large-size particles, it is higher than containing for 450 DEG C of the hydrocarbon components containing normal boiling point Liquid phase material XSX0-F is selected from one of the following or several:

15. method according to claim 1, it is characterised in that；

(3) in mechanically decoupled process XSX0, the BP of catalyst containing large-size particles, it is higher than containing for 450 DEG C of the hydrocarbon components containing normal boiling point Liquid phase material XSX0-F is separated at least 2 road materials: rich catalyst feed KSX, the poor catalyst liquid material that may contain gas phase XSX0-F-LP；

In mechanically decoupled process XSX0, the hydrocyclone or device fixed using centrifugal settling method, use device are rotated heavy Centrifuge drops, and separating effect is selected from one of the following or several:

1. by weight, 50% or more of the distributed beaded catalyst R10C in material XSX0-F, is enriched in rich catalyst In material KSX；

2. by weight, 80% or more of the distributed beaded catalyst R10C in material XSX0-F, is enriched in rich catalyst In material KSX；

3. by weight, 95% or more of the distributed beaded catalyst R10C in material XSX0-F, is enriched in rich catalyst In material KSX；

4. by weight, 99% or more of the distributed beaded catalyst R10C in material XSX0-F, is enriched in rich catalyst In material KSX；

5. by weight, 99.9% or more of the distributed beaded catalyst R10C in material XSX0-F, is enriched in rich catalysis In agent material KSX.

16. method according to claim 1, it is characterised in that:

17. method according to claim 1, it is characterised in that:

1. the grain diameter of 50% or more ratio is greater than 10.0 microns of large-size particles catalyst BP, into rich catalyst feed In KSX；

2. the grain diameter of 50% or more ratio is greater than 3.00 microns of large-size particles catalyst BP, into rich catalyst feed In KSX；

3. the grain diameter of 50% or more ratio is greater than 1.00 microns of large-size particles catalyst BP, into rich catalyst feed In KSX；

4. the grain diameter of 50% or more ratio is greater than 0.50 micron of large-size particles catalyst BP, into rich catalyst feed In KSX；

5. the grain diameter of 50% or more ratio is greater than 0.20 micron of large-size particles catalyst BP, into rich catalyst feed In KSX.

18. method according to claim 1, it is characterised in that:

19. method according to claim 1, it is characterised in that:

20. method according to claim 1, it is characterised in that:

(3) in mechanically decoupled process XSX0, it is higher than 450 DEG C of the hydrocarbon components containing distributed beaded catalyst R10C, containing normal boiling point XSX0-F containing liquid phase material is separated at least 2 road materials: rich catalyst feed KSX, the poor catalyst liquid material that may contain gas phase XSX0-F-LP；

In mechanically decoupled process XSX0, using centrifugal filtration process, using centrifugal filter, separating effect is selected from one of the following Or it is several:

1. intercepted grain diameter is greater than 10.0 microns of large-size particles catalyst BP, into rich catalyst feed KSX；

2. intercepted grain diameter is greater than 3.00 microns of large-size particles catalyst BP, into rich catalyst feed KSX；

3. intercepted grain diameter is greater than 1.00 microns of large-size particles catalyst BP, into rich catalyst feed KSX；

4. intercepted grain diameter is greater than 0.20 micron of large-size particles catalyst BP, into rich catalyst feed KSX；

5. intercepted grain diameter is greater than 0.05 micron of large-size particles catalyst BP, into rich catalyst feed KSX.

21. method according to claim 1, it is characterised in that:

(3) in mechanically decoupled process XSX0, the BP of catalyst containing large-size particles, it is higher than containing for 450 DEG C of the hydrocarbon components containing normal boiling point Liquid phase material XSX0-F, the operation temperature of material XSX0-F are selected from one of the following or several:

1. 120~200 DEG C；

2. 200~250 DEG C；

3. 250~300 DEG C；

4. 300~350 DEG C；

5. 350~400 DEG C；

6. 400~450 DEG C.

22. method according to claim 1, it is characterised in that:

(3) in mechanically decoupled process XSX0, the BP of catalyst containing large-size particles, it is higher than containing for 450 DEG C of the hydrocarbon components containing normal boiling point The component of large-size particles catalyst BP in liquid phase material XSX0-F, material XSX0-F is selected from one of the following or several:

1. the sulfide of molybdenum；

2. the sulfide of iron；

3. the sulfide of nickel；

4. the sulfide of vanadium；

5. the sulfide of tungsten.

23. method according to claim 1, it is characterised in that:

(3) in mechanically decoupled process XSX0, the BP of catalyst containing large-size particles, it is higher than containing for 450 DEG C of the hydrocarbon components containing normal boiling point The size distribution of large-size particles catalyst BP in liquid phase material XSX0-F, material XSX0-F, selected from one of the following or It is several:

24. method according to claim 1, it is characterised in that:

(1) in hydrogenation process R10, a floating bed hydrogenation reactor is at least used；In floating bed hydrogenation reactor It is molybdenum disulfide MoS there are body of work form in liquid phase₂Molybdenum base particle dispersion hydrogenation catalyst large-size particles catalysis Agent BP；

25. method according to claim 1, it is characterised in that:

(3) in mechanically decoupled process XSX0, it is higher than 450 DEG C of hydrocarbon groups by isolated large-size particles catalyst BP, containing normal boiling point The XSX0-F containing liquid phase material divided, selected from one or more of following materials:

Selection 3, the liquid material that the intermediate reaction product of separation floating bed hydrogenation reaction process R10 obtains, is used as material XSX0-F；

Selection 6, the liquid material that the final reacting product of separation floating bed hydrogenation reaction process R10 obtains, is used as material XSX0-F；

Selection 8, it is understood that there may be hot high score liquid THPS-L the obtained hot low liquid separation body TLPS-L of decompression flash process, be used as Material XSX0-F；

Low point of gas TLPS-V of heat and the low liquid separation body of heat are separated into heat low separation process TLPS, hot high score liquid THPS-L TLPS-L；

Selection 9, in the decompression flash separation without using fractionating column of hot high score liquid THPS-L that may be present, obtains Based on hot high score liquid THPS-L be higher than 450 DEG C of the hydrocarbon components containing distributed beaded catalyst R10C, containing normal boiling point contain liquid Material material is used as material XSX0-F；

Selection 10, in the decompression flash separation without using fractionating column of hot high score liquid THPS-L that may be present, obtains Based on hot high score liquid THPS-L containing distributed beaded catalyst R10C, containing normal boiling point be higher than 450 DEG C of the hydrocarbon components liquid Material is used as material XSX0-F；

Selection 11, in the fractional distillation process using fractionating column of hot high score liquid THPS-L that may be present, obtain based on containing point Dispersing granule catalyst R10C, the material containing liquid material for being higher than 450 DEG C of the hydrocarbon components containing normal boiling point, are used as material XSX0-F；

Selection 12, in the fractional distillation process using fractionating column of hot high score liquid THPS-L that may be present, obtain based on containing point Dispersing granule catalyst R10C, the liquid material for being higher than 450 DEG C of the hydrocarbon components containing normal boiling point, it may be possible to which fractionating column feeds flash tank tank bottom Flash oil or fractionation after the heating of the decompression flash oil or fractionation column base oil of oil or fractionation column base oil or fractionation column base oil The air lift flash oil of tower tower bottom oil is used as material XSX0-F；

Selection 13, in the fractional distillation process using fractionating column of hot high score liquid THPS-L that may be present, what is obtained contains dispersing type Beaded catalyst R10C, be higher than containing normal boiling point 450 DEG C of the hydrocarbon components containing colloid or with the hydrocarbon-bearing material S888 of asphalitine, adopting With the solvent extraction and separation process VS-EU of solvent segregation, it is separated into light phase material VS-EU-L and heavy phase material VS-EU-H；

It is isolated after being mixed with extractant in extraction separation process VS-EU, material S888 containing extractant, containing low relative molecular The liquid material VS-EU-ML of light phase containing agent for measuring the hydrocarbon component is isolated containing extractant, the hydrocarbon component containing relatively high molecular weight, enrichment dispersion The liquid material of heavy phase containing the agent VS-EU-MH of type beaded catalyst R10C；

Selection 14, in the fractional distillation process using fractionating column of hot high score liquid THPS-L that may be present, what is obtained contains dispersing type Beaded catalyst R10C, be higher than containing normal boiling point 450 DEG C of the hydrocarbon components containing colloid or with the hydrocarbon-bearing material S888 of asphalitine, adopting With the solvent extraction and separation process VS-EU of solvent segregation, it is separated into light phase material VS-EU-L and heavy phase material VS-EU-H；

In the fractional distillation process of the liquid material of heavy phase containing the agent VS-EU-MH of distillation abjection extractant, the liquid material VS-EU-MH of heavy phase containing agent steams Become heavy phase material VS-EU-H after evaporating removing extractant；

At least part heavy phase material VS-EU-H is used as material XSX0-F；

Selection 15, in the fractional distillation process using fractionating column of hot high score liquid THPS-L that may be present, what is obtained contains dispersing type Beaded catalyst R10C, be higher than containing normal boiling point 450 DEG C of the hydrocarbon components containing colloid or with the hydrocarbon-bearing material S888 of asphalitine, adopting With the solvent extraction and separation process VS-EU of solvent segregation, it is separated into light phase material VS-EU-L and heavy phase material VS-EU-H；

In extraction separation process VS-EU, material S888 and extractant be mixed into after mixture QQ77 isolate containing extractant, The liquid material VS-EU-ML of the light phase containing agent of the hydrocarbon component containing relatively low molecular weight, is isolated containing extractant, hydrocarbon containing relatively high molecular weight Component, the liquid material of heavy phase containing the agent VS-EU-MH for being enriched with distributed beaded catalyst R10C；

At least part mixture QQ77 is used as material XSX0-F.

