CN107892945A

CN107892945A - With the hydrocarbon material expanded bed hydrogenation reactor system of air lift hydrogen and liquid collection cups

Info

Publication number: CN107892945A
Application number: CN201610884037.4A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Luoyang Rui Hua New Energy Technology Development Co Ltd
Priority date: 2016-10-01
Filing date: 2016-10-01
Publication date: 2018-04-10

Abstract

With the hydrocarbon material expanded bed hydrogenation reactor system of air lift hydrogen and liquid collection cups, it is hydrogenated with suitable for petroleum based heavy fuel oils, coal tar hydrogenating, the processing of middle part product R10ZE IP inside the end hydrogenation reactor R10ZE of Coal Liquefaction process, use air lift hydrogen BH and liquid collection cups LD, at least a portion low boiling hydrocarbon component in the product R10ZE IP liquid phases of middle part is vaporizated into gas phase discharge hydrogenation reactor R10ZE, the collection liquid R10ZE TL being mainly made up of heavy hydrocarbon of de- low boiling hydrocarbon are obtained simultaneously, collection liquid R10ZE TL export the unconverted oil as setting boiling point boundary from liquid collection cups, form the reactive moieties short-circuit cycle hydrogenation pattern of unconverted oil；Air lift hydrogen BH enters the de- liquid space in liquid collection cups LD tops by the dual formula distributor that " the nozzle reflecting plate " of horizontally disposed cartridge type distributing chamber locular wall forms with rising cocurrent after material mixes.

Description

With the hydrocarbon material expanded bed hydrogenation reactor system of air lift hydrogen and liquid collection cups

Technical field

With the hydrocarbon material expanded bed hydrogenation reactor system of air lift hydrogen and liquid collection cups, suitable for petroleum based heavy fuel oils plus Hydrogen, coal tar hydrogenating, Coal Liquefaction process end hydrogenation reactor R10ZE inside middle part product R10ZE-IP place Reason, using air lift hydrogen BH and liquid collection cups LD, by least a portion low boiling hydrocarbon in the product R10ZE-IP liquid phases of middle part Component is vaporizated into gas phase discharge hydrogenation reactor R10ZE, while obtains the collection being mainly made up of heavy hydrocarbon of de- low boiling hydrocarbon Liquid R10ZE-TL, collection liquid R10ZE-TL export the unconverted oil as setting boiling point boundary from liquid collection cups, and composition does not turn The reactive moieties short-circuit cycle hydrogenation pattern of carburetion；Air lift hydrogen BH by horizontally disposed cartridge type distributing chamber locular wall " nozzle- The dual formula distributor of reflecting plate " composition enters the de- liquid space in liquid collection cups LD tops with rising cocurrent after material mixes.

Background technology

Hydrocarbon material of the present invention, carbon containing, protium liquid and/or solid are referred to, such as oil and/or coal.

Hydrocarbon material hydrogenation reaction of the present invention, refer to hydrogen exist and pressurized conditions under, carbon containing, protium liquid Body and/or the solid hydrogenation reaction that such as oil and/or coal occur, wherein hydrofinishing and/or hydrogenation occur for the feedstock oil of oily hydrogenation process Thermosol occurs for the product of heat cracking reaction generation at least a portion more low molecule amount, the wherein feed coal of coal liquifaction process swollen, hot The reactions such as cracking, free radical stabilized hydrogenation generate the hydrocarbon products that at least a portion normal boiling point is less than 450 DEG C.

Hydrocarbon material hydrogenation process of the present invention, exemplary are coal tar suspension bed hydrogenation heat cracking reaction mistakes Journey, direct hydrogenation liquefaction of coal course of reaction, oily coal refine hydrogenation process, petroleum based heavy fuel oils suspension bed or boiling bed hydrogenation and split altogether Change course of reaction.

Hydrocarbon material hydrogenation reaction of the present invention, its reaction product BASE-R10P, at least gas-liquid two-phase logistics are most Situation belongs to gas, liquid, solid three-phase logistics.

Hydrogenation reaction effluent R10P-X of the present invention is used to discharge hydrogenation reaction product BASE-R10P, to contain hydrogen Gas, liquid hydrocarbon simultaneously may the material containing solid particle.

Expanded bed hydrogenation reactor of the present invention, it is vertical up-flow reactor, belongs to expanded bed during using catalyst Hydrogenation reactor；The vertical central axis upright for referring to working condition reactor after installing is in ground；Up flow type refers to instead Answer process materials main body flow direction travel through from bottom to top reaction compartment or beds or with up catalyst concurrent It is dynamic；Expanded bed refers to that working condition beds are in swelling state, and beds expansion ratio is defined as catalyst bed Layer have reaction raw materials by when working condition maximum height CWH and the beds empty bed static condition height CUH ratio KBED, generally, KBED are referred to as slight expanded-bed when being less than 1.10, KBED between 1.25~1.55 when be referred to as ebullated bed, And suspension bed is considered as the expanded bed of most extreme form.

Air lift hydrogen of the present invention, referring to will be low in the hydrogenation reactor R10ZE inside end material liquid phases of end The hydrogen BH that the process that boiling point hydrocarbon is vaporizated into gas phase uses.

Body collection cups LD of the present invention, refer to being arranged at the product inside the hydrogenation reactor R10ZE of end and take off liquid system The cup disk dehisced upwards of the collection liquid of system, collection liquid R10ZE-TL enter pressurized circulation system by catheter LK.

The present invention relates to middle coalite tar raw material hydrocarbon R10F hydrogenation process, specifically, it is swollen to be directed to use with up flow type The liquid phase distribution mode of hydrocarbon component in the end hydrogenation reaction product of the middle coalite tar heavy distillat of swollen bed, key, which is related to, to be followed The composition and its circulation hydrogenation selectivity of ring oil, further relate to the structural shape and inner parts structure of reactor.