26. method according to claim 1, it is characterised in that:

(2) in removal process SU10, in the use of the generation oil of the reaction effluent R10-ENDP of recycling hydrogenation process R10 The fractional distillation process of fractionating column, obtained large-size particles catalyst BP, be higher than containing normal boiling point 450 DEG C of the hydrocarbon components containing colloid or With the hydrocarbon-bearing material S888 of asphalitine, using solvent segregation solvent extraction and separation process VS-EU, obtained object containing liquid material Material, the feed material XSX0-F as mechanically decoupled process XSX0；

The method that light liquid phase and heavy-fluid phase are isolated using the separation process VS-EU of solvent segregation, a kind in following or It is several:

27. method according to claim 1, it is characterised in that:

In mechanically decoupled process XSX0, worked using centrifuge separation principle, a kind in following of working method:

Selection 3, centrifugal filtration process uses centrifugal filter；

In mechanically decoupled process XSX0, worked using centrifuge separation principle, the series of step with centrifugal separation, 1 in following Kind:

1. level-one partition method；

28. method according to claim 1, it is characterised in that:

In mechanically decoupled process XSX0, worked using centrifuge separation principle, the series of step with centrifugal separation is two-stage, containing 2 from Heart separating step, a kind in following of working method:

1. material XSX0-F is separated into 2 road materials: the first rich large-size particles catalysis in first order step with centrifugal separation XSX0-1 The XSX0-1-BTM containing liquid phase material of agent BP, may contain gas phase the first poor large-size particles catalyst BP containing liquid phase material XSX0-1-TOP；

In second level step with centrifugal separation XSX0-2, the XSX0-1-TOP containing liquid phase material of the first poor large-size particles catalyst BP It is separated into 2 road materials: the second of gas phase the XSX0-2-BTM containing liquid phase material of the second rich large-size particles catalyst BP, may be contained The XSX0-2-TOP containing liquid phase material of poor large-size particles catalyst BP；

The XSX0-1-BTM containing liquid phase material of first rich large-size particles catalyst BP at least partially, is used as rich catalyst feed KSX；

At least part may contain the XSX0-2-TOP containing liquid phase material of the second poor large-size particles catalyst BP of gas phase, be used as The poor large-size particles catalyst BP liquid material XSX0-F-LP of gas phase may be contained；

There may be the XSX0-2-BTM containing liquid phase material of the rich large-size particles catalyst BP of at least part second, return to the first order Step with centrifugal separation XSX0-1 multi-cycle separation；

2. material XSX0-F is separated into 2 road materials: the first rich large-size particles catalysis in first order step with centrifugal separation XSX0-A The XSX0-A-BTM containing liquid phase material of agent BP, may contain gas phase the first poor large-size particles catalyst BP containing liquid phase material XSX0-A-TOP；

In second level step with centrifugal separation XSX0-B, the XSX0-A-BTM containing liquid phase material of the first rich large-size particles catalyst BP It is separated into 2 road materials: the second of gas phase the XSX0-B-BTM containing liquid phase material of the second rich large-size particles catalyst BP, may be contained The XSX0-B-TOP containing liquid phase material of poor large-size particles catalyst BP；

The XSX0-B-BTM containing liquid phase material of second rich large-size particles catalyst BP at least partially, is used as rich large-size particles Catalyst BP material KSX；

At least part may contain the XSX0-A-TOP containing liquid phase material of the first poor large-size particles catalyst BP of gas phase, be used as The poor large-size particles catalyst BP liquid material XSX0-F-LP of gas phase may be contained；

There may be at least part that may contain the XSX0-B- containing liquid phase material of the second poor large-size particles catalyst BP of gas phase TOP returns to first order step with centrifugal separation XSX0-A multi-cycle separation.

29. method according to claim 1, it is characterised in that:

(3) in mechanically decoupled process XSX0, the BP of catalyst containing large-size particles, it is higher than containing for 450 DEG C of the hydrocarbon components containing normal boiling point Liquid phase material XSX0-F is separated at least 2 road materials: rich large-size particles catalyst BP material KSX, may contain the poor big of gas phase Particles catalyst BP liquid material XSX0-F-LP；

In mechanically decoupled process XSX0, worked using centrifuge separation principle, the series of step with centrifugal separation is three-level, containing 3 from Heart separating step, a kind in following of working method:

In third level step with centrifugal separation XSX0-3A, may contain the second poor large-size particles catalyst BP of gas phase contains liquid phase Material XSX0-2-TOP is separated into 2 road materials: the XSX0-3A-BTM containing liquid phase material of third richness large-size particles catalyst BP, The XSX0-3A-TOP containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase may be contained；

The XSX0-1-BTM containing liquid phase material of first rich large-size particles catalyst BP at least partially, is used as rich large-size particles Catalyst BP material KSX；

At least part may contain the XSX0-3A-TOP containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase, use Make the poor large-size particles catalyst BP liquid material XSX0-F-LP that may contain gas phase；

There may be the XSX0-2-BTM containing liquid phase material of the rich large-size particles catalyst BP of at least part second, be used as rich big grain Diameter beaded catalyst BP material KSX；

There may be the XSX0-3A-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, be used as rich big Particles catalyst BP material KSX；

There may be the XSX0-3A-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, return to first Grade step with centrifugal separation XSX0-1 multi-cycle separation；

There may be the XSX0-3A-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, return to second Grade step with centrifugal separation XSX0-2 multi-cycle separation；

2. material XSX0-F is separated into 2 road materials: the first rich large-size particles catalysis in first order step with centrifugal separation XSX0-1 The XSX0-1-BTM containing liquid phase material of agent BP, may contain gas phase the first poor large-size particles catalyst BP containing liquid phase material XSX0-1-TOP；

In third level step with centrifugal separation XSX0-3B, the XSX0-2- containing liquid phase material of the second rich large-size particles catalyst BP BTM is separated into 2 road materials: the XSX0-3B-BTM containing liquid phase material of third richness large-size particles catalyst BP, may contain gas phase The XSX0-3B-TOP containing liquid phase material of the poor large-size particles catalyst BP of third；

At least part may contain the XSX0-3B-TOP containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase, use Make the poor large-size particles catalyst BP liquid material XSX0-F-LP that may contain gas phase；

At least part may contain the XSX0-3B-TOP containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase, return Return first order step with centrifugal separation XSX0-1 multi-cycle separation；

At least part may contain the XSX0-3B-TOP containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase, return Return second level step with centrifugal separation XSX0-2 multi-cycle separation；

There may be the XSX0-3B-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, be used as rich big Particles catalyst BP material KSX；

There may be the XSX0-3B-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, return to first Grade step with centrifugal separation XSX0-1 multi-cycle separation；

There may be the XSX0-B3A-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, return to second Grade step with centrifugal separation XSX0-2 multi-cycle separation；

3. material XSX0-F is separated into 2 road materials: the first rich large-size particles catalysis in first order step with centrifugal separation XSX0-A The XSX0-A-BTM containing liquid phase material of agent BP, may contain gas phase the first poor large-size particles catalyst BP containing liquid phase material XSX0-A-TOP；

In third level step with centrifugal separation XSX0-C1, the XSX0-B- containing liquid phase material of the second rich large-size particles catalyst BP BTM is separated into 2 road materials: the XSX0-C1-BTM containing liquid phase material of third richness large-size particles catalyst BP, may contain gas phase The XSX0-C1-TOP containing liquid phase material of the poor large-size particles catalyst BP of third；

The XSX0-C1-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP is used as rich big partial size Grain catalyst BP material KSX；

There may be at least part that may contain the XSX0-B- containing liquid phase material of the second poor large-size particles catalyst BP of gas phase TOP, as the poor large-size particles catalyst BP liquid material XSX0-F-LP that may contain gas phase；

There may be at least part that may contain the XSX0-B- containing liquid phase material of the second poor large-size particles catalyst BP of gas phase TOP returns to first order step with centrifugal separation XSX0-A multi-cycle separation；

There may be at least part that may contain the XSX0-C1- containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase TOP returns to first order step with centrifugal separation XSX0-A multi-cycle separation；

There may be at least part that may contain the XSX0-C1- containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase TOP returns to second level step with centrifugal separation XSX0-B multi-cycle separation；

4. material XSX0-F is separated into 2 road materials: the first rich large-size particles catalysis in first order step with centrifugal separation XSX0-A The XSX0-A-BTM containing liquid phase material of agent BP, may contain gas phase the first poor large-size particles catalyst BP containing liquid phase material XSX0-A-TOP；

In third level step with centrifugal separation XSX0-C2, may contain the second poor large-size particles catalyst BP of gas phase contains liquid phase Material XSX0-B-TOP is separated into 2 road materials: the XSX0-C2-BTM containing liquid phase material of third richness large-size particles catalyst BP, The XSX0-C2-TOP containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase may be contained；

At least part may contain the XSX0-B-TOP containing liquid phase material of the second poor large-size particles catalyst BP of gas phase, return First order step with centrifugal separation XSX0-A multi-cycle separation；

At least part may contain the XSX0-C2-TOP containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase, use Make the poor large-size particles catalyst BP liquid material XSX0-F-LP that may contain gas phase；

At least part may contain the XSX0-C2-TOP containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase, return Return first order step with centrifugal separation XSX0-A multi-cycle separation；

At least part may contain the XSX0-C2-TOP containing liquid phase material of the poor large-size particles catalyst BP of third of gas phase, return Return second level step with centrifugal separation XSX0-B multi-cycle separation；

There may be the XSX0-C2-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, be used as rich big Particles catalyst BP material KSX；

There may be the XSX0-C2-BTM containing liquid phase material of at least part third richness large-size particles catalyst BP, return to first Grade step with centrifugal separation XSX0-A multi-cycle separation；

May have an XSX0-C2-BTM containing liquid phase material of at least part third richness beaded catalyst R10C, return the second level from Heart separating step XSX0-B multi-cycle separation.

30. method according to claim 1, it is characterised in that:

The preprocessing process of material XSX0-F is set, a kind in following of working method:

1. the flash liberation process of material XSX0-F is separated into degassing oil, flashed vapour, obtained degassing oil enters mechanically decoupled mistake Journey XSX0；

2. material XSX0-F in air lift flash process, contacted with gas stripping gas make part low boiling component vaporize, be separated into degassing oil, Air lift flashed vapour, obtained degassing oil enter mechanically decoupled process XSX0；

Part low boiling component is vaporized 3. material XSX0-F first passes through heating up process, is then separated in flash liberation process For degassing oil, flashed vapour, obtained degassing oil enters mechanically decoupled process XSX0；

The temperature of material is set to become supercooling liquid material lower than bubble point temperature 4. material XSX0-F first passes through the process of cooling, then mistake Cold liquid material enters mechanically decoupled process XSX0.

31. method according to claim 1, it is characterised in that:

In a mechanically decoupled step, separated using at least dividing the separative unit packaging type that parallel operation forms rotation to divide by 2 rotations Device.

32. method according to claim 1, it is characterised in that:

In a mechanically decoupled step, separated using at least dividing the separative unit packaging type that parallel operation forms rotation to divide by 2 rotations Device, working method, a kind or several in following:

2. using packaging shell, by 2 or multiple rotations divide separative unit, are installed in parallel, and constitute charging distributor chamber, underflow collects Room, top stream merging chamber；

Underflow merging chamber is connected to positioned at the side of charging distributor chamber, and with the corresponding underflow total material discharge gate for leaving packaging shell；

Top stream merging chamber positioned at the other side of charging distributor chamber, and flows total material discharge gate with the corresponding top for leaving packaging shell and connects It is logical；

3. using packaging shell, by 2 or multiple rotations divide separative unit, are installed in parallel, and constitute charging distributor chamber, underflow collects Room, top stream merging chamber；

Underflow merging chamber is connected to positioned at the center of packaging shell, and with the discharge gate for the underflow total material for leaving packaging shell；

4. using packaging shell, by 2 or multiple rotations divide separative unit, are installed in parallel, and constitute charging distributor chamber, underflow collects Room, top stream merging chamber；

Top stream merging chamber is connected to positioned at the center of packaging shell, and with the discharge gate for the top stream total material for leaving packaging shell.

33. method according to claim 1, it is characterised in that:

In a mechanically decoupled step, divide separator using rotation, the rotation used divides the work shape of the separation axis of cone line of separative unit The mounting means of state, a kind or several in following:

1. being horizontally mounted；

2. right angle setting；

3. inclination installation, i.e., separation axis of cone line working condition and horizontal plane angle, neither 0 degree angle, be also not an angle of 90 degrees.

34. method according to claim 1, it is characterised in that:

Divide process XSX0 in rotation, the rotation used divides separative unit, is manufactured with wear-resistant material or makees liner using wear-resistant material.

35. method according to claim 1, it is characterised in that:

Hydrocarbon-bearing material R10F is the material for being higher than 450 DEG C of the hydrocarbon components comprising normal boiling point, is selected from one of following materials or several Kind:

Option 1, the high hydrocarbon ils of gluey pitch shape constituent content；

Option 2, the high hydrocarbon ils of content of ashes；

Option 3, the high hydrocarbon ils of easy coking constituent content；

Option 5, the hydrocarbon ils of high aromatic carbon rate.

36. method according to claim 1, it is characterised in that:

37. method according to claim 1, it is characterised in that:

Option 1, the hydrocarbon material based on coalite tar are coalite tar or its distillate or its extraction oil or its hot procedure Gained oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis mistake Journey；

Option 2, the hydrocarbon material based on medium temperature coal tar are medium temperature coal tar or its distillate or its extraction oil or its hot procedure Gained oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis mistake Journey；

Option 3, the hydrocarbon material based on high temperature coal-tar are high temperature coal-tar or its distillate or its extraction oil or its hot procedure Gained oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis mistake Journey；

Option 4, based on the hydrocarbon material of direct hydrogenation liquefaction of coal product oil, be oil product obtained by direct hydrogenation liquefaction of coal liquefaction process or its Oil product obtained by extraction oil or its hot procedure, direct hydrogenation liquefaction of coal liquefaction process includes the coal hydrogenation using hydrogen supply dissolvent oil Direct liquefaction liquefaction process, coal refines process to oil altogether, coal faces hydrogen thermosol liquefaction process, and hot procedure is distillation process or thermal cracking Process or coking or catalytic cracking process or catalytic pyrolysis process；

Option 5, the hydrocarbon material based on petroleum based heavy fuel oils are petroleum based heavy fuel oils or its distillate or its extraction oil or its hot procedure Gained oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis mistake Journey；

Oil product obtained by option 6, the hydrocarbon material based on shale oil, shale oil or its distillate or its extraction oil or its hot procedure, Hot procedure is distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis process；

Option 7 is tar sand base weight oil or its distillate or its extraction oil or its hot-working based on the hydrocarbon material of tar sand base weight oil Oil product obtained by process, hot procedure are that distillation process or thermal cracking process or coking or catalytic cracking process or catalysis are split Solution preocess；

Option 8, the hydrogenation process of ethylene cracking tar；

38. method according to claim 1, it is characterised in that:

Take off solid particle step in guide, finally enter floating bed hydrogenation modified-reaction process BRA or with hydrogenation process R10 Material or its precursor, first deviate from the minimum grain size that granularity is equal to the large-size particles catalyst BP that is easy to mechanically decoupled Particle obtains poor granule materials, then poor granule materials enter floating bed hydrogenation modified-reaction process BRA or with hydrogenation reaction mistake Journey R10.

39. method according to claim 1, it is characterised in that:

Take off solid particle step in guide, finally enter floating bed hydrogenation modified-reaction process BRA or with hydrogenation process R10 Material or its precursor, first deviate from granularity be less than be easy to mechanically decoupled large-size particles catalyst BP minimum grain size Grain obtains poor granule materials, and then poor granule materials enter floating bed hydrogenation modified-reaction process BRA or and hydrogenation process R10。

40. method according to claim 1, it is characterised in that:

Take off solid particle step in guide, finally enter floating bed hydrogenation modified-reaction process BRA or with hydrogenation process R10 Material or its precursor, first deviate from the minimum grain size that granularity is equal to the large-size particles catalyst BP that is easy to mechanically decoupled The particle of 50% partial size obtains poor granule materials, then poor granule materials enter floating bed hydrogenation modified-reaction process BRA or and Hydrogenation process R10.