The raw material hydrocarbon R10F that heavy distillat of the normal boiling point of middle coalite tar higher than 350 DEG C forms, because comprising coal tar pitch, Its suitable method of hydrotreating is the hydrogenation process R10 using up flow type expanded bed；Hydrogenation process R10 can be to add Process based on hydrogen refining reaction is that the hydrocracking reaction of substantial amounts of hydrofining reaction and relatively small amount occurs；Hydro-upgrading Process R10 can also be that substantial amounts of hydrofining reaction, substantial amounts of hydrocracking reaction occur for hydrocracking process.

The raw material hydrocarbon R10F that heavy distillat of the normal boiling point of middle coalite tar higher than 350 DEG C forms, it is swollen using up flow type The unifining process of swollen bed or the hydrofinishing section of hydrocracking process, operation temperature is generally higher, typically up to 350~ 430 DEG C, generally up to 380~415 DEG C, but reaction temperature of the reaction temperature value typically compared with hydrocracking process is worth low one A bit, for example, generally it is low go out 15~50 DEG C.

The raw material hydrocarbon R10F that heavy distillat of the normal boiling point of middle coalite tar higher than 350 DEG C forms, it is swollen using up flow type The hydrocracking process of swollen bed is hydrocracked section, and operation temperature is generally higher, typically up to 410~470 DEG C, generally up to 425~455 DEG C, the reaction temperature typically it is higher compared with the reaction temperature of unifining process be such as generally higher by 15~50 DEG C or It is higher.

Below in conjunction with the floating bed hydrogenation heat cracking reaction of heavy distillat of the normal boiling point of middle coalite tar higher than 350 DEG C Process and its product separation, Liquid product recycle cracking process, the description present invention.

The raw material hydrocarbon R10F that heavy distillat of the normal boiling point of middle coalite tar higher than 350 DEG C forms, low boiling therein Hydrocarbon-fraction is compared with high boiling hydrocarbon cut, and usual impurity content is relatively low, residual carbon content is relatively low, is using up flow type expanded bed As suspension bed hydrofining reaction process R1 in, low boiling hydrocarbon cut compared with high boiling hydrocarbon-fraction, generally it is therein miscellaneous Prime element is easier to be hydrogenated with hydrogenolysis abjection, the colloid therein easily de- carbon residue of hydrogenation, therefore as hydrogenation degree is deepened, low boiling The de- carbon residue task of the hydrogenation removing impurities matter of the hydrocarbon-fraction of point, hydrogenation is completed first, but now the hydrogenation of high boiling hydrocarbon-fraction takes off The de- carbon residue task of impurity, hydrogenation is not yet completed, if continuing combined depth hydrogenation, the excessive of low boiler cut certainly will be caused to add Hydrogen, excessive thermal cracking, and the deep hydrogenation process of high boiling hydrocarbon-fraction certainly will need more subsequent reactions spaces, and it is low The middle hydrogenation products of boiling point fraction reduce the concentration of high boiling hydrocarbon cut as diluent therefore reduce reaction speed, and low boiling The middle hydrogenation products of cut participate in the competitive Adsorption of catalyst surface and the contention to reactive hydrogen, now, in order to improve height boiling The selectivity of hydrocarbon hydrogenation process is put, wishes low boiling intermediate product discharging course of reaction in time in technique, and by higher boiling Between product continue to be hydrogenated with such as recycled hydrofining, can so utilize overall liquid phase under low boiling raw material components existence condition Viscosity is greatly lowered, the diffusion velocity of high boiling component accelerate advantage accelerate hydrogenation reaction, and high boiling hydrocarbon component plus The quality of hydrogen final products can be controlled by flexibly adjusting the realizations such as recycle ratio, reaction temperature, in other words, now inevitable In the presence of the hydrofinishing recycle oil being made up of heavy distillat unconverted oil.

The raw material hydrocarbon R10F that heavy distillat of the normal boiling point of middle coalite tar higher than 350 DEG C forms, is using up flow type In the hydrogenation heat cracking reaction process R10 of expanded bed such as suspension bed, it is often impossible to 100% full conversion is realized, because too high Hydrogenation thermal cracking conversion per pass can cause low boiling hydrocarbon overcracking fecund gas, the more green cokes of the excessive thermal condensation of high boiling hydrocarbon Charcoal, the distribution of severe exacerbation product, shorten the continuous cycle of operation, in other words, in order to utilize feedstock oil to greatest extent and improve liquid Body yield, generally certainly exist the thermal cracking recycle oil being made up of heavy distillat unconverted oil.

On the premise of it unconverted oil circulation hydrogenation be present, unconverted oil purity or concentration greatly influence to follow in recycle oil Catalyst concn, subsequent thermal high score oil quantity and the group that the selectivity of ring hydrogenation process, recycle oil quantity, recycle oil carry Into, or even decide the good and bad success or failure of technical process.

Generally, it is to set solely to deviate from the low boiling hydrocarbon in hydrogenation process R10 products R10P-X into the mode of gas phase Vertical high pressure hot separator, it is the shortcomings that the program：

1. independent high pressure hot separator, volume is big, and investment is big；

2. independent high pressure hot separator, instrument system complexity is, it is necessary to which supporting flushing oil system, generally also sets up ray material Position meter；Staff often in contact with equipment, its security is essential, and its operating condition generally tends to relax as far as possible；

3. fluid cushion area belongs to the prolonged liquid area of slack water (close to stagnant area) of scarce hydrogen/reactive hydrogen, liquid phase