41. method according to claim 1, it is characterised in that:

(2) hydrogen rich gas gas SRV is obtained in removal process SU10, returned logistics R10-ENDP, obtained containing conventional liquid hydrocarbon Material containing distributed beaded catalyst R10C；

At least part hydrogen rich gas gas SRV enters floating bed hydrogenation modified-reaction process BRA or makees with hydrogenation process R10 It is used for hydrogen rich gas SRV-RH bis- times；

The reaction effluent R10-ENDP of the hydrogenation process R10, with 1 tunnel or 2 tunnels or the shape of multichannel material R10-ENDP Formula occurs, and the composition and phase of different R10-ENDP logistics are identical or different.

42. method according to claim 1, it is characterised in that:

(2) hydrogen rich gas gas SRV, at least part hydrogen rich gas gas are obtained in removal process SU10, returned logistics R10-ENDP SRV enters floating bed hydrogenation modified-reaction process BRA or with hydrogenation process R10 as hydrogen rich gas SRV-RH bis- times uses；

43. method according to claim 1, it is characterised in that:

In removal process SU10, thermal high separation process THPS is set；

It obtains in thermal high separation process THPS, returned logistics R10-ENDP containing hydrogen, impurity hydrogenation products, conventional gas hydrocarbon It is lower than the hot high score gas THPS-V of 350 DEG C of conventional liquid hydrocarbon with normal boiling point and is higher than containing dissolution hydrogen, normal boiling point The possibility of 350 DEG C of conventional liquid hydrocarbon contains the hot high score liquid THPS-L of solid particle；

In thermal high separation process THPS, for the hot high score isolated based on hydrogenation process R10 effluent R10-ENDP Gas BASE-THPS-V, setting gas phase take off the liquid scrubbing settling section DWU66 of solid, obtain the lower gas of solid content；

The liquid scrubbing settling section DWU66 of solid is taken off in gas phase, at least part cleaning solution that may be used is condensation based on heat The lime set that the logistics of high score gas THPS-V obtains.

44. method according to claim 1, it is characterised in that:

The component materials BRAF of wax oil containing aryl of floating bed hydrogenation modified-reaction process BRA processing is rich in aryl wax oil component Material.

45. method according to claim 1, it is characterised in that:

The hydrogen supply hydrocarbon total amount concentration of hydro carbons in floating bed hydrogenation modified-reaction process BRA, hydrogenation modification reaction product BRAP, than The hydrogen supply hydrocarbon total amount concentration of hydro carbons in the component materials of wax oil containing aryl BRAF improves DATA10, is selected from one of the following:

Selection 1 is greater than 5%；

Selection 2 is greater than 10%；

Selection 3 is greater than 15%:

Selection 4 is greater than 20%；

Selection 5 is greater than 25%；

Selection 6 is greater than 35%；

Selection 7 is greater than 45%；

Selection 8 is greater than 55%；

Normal boiling point in floating bed hydrogenation modified-reaction process BRA, hydrogenation modification reaction product BRAP is higher than 350 DEG C of hydrocarbon The heat from hydrogenation cracking weight conversion rate of component is selected from one of the following:

Selection 1, less than 5%；

Selection 2, less than 10%；

Selection 3, less than 15%；

Selection 4, less than 20%；

Selection 5, less than 25%；

Selection 6, less than 30%；

Selection 7, less than 35%；

Selection 8, less than 40%.

46. method according to claim 1, it is characterised in that:

Normal boiling point in the process U100 of hydrocarbon-bearing material R10F, hydrocarbon-bearing material R10F is higher than adding for 530 DEG C of the hydrocarbon component Hydrogen thermal cracking weight conversion rate is selected from one of the following:

Selection 1 is greater than 25%；

Selection 2 is greater than 40%；

Selection 3 is greater than 55%；

Selection 4 is greater than 70%；

Selection 5 is greater than 85%；

Selection 6 is greater than 95%；

Selection 7 is greater than 96%；

Selection 8 is greater than 97%；

Selection 9 is greater than 98%；

Selection 10 is greater than 99%.

47. method according to claim 1, it is characterised in that:

(2) in floating bed hydrogenation reaction process R10, the material R10F of hydrogen supply hydrocarbon material DSF and the HAC of component containing high boiling hydrocarbon are used Or in which the working method of hydrogenation products contact, it is selected from one of the following or several:

Option 1, the weight concentration absolute value of hydrogen supply the hydrocarbon component DS is higher than the HAC's of component containing high boiling hydrocarbon in hydrogen supply hydrocarbon material DSF The weight concentration absolute value at least 10% of hydrogen supply the hydrocarbon component DS in material R10F；

Option 2, hydrogen supply hydrocarbon material DSF are mainly that 250~530 DEG C of hydro carbons form by normal boiling point, part saturation aromatic hydrocarbons It is 0.35~0.70 that weight content, which is greater than 15%, aromatic carbon rate,；

Option 3, the weight flow of hydrogen supply hydrocarbon material DSF and the ratio between the weight flow of high boiling hydrocarbon component HAC in material R10F are 0.05~4.0；

Option 6, high boiling hydrocarbon component HAC in the weight flow of hydrogen supply dissolvent component DS and material R10F in hydrogen supply hydrocarbon material DSF The ratio between weight flow be 0.05~2.0.

48. method according to claim 1, it is characterised in that:

(2) in floating bed hydrogenation reaction process R10, the material R10F of hydrogen supply hydrocarbon material DSF and the HAC of component containing high boiling hydrocarbon are used Or in which hydrogenation products contact；

Based on the hydrogen material of stabilized hydrogenation reaction process MR, it is used in series into hydrogenation process R10；

For producing the stabilized hydrogenation reaction process MR raw material MRF of hydrogen supply hydrocarbon material DSF, separation hydrogenation process may include R10 effluent R10-ENDP obtains hydrocarbon-bearing material.

49. method according to claim 1, it is characterised in that:

In removal process SU10, thermal high separation process THPS is set；

Based on the hydrogen material of hot high score gas THPS-V, it is used in series into stabilized hydrogenation reaction process MR；

50. method according to claim 1, it is characterised in that:

(1) in floating bed hydrogenation modified-reaction process BRA, the absolute value ratio component of wax oil containing aryl of the aromatic carbon rate of the dilution hydrocarbon The absolute value at least low 0.1 of the aromatic carbon rate of material BRAF；

(2) in floating bed hydrogenation reaction process R10, aromatic carbon rate of the absolute value than material R10F of the aromatic carbon rate of the dilution hydrocarbon Absolute value at least low 0.1.

51. method according to claim 1, it is characterised in that:

Dilution hydrocarbon WWF is mainly made of the hydrocarbon component that normal boiling point is 250~350 DEG C.

52. method according to claim 1, it is characterised in that:

In removal process SU10, thermal high separation process THPS is set；

Hydrogen, hydrocarbonaceous oil material based on hot high score gas THPS-V, into adding hydrogen upgrading reaction process HT66 to carry out plus hydrogen HT66-R is reacted in upgrading, is converted into and adds hydrogen upgrading reaction product HT66-P；

Hydrogen upgrading is added to react HT66-R, including hydrogenated olefin saturated reaction, hydrodesulfurization reaction, hydrodenitrogeneration reaction plus hydrogen virtue One or more of hydrocarbon saturated reaction, hydrocracking reaction, hygrogenating isomerization reaction；

Recycling plus hydrogen upgrading reaction product HT66-P.

53. method according to claim 1, it is characterised in that:

In removal process SU10, thermal high separation process THPS is set；

Condense and separate the degassing hydrocarbonaceous oil material that hot high score gas THPS-V is obtained, into add hydrogen upgrading reaction process HT66 carry out Add hydrogen upgrading to react HT66-R, is converted into and adds hydrogen upgrading reaction product HT66-P；

Recycling plus hydrogen upgrading reaction product HT66-P.

54. method according to claim 1, it is characterised in that:

In removal process SU10, thermal high separation process THPS is set；

Recycling plus hydrogen upgrading reaction product HT66-P.

55. method according to claim 1, it is characterised in that:

In removal process SU10, thermal high separation process THPS is set；

In separation fractional distillation process, at least part for the narrow fraction oil that heat of dissociation high score liquid THPS-L is obtained, is returned plus hydrogen is anti- The starting position or middle position for answering the reaction process of process R10 carry out circulation plus hydrogen.

56. method according to claim 1, it is characterised in that:

In removal process SU10, thermal high separation process THPS is set；

In separation fractional distillation process, what what heat of dissociation high score liquid THPS-L was obtained mainly formed by wax oil component or with residue fraction At least part of narrow fraction hydrocarbon material returns to the starting position or middle position of the reaction process of hydrogenation process R10, carries out Circulation plus hydrogen.

57. method according to claim 1, it is characterised in that:

(2) in floating bed hydrogenation reaction process R10, sub- hydroconversion reaction zone R10-1, R10-2 comprising 2 or multiple serial operations Deng at this point, the logistics comprising at least part conventional liquid hydrocarbon of the reaction effluent based on upper alien hydroconversion reaction zone enters The adjacent sub- hydroconversion reaction zone in downstream, the first sub- hydroconversion reaction zone R10-1 obtain reaction effluent R10-1P, are based on reaction effluent The logistics R10-1PX comprising at least part hydrogenated oil R10-1PO of R10-1P enters the second sub- hydroconversion reaction zone R10- 2, the reaction effluent of last sub- hydroconversion reaction zone is used as reaction effluent R10P；

Material R10F is divided into the sub- hydroconversion reaction zone of difference that at least 2 tunnel branch raw materials enter serial operation.

58. according to the method described in claim 1, it is characterized by:

(2) in floating bed hydrogenation reaction process R10, the initial additive of existing dispersing type particle hydrogenation catalyst R10C is Nanometer ultra-fine grain aqua oxidation iron catalyst, iron oxide, pyrite, bloodstone, molybdenum oxide, molybdenum sulfide, ammonium molybdate, nickel sulfide One or more of.

59. method according to claim 1, it is characterised in that:

(2) in floating bed hydrogenation reaction process R10, using floating bed hydrogenation reactor, the hydrogenation catalyst R10C used, is one Kind composite hydrogenation catalyst, includes high-activity component and low activity component；The high-activity component metal and low activity component The weight ratio of metal is 1: 10 to 10: 1；The high-activity component is or mixtures thereof the water soluble salt compound of molybdenum；It is described Low activity group is divided into ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, catalyst R10C water Content is lower than 2wt%；The powdered granule that R10C particle diameter is 1~100 μm；

The operating condition of hydrogenation process R10 are as follows: temperature is 300~480 DEG C, pressure is 4.0~30.0MPa, hydrogen/raw material Oil volume ratio be 0.01: 1~4000: 1, hydrogenation catalyst R10C there are the materials that weight is the HAC of component containing high boiling hydrocarbon R10F weight 0.001%~8.0%, volume space velocity be 0.1~10.0hr^-1；The material R10F weight of the HAC of component containing high boiling hydrocarbon It is 0.05%~4.0% that hydrogen consumption is learned in quantization.

60. method according to claim 1, it is characterised in that:

(2) in floating bed hydrogenation reaction process R10, using floating bed hydrogenation reactor, the hydrogenation catalyst R10C used, at least Comprising Mo element, Mo is molybdenum disulfide MoS in the body of work form of hydrogenation process R10₂, hydrogenation catalyst R10C is 0.0001~100 μm of powdered granule；

The operating condition of hydrogenation process R10 are as follows: temperature is 360~460 DEG C, pressure is 6.0~22.0MPa, hydrogen/raw material Oil volume ratio be 50: 1~2000: 1, hydrogenation catalyst R10C there are the material R10F that weight is the HAC of component containing high boiling hydrocarbon Weight 0.001%~5.0%, volume space velocity be 0.2~5.0hr^-1；The material R10F of the HAC of component containing high boiling hydrocarbon is re-quantization Learning hydrogen consumption is 0.25%~3.0%.

61. method according to claim 1, it is characterised in that:

The operating condition of hydrogenation process R10 are as follows: temperature is 360~460 DEG C, pressure is 8.0~16.0MPa, hydrogen/raw material Oil volume ratio be 200: 1~1200: 1, hydrogenation catalyst R10C there are the material R10F that weight is the HAC of component containing high boiling hydrocarbon Weight 0.001%~20.0%, volume space velocity be 0.5~3.0hr^-1；The material R10F of the HAC of component containing high boiling hydrocarbon is re-quantization Learning hydrogen consumption is 0.25%~2.5%.

62. method according to claim 1, it is characterised in that:

In removal process SU10, thermal high separation process THPS is set；

Hot high score liquid THPS-L is separated and recovered, the distillation being mainly made of the hydrocarbon component that normal boiling point is 250~530 DEG C is obtained Oily R10-P-ML, at least part distilled oil R10-P-ML enter hydrogenation process R10A.

63. method according to claim 1, it is characterised in that:

In removal process SU10, thermal high separation process THPS is set；

Hot high score liquid THPS-L is separated and recovered, obtains mainly being rich in by what the hydrocarbon component that normal boiling point is 350~530 DEG C formed The distilled oil R10-P-ML of aromatic hydrocarbons, at least part distilled oil R10-P-ML enter floating bed hydrogenation modified-reaction process BRA.

64. method according to claim 1, it is characterised in that:

In removal process SU10, thermal high separation process THPS is set；

Hot high score liquid THPS-L is separated and recovered, obtains mainly being rich in by what the hydrocarbon component that normal boiling point is 450~530 DEG C formed The distilled oil R10-P-ML of aromatic hydrocarbons, at least part distilled oil R10-P-ML enter floating bed hydrogenation modified-reaction process BRA.

65. method according to claim 1, it is characterised in that:

(1) the flow B RAP- comprising large-size particles catalyst BP based on hydrogenation modification reaction product BRAP at least partially BP-X participates in reaction by least part reaction compartment of floating bed hydrogenation reaction process R10, reacted with floating bed hydrogenation The charging R10F of journey R10 or the contact of its hydro-conversion object；

Flow B RAP-BP-X, selected from the one or several of following logistics:

2. the hydrogenation modification reaction product BRAP of the BP of catalyst containing large-size particles enters thermal high separation process BRAP-BP-X- HS is separated into the hot high score oil BRAP-BP-X-HSO and hot high score gas BRAP-BP-X-HSV of the BP of catalyst containing large-size particles, until Few a part of hot high score oil BRAP-BP-X-HSO is used as flow B RAP-BP-X；

3. the hydrogenation modification reaction product BRAP of the BP of catalyst containing large-size particles enters thermal high separation process BRAP-BP-X- HS is separated into the hot high score oil BRAP-BP-X-HSO and hot high score gas BRAP-BP-X-HSV of the BP of catalyst containing large-size particles, until The hot high score oil BRAP-BP-X-HSO of few a part catalyst containing large-size particles BP is depressured, gained contains big partial size after degassing The liquid B RAP-BP-X-HSOA of grain catalyst BP is used as flow B RAP-BP-X；

4. separation hydrogenation modification reaction product BRAP obtains the hydrogenated oil BRAP-BP-XPO of the BP of catalyst containing large-size particles And hydrogen-rich gas；In hydrogenated oil BRAP-BP-XPO fractionating section, separates hydrogenated oil BRAP-BP-XPO and obtain containing big The logistics of particles catalyst BP, the logistics rich in hydrogen supply the hydrocarbon component is used as flow B RAP-BP-X at least partially；

5. separation hydrogenation modification reaction product BRAP obtains the hydrogenated oil BRAP-BP-XPO of the BP of catalyst containing large-size particles And hydrogen-rich gas；In hydrogenated oil BRAP-BP-XPO fractionating section, separates hydrogenated oil BRAP-BP-XPO and obtain containing big The logistics rich in hydrogen supply the hydrocarbon component of particles catalyst BP, being rich in for the BP of catalyst containing large-size particles supplies at least partially The logistics of hydrogen the hydrocarbon component is used as flow B RAP-BP-X；

6. separation hydrogenation modification reaction product BRAP obtains hydrogenated oil BRAP-BP-XPO and hydrogen-rich gas；It is being hydrogenated to Oily BRAP-BP-XPO fractionating section, separation hydrogenated oil BRAP-BP-XPO obtain the main of the BP of catalyst containing large-size particles It is that the logistics that hydrogen supply the hydrocarbon component forms of being rich in greater than 350 DEG C is used as flow B RAP-BP-X by normal boiling point.

66. method according to claim 1, it is characterised in that:

In removal process SU10, thermal high separation process THPS is set；

Hot high score liquid THPS-L is separated and recovered, the hydrocarbon component mainly by normal boiling point higher than 530 DEG C forms plus hydrogen tail is obtained Oily R10-P-VS, at least part tail oil R10K-P-VS do not enter hydrogenation process.

67. method according to claim 1, it is characterised in that:

Based on the hydrocarbon material RKKC rich in catalyst that logistics R10-ENDP is obtained, it is recycled back into floating bed hydrogenation modified-reaction mistake Journey BRA is mixed with the component materials BRAF of wax oil containing aryl or its hydrogenation products；

Hydrocarbon material RKKC containing catalyst, selected from one or more of following materials:

Option 1, the hot high score that a part is obtained in the thermal high separation process of hydrogenation process R10 effluent R10-ENDP Oil, as the hydrocarbon material RKKC containing catalyst；

Option 2, a part contain what the destilling tower of the separation fractional distillation process of hydrogenation process R10 effluent R10-ENDP was discharged The hydrocarbon material of catalyst, as the hydrocarbon material RKKC containing catalyst；

Option 3, a part contain what the destilling tower of the separation fractional distillation process of hydrogenation process R10 effluent R10-ENDP was discharged The distillation cold oil of catalyst, as the hydrocarbon material RKKC containing catalyst；

Option 4, a part contain what the destilling tower of the separation fractional distillation process of hydrogenation process R10 effluent R10-ENDP was discharged The destilling tower base oil of catalyst, as the hydrocarbon material RKKC containing catalyst；

Option 5, at least part separate the hydrocarbon ils for the bituminous component that hydrogenation process R10 effluent R10-ENDP is obtained, Raw material VS-EF as solvent extraction and separation process VS-EU, solvent extraction and separation process VS-EU obtain containing catalyst Hydrocarbon material, as the hydrocarbon material RKKC containing catalyst；

Option 6, at least part separate the hydrocarbon ils for the bituminous component that hydrogenation process R10 effluent R10-ENDP is obtained, Raw material VS-EF as solvent extraction and separation process VS-EU, solvent extraction and separation process VS-EU obtain containing catalyst Heavy asphalt hydrocarbon material, as the hydrocarbon material RKKC containing catalyst；

Option 7, at least part separate the hydrocarbon ils for the bituminous component that hydrogenation process R10 effluent R10-ENDP is obtained, Raw material VS-EF as solvent extraction and separation process VS-EU, solvent extraction and separation process VS-EU obtain containing catalyst Light asphalt hydrocarbon material, as the hydrocarbon material RKKC containing catalyst；

Option 8, at least part separate the hydrocarbon ils for the bituminous component that hydrogenation process R10 effluent R10-ENDP is obtained, Raw material VS-EF as solvent extraction and separation process VS-EU, solvent extraction and separation process VS-EU obtain containing catalyst Middle matter pitch hydrocarbon material, as the hydrocarbon material RKKC containing catalyst.

68. method according to claim 1, it is characterised in that:

The material R10F of the HAC of component containing high boiling hydrocarbon comes from high temperature coal-tar, contains coal tar pitch component；

The extraction needle-shape coke raw material of containing hydrogenated coal tar pitch material based on hydrogenation process R10 effluent R10-ENDP is set Using the solvent extraction and separation process VS-EU of solvent segregation；

Based on the hydrocarbon material RKKC rich in catalyst that hydrogenation process R10 effluent R10-ENDP is obtained, it is recycled back into and adds Hydrogen reaction process R10 is mixed with the raw material of hydrogenation process R10 or intermediate product or final product；

Option 1 is used as in the hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained containing catalyst at least partially Hydrocarbon material RKKC；

Option 2 is used as in the heavy asphalt hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained at least partially Hydrocarbon material RKKC containing catalyst；

Option 3 is used as in the light asphalt hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained at least partially Hydrocarbon material RKKC containing catalyst；

Option 4 is used as in the middle matter pitch hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained at least partially Hydrocarbon material RKKC containing catalyst；

69. method according to claim 1, it is characterised in that:

In the process U100 of hydrocarbon-bearing material R10F, in the hydrogenated oil R10P-OIL based on hydrogenation reaction effluent R10P The material containing liquid material separation process, obtain being higher than 450 DEG C of the hydrocarbon components containing distributed metal compound particles, containing normal boiling point Containing colloid or with the hydrocarbon-bearing material S333 of asphalitine；

It isolated after being mixed with extractant containing extractant in solvent extraction and separation process VS-EU-SPU60, material S333, contained The liquid material VS-EU-SPU60-SL of light phase containing agent of relatively low molecular weight the hydrocarbon component is isolated containing extractant, containing opposite macromolecule The liquid material of heavy phase containing the agent VS-EU-SPU60-SH for measuring the hydrocarbon component, being enriched with distributed beaded catalyst R10C；

Solvent extraction and separation process VS-EU-SPU60, the extractant used be dissolve colloid or with asphalitine ability is strong has Machine low boiling point solvent；

The method that solvent extraction and separation process VS-EU-SPU60 isolates light liquid phase and heavy-fluid phase, a kind in following:

It is light containing agent in the fractional distillation process of the liquid material of light phase containing the agent VS-EU-SPU60-SL of distillation abjection extractant that may be present Become light phase material VS-EU-SPU60-LP after phase liquid material VS-EU-SPU60-SL distillation removing extractant；

In the fractional distillation process of the liquid material of heavy phase containing the agent VS-EU-SPU60-SH of distillation abjection extractant that may be present, weight containing agent Become heavy phase material VS-EU-SPU60-HP after phase liquid material VS-EU-SPU60-SH distillation removing extractant；

The material of the distributed beaded catalyst R10C of richness of at least part based on heavy phase material VS-EU-SPU60-H, is used as desiccation Expect that VS-EU-SPU60-H-R10C-OUT is used；

70. according to claim 69 the method, it is characterised in that:

Solvent extraction and separation process VS-EU-SPU60, the extractant used are selected from one of the following or several:

Option 1, the solvent containing benzene or toluene；

Option 2, the solvent containing tetrahydrofuran；

Option 3, the solvent containing carbon disulfide；

Option 4, the solvent containing quinoline；

Option 5, the solvent containing cyclohexanone；

Option 6, the solvent containing pyridine；

Option 7, the solvent containing N-Methyl pyrrolidone；

Option 8, the solvent containing dimethyl ether；

Option 9, the solvent containing dimethyl sulfoxide；

Option 10, the solvent containing dimethylformamide；

Option 11, the solvent containing ethylenediamine；

Option 12, the solvent containing acetone；

Option 13, the solvent containing phenolic groups；

71. according to claim 69 the method, it is characterised in that:

Dispersing type metal compound particles contained by hydrocarbon-bearing material S333, including distributed beaded catalyst R10C.

72. according to claim 69 the method, it is characterised in that:

Dispersing type metal compound particles contained by hydrocarbon-bearing material S333, including molybdenum sulfide dispersing type beaded catalyst R10C.

73. according to claim 69 the method, it is characterised in that:

At least part liquid material VS-EU-SPU60-SL of light phase containing agent, working method are selected from one of the following or several:

Option 1 is used as outer discharge and process U100 is discharged；

74. according to claim 69 the method, it is characterised in that:

Light phase material VS-EU-SPU60-LP after at least part distillation removing extractant, working method in following one Kind is several:

Option 1 is used as outer discharge and process U100 is discharged；

75. according to claim 69 the method, it is characterised in that:

Solvent extraction and separation process VS-EU-SPU60 uses 1 grade of extraction separation process or 2 grades of extraction separation processes or more Grade extraction separation process.

76. according to claim 69 the method, it is characterised in that:

Solvent extraction and separation process VS-EU-SPU60 obtains desiccation material VS-EU-SPU60-H-R10C-OUT；

Desiccation material VS-EU-SPU60-H-R10C-OUT containing metal molybdenum or with vanadium or and nickel, the raw material as tamping coking technique, After mixing with coal, the high coke of production tenor produces stamp-charging coke.

77. according to claim 69 the method, it is characterised in that:

Desiccation material VS-EU-SPU60-H-R10C-OUT containing metal molybdenum or with vanadium or and nickel, the raw material as tamping coking technique, After mixing with coal, the high coke of production tenor, the step of producing stamp-charging coke is as follows:

1. being mixed with coking with clean fine coal after desiccation material VS-EU-SPU60-H-R10C-OUT solidification, crushing, crushing, make firm by ramming Cake of press obtains briquette；

2. sending into coke oven in isolation heated under air and keeping the temperature briquette, then through cooling and screening process, coke is obtained.

78. according to claim 69 the method, it is characterised in that:

Desiccation material VS-EU-SPU60-H-R10C-OUT is used containing metal molybdenum or with vanadium or with nickel, the raw material as recycling metal.

79. according to claim 69 the method, it is characterised in that:

Desiccation material VS-EU-SPU60-H-R10C-OUT is used containing metal molybdenum or with vanadium or with nickel, the raw material as recycling metal；

The working method for recycling metal is selected from one of the following or several:

The desiccation material VS-EU-SPU60-H-R10C-OUT of liquid condition or solid particle state is first burnt, is then used by option 1 Ammonia and ammonium carbonate handle to obtain ammonium molybdate flue dust；

Desiccation material VS-EU-SPU60-H-R10C-OUT progress coking is first obtained coke, then combustion of coke, then by option 2 Flue dust is handled to obtain ammonium molybdate with ammonia and ammonium carbonate；

Option 3 is reacted using sulfuric acid with desiccation material VS-EU-SPU60-H-R10C-OUT in the presence of first alcohol and oxidizing agent, Molybdenum is extracted into water phase and is recycled；Oxidant may be hydrogen peroxide；

Option 4, the high temperature high pressure process under molten, ammonia pressure using acid, add inorganic acid, separate, be passed through hydrogen sulfide, separation etc. Molybdenum is converted to molybdenum sulfide and recycles molybdenum by step；

Option 5, the first step will roast after desiccation material VS-EU-SPU60-H-R10C-OUT and solid base ground and mixed；Second step, The solid obtained after roasting is subjected to water logging, obtained leaching liquid obtains molybdate by condensing crystallizing and crystallizes.

80. according to the method described in claim 1, it is characterized by:

The component materials BRAF of wax oil containing aryl is mainly made of the hydrocarbon that normal boiling point is 350~570 DEG C and may contain solid Grain, selected from one or more of following materials:

1. logistics containing oil product obtained by middle coalite tar or its distillate or its hot procedure；Hot procedure is selected from coking Journey or catalytic cracking process or catalytic pyrolysis process or hydrogenation process；

3. logistics containing oil product obtained by direct hydrogenation liquefaction of coal liquefaction process, the direct hydrogenation liquefaction of coal including using hydrogen supply dissolvent oil Liquefaction process, coal refines process to oil altogether, coal faces hydrogen thermosol liquefaction process；

81. according to the method described in claim 1, it is characterized by:

The component materials of wax oil containing aryl BRAF is the high aromatic hydrocarbons wax oil containing solid particle, is mainly 350~570 by normal boiling point DEG C hydrocarbon composition, one or more of selected from following materials:

1. the wax slop of petroleum base viscous crude；

82. according to the method described in claim 1, it is characterized by:

The component materials BRAF of wax oil containing aryl is mainly made of the hydrocarbon that normal boiling point is 350~570 DEG C and contains solid particle.

83. according to the method described in claim 1, it is characterized by:

The hydro carbons in hydrogenation modification reaction product BRAP is separated, the wax oil KKAA rich in double ring arene or polycyclic aromatic hydrocarbon is obtained, until Few a part of wax oil KKAA returns to floating bed hydrogenation modified-reaction process BRA and participates in reaction by least part reaction compartment, It is contacted with the charging richness aromatic hydrocarbons wax oil BRAF of floating bed hydrogenation reaction process R10 or its hydro-conversion object.

84. according to the method described in claim 1, it is characterized by:

The hydro carbons in hydrogenation reaction product R10P is separated, obtains the wax oil KKBB rich in double ring arene or polycyclic aromatic hydrocarbon, at least one Part wax oil KKBB returns to floating bed hydrogenation modified-reaction process BRA and participates in reaction by least part reaction compartment, and outstanding The charging richness aromatic hydrocarbons wax oil BRAF of floating bed hydrogenation process R10 or the contact of its hydro-conversion object.

85. according to the method described in claim 1, it is characterized by:

The operating condition of floating bed hydrogenation modified-reaction process BRA are as follows: reaction temperature is 390~445 DEG C, reactor pressure 6 ~30MPa, vapor phase hydrogen volumetric concentration 50~95%, gas-liquid volume ratio are 100~2000 standard cubic meters/ton, hydrogenation modification Catalyst BRA-CAT additive amount is the 0.001 mass % of mass %~5 of the weight of high aromatic hydrocarbons wax oil BRF, co-catalyst additive amount It is 1.0~2.0 for sulphur in co-catalyst/catalyst activity metal molar ratio, reaction time TRU is 5 minutes~120 points Clock.

86. according to the method described in claim 1, it is characterized by:

The hydrogenation catalyst that floating bed hydrogenation modified-reaction process BRA is used, is a kind of composite hydrogenation catalyst, comprising high living Property component and low activity component；The weight ratio of the high-activity component metal and low activity component metals is 1: 10 to 1000: 1； The high-activity component contains or mixtures thereof oil-soluble salt compounds or water soluble salt compound of molybdenum；The low activity Component contains ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, and catalyst water content is lower than 2wt%.

87. according to the method described in claim 1, it is characterized by:

The hydrogenation catalyst that floating bed hydrogenation modified-reaction process BRA is used is catalyzed comprising nanometer ultra-fine grain hydrated ferric oxide Agent or with iron oxide or with pyrite or with bloodstone or with molybdenum oxide or with molybdenum sulfide or with ammonium molybdate or and nickel sulfide.

88. according to the method described in claim 1, it is characterized by:

Floating bed hydrogenation modified-reaction process BRA, uses at least part hydrogen supply dissolvent BRA-DS；

Hydrogen supply dissolvent BRA-DS, it may be possible to contained in gas phase obtained by the intermediate reaction product based on separation hydrogenation process A10 The hydrocarbon component or its stabilized hydrogenation the hydrocarbon component；

Hydrogen supply dissolvent BRA-DS, it may be possible to the hydrocarbon component obtained by the final reacting product A10P based on separation hydrogenation process A10 Or its stabilized hydrogenation the hydrocarbon component；

Hydrogen supply dissolvent BRA-DS, it may be possible to the hydrogen supply the hydrocarbon component BRA- generated based on high aromatic hydrocarbons wax oil BRAF in hydrogenation process BRA CDC；

89. according to the method described in claim 1, it is characterized by:

Normal boiling point is high in the weight flow rate BRA-DS-W and the component materials of wax oil containing aryl BRAF of hydrogen supply dissolvent flow B RA-DS In 450 DEG C of the hydrocarbon components weight flow rate BRAF-D-W ratio be oil ratio BK100=(BRA-DS-W)/(BRAF-D-W), BK100 is 0.1~10.0.

90. according to the method described in claim 1, it is characterized by:

Hydrogen supply dissolvent BRA-DS is mainly that 250~530 DEG C of hydro carbons form by normal boiling point, and the weight of part saturation aromatic hydrocarbons contains It is 0.35~0.70 that amount, which is greater than 15%, aromatic carbon rate,.

91. according to the method described in claim 1, it is characterized by:

Hydrogen supply dissolvent BRA-DS is mainly that 250~530 DEG C of hydro carbons form by normal boiling point, and the weight of part saturation aromatic hydrocarbons contains It is 0.45~0.60 that amount, which is greater than 25%, aromatic carbon rate,.

92. according to the method described in claim 1, it is characterized by:

(1) in the floating bed hydrogenation modified-reaction process BRA of the component materials of wax oil containing aryl BRAF, it is based on product at least partially The flow B RAP-BP-WX comprising large-size particles catalyst BP, the hydrocarbon containing hydrogen supply of BRAP, by processing the object containing residue fraction Expect that at least part reaction compartment of the floating bed hydrogenation reaction process CR of CRF participates in reaction, with material CRF or its hydro-conversion Object contact；

In floating bed hydrogenation reaction process CR, simultaneously can there are hydrogen, conventional liq, dispersing type large-size particles catalyst BP Can exist hydrogen supply hydrocarbon, there may be dilution hydrocarbon, there may be under conditions of distributed small size particle catalyst LP, at least one Divide the material CRF for being higher than 530 DEG C of hydrocarbon containing normal boiling point to carry out hydrogenation reaction R10R and the reaction of at least part removal of ccr by hydrotreating occurs It is converted into hydrogenation reaction product CRP；

Flow B RAP-BP-W comprising large-size particles catalyst BP of at least part based on product CRP, by suspension bed plus At least part reaction compartment of hydrogen reaction process R10 participates in reaction, with the charging R10F of floating bed hydrogenation reaction process R10 or The contact of its hydro-conversion object.

93. the method according to claim 92, it is characterised in that:

Flow B RAP-BP-W comprising large-size particles catalyst BP of at least part based on product CRP, by suspension bed plus At least part reaction compartment of hydrogen reaction process R10 participates in reaction, with the charging R10F of floating bed hydrogenation reaction process R10 or The contact of its hydro-conversion object；

Flow B RAP-BP-W, selected from the one or several of following logistics:

2. the hydrogenation reaction product CRP of the BP of catalyst containing large-size particles enters thermal high separation process BRAP-BP-W-HS separation For the hot high score oil BRAP-BP-W-HSO and hot high score gas BRAP-BP-W-HSV of the BP of catalyst containing large-size particles, at least one Hot high score oil BRAP-BP-W-HSO is divided to be used as flow B RAP-BP-W；

3. the hydrogenation reaction product CRP of the BP of catalyst containing large-size particles enters thermal high separation process BRAP-BP-W-HS separation For the hot high score oil BRAP-BP-W-HSO and hot high score gas BRAP-BP-W-HSV of the BP of catalyst containing large-size particles, at least one Gained is containing large-size particles catalysis after dividing the hot high score oil BRAP-BP-W-HSO decompression of the BP of catalyst containing large-size particles, deaerating The liquid B RAP-BP-W-HSOA of agent BP is used as flow B RAP-BP-W；

94. the method according to claim 92, it is characterised in that:

The hydro carbons in hydrogenation reaction product CRP is separated, obtains the wax oil KK66 rich in double ring arene or polycyclic aromatic hydrocarbon, at least one Divide wax oil KK66 to return to floating bed hydrogenation modified-reaction process BRA or passes through at least part with floating bed hydrogenation reaction process CR Reaction compartment participates in reaction.

95. the method according to claim 92, it is characterised in that:

The hydro carbons in hydrogenation reaction product R10P is separated, obtains the wax oil KK77 rich in double ring arene or polycyclic aromatic hydrocarbon, at least one Part wax oil KK77 returns to floating bed hydrogenation modified-reaction process BRA or adds with floating bed hydrogenation reaction process CR or with suspension bed Hydrogen reaction process R10 participates in reaction by least part reaction compartment.

96. the method according to claim 92, it is characterised in that:

Separate hydrogenation reaction product CRP or with the hydro carbons in hydrogenation reaction product R10P, obtain rich in double ring arene or polycyclic virtue The wax oil KK77 of hydrocarbon obtains mainly being contained by what the hydrocarbon component that normal boiling point is higher than 520 DEG C formed rich in colloid, the possibility of asphalitine There is the hydrocarbon stream KK255 of solid particle；

At least part wax oil KK77 returns to floating bed hydrogenation modified-reaction process BRA and is participated in by least part reaction compartment Reaction；

At least part wax oil KK255 returns to floating bed hydrogenation reaction process CR and is participated in instead by least part reaction compartment It answers.

97. the method according to claim 92, it is characterised in that:

Hydrocarbon CRF inferior is mainly to be contained by what the hydrocarbon component that normal boiling point is higher than 570 DEG C formed rich in colloid, the possibility of asphalitine The hydrocarbon stream of solid particle, carbon residue content are 20~65 weight %.

98. the method according to claim 92, it is characterised in that:

Hydrocarbon CRF inferior is mainly to be contained by what the hydrocarbon component that normal boiling point is higher than 570 DEG C formed rich in colloid, the possibility of asphalitine The hydrocarbon stream of solid particle, carbon residue content are 30~45 weight %.

99. the method according to claim 92, it is characterised in that:

Hydrocarbon CRF inferior is mainly to contain solid rich in colloid, asphalitine higher than what 570 DEG C of the hydrocarbon component formed by normal boiling point The high carbon residue hydrocarbon of particle, the weight concentration of solid particle are 0.010 weight of weight %~40.0 %.

100. the method according to claim 92, it is characterised in that:

Hydrocarbon CRF inferior is mainly to contain solid rich in colloid, asphalitine higher than what 570 DEG C of the hydrocarbon component formed by normal boiling point The high carbon residue hydrocarbon of particle, the weight concentration of solid particle are 0.10 weight of weight %~20.0 %.

101. the method according to claim 92, it is characterised in that:

Hydrocarbon CRF inferior is mainly to contain solid rich in colloid, asphalitine higher than what 570 DEG C of the hydrocarbon component formed by normal boiling point The high carbon residue hydrocarbon of particle, the weight concentration of solid particle are 0.10 weight of weight %~5.0 %.

102. the method according to claim 92, it is characterised in that:

In hydrocarbon CRF floating bed hydrogenation reaction process CR inferior, the heat from hydrogenation cracking rate of hydrocarbon CRF inferior is 5~45%.

103. the method according to claim 92, it is characterised in that:

The operating condition of floating bed hydrogenation reaction process CR are as follows: reaction temperature be 390~445 DEG C, reactor pressure be 6~ 30MPa, vapor phase hydrogen volumetric concentration 50~95%, gas-liquid volume ratio are 100~2000 standard cubic meters/ton, and hydrogenation modification is urged Agent CRA-CAT additive amount is the 0.001 mass % of mass %~5 of the weight of hydrocarbon CRF inferior, and co-catalyst additive amount is to help to urge Sulphur/catalyst activity metal molar ratio is 1.0~2.0 in agent, and reaction time TRU is 5 minutes~120 minutes.

104. the method according to claim 92, it is characterised in that:

The hydrogenation catalyst that floating bed hydrogenation reaction process CR is used is a kind of composite hydrogenation catalyst, includes high activity group Divide and low activity component；The weight ratio of the high-activity component metal and low activity component metals is 1: 10 to 1000: 1；It is described High-activity component contains or mixtures thereof oil-soluble salt compounds or water soluble salt compound of molybdenum；The low activity component Containing ferric oxide ore or iron sulfide ore, wherein iron in ore content is not less than 40wt%, and catalyst water content is lower than 2wt%；The powdered granule that deliquescence accelerant particle diameter is 0~100 μm.

105. the method according to claim 92, it is characterised in that:

The hydrogenation catalyst that floating bed hydrogenation reaction process CR is used, comprising nanometer ultra-fine grain aqua oxidation iron catalyst or and Iron oxide or with pyrite or with bloodstone or with molybdenum oxide or with molybdenum sulfide or with ammonium molybdate or and nickel sulfide.

106. the method according to claim 92, it is characterised in that:

In hydrocarbon CRF floating bed hydrogenation reaction process CR inferior, at least part hydrogen supply dissolvent CR-DS is used；

Hydrogen supply dissolvent CR-DS, it may be possible to contained in gas phase obtained by the intermediate reaction product based on separation hydrogenation process R10 The hydrocarbon component or its stabilized hydrogenation the hydrocarbon component；

Hydrogen supply dissolvent CR-DS, it may be possible to based on separation hydrogenation process R10 final reacting product obtained by the hydrocarbon component or its add hydrogen Stablize the hydrocarbon component；

Hydrogen supply dissolvent CR-DS, it may be possible to contained in gas phase obtained by the intermediate product based on separation hydrogenation modification reaction process BRA The hydrocarbon component or its stabilized hydrogenation the hydrocarbon component；

Hydrogen supply dissolvent CR-DS, it may be possible to based on separation hydrogenation modification reaction process BRA final product obtained by the hydrocarbon component or its add hydrogen Stablize the hydrocarbon component；

Hydrogen supply dissolvent CR-DS, it may be possible to the hydrocarbon component contained in gas phase obtained by the intermediate product based on separation reaction process CR or Its stabilized hydrogenation the hydrocarbon component；

Hydrogen supply dissolvent CR-DS, it may be possible to the hydrocarbon component obtained by the final product based on separation reaction process CR or its stabilized hydrogenation hydrocarbon Component；

Hydrogen supply dissolvent CR-DS, it may be possible to the hydrogen supply the hydrocarbon component CR- generated based on hydrocarbon CRF floating bed hydrogenation reaction process CR inferior CDC；

107. the method according to claim 92, it is characterised in that:

The weight flow rate CR-DS-W of hydrogen supply dissolvent flow C R-DS and the ratio of the weight flow rate CRF-W of hydrocarbon stream CRF inferior are Oil ratio BK100=(CR-DS-W)/(CRF-W), CK100 are 0.05~5.0.

108. the method according to claim 92, it is characterised in that:

Normal boiling point is higher than the weight of 450 DEG C of the hydrocarbon components in the weight flow rate CR-DS-W and material CRF of hydrogen supply dissolvent flow C R-DS The ratio for measuring flow rate CRF-H-W is oil ratio BK100=(CR-DS-W)/(CRF-H-W), and CK100 is 0.5~1.5.

109. the method according to claim 92, it is characterised in that:

Hydrogen supply dissolvent flow C R-DS is mainly that 250~530 DEG C of hydro carbons form by normal boiling point, the weight of part saturation aromatic hydrocarbons Measuring content to be greater than 15%, aromatic carbon rate is 0.35~0.70.

110. the method according to claim 92, it is characterised in that:

Hydrogen supply dissolvent flow C R-DS is mainly that 250~530 DEG C of hydro carbons form by normal boiling point, the weight of part saturation aromatic hydrocarbons Measuring content to be greater than 25%, aromatic carbon rate is 0.45~0.60.

111. the method according to claim 92, it is characterised in that:

The operation target of up flow type expanded bed hydrogenation modification reaction process CRA are as follows: hydrogen consumption is high aromatic hydrocarbons wax oil BRF weight The 0.1 mass % of mass %~1.5, heat from hydrogenation cracking reaction conversion ratio are 20~35 mass %.

112. the method according to claim 92, it is characterised in that:

The operation target of up flow type expanded bed hydrogenation modification reaction process CRA are as follows: hydrogen consumption is high aromatic hydrocarbons wax oil BRF weight The 0.1 mass % of mass %~1.5, heat from hydrogenation cracking reaction conversion ratio are 5~25 mass %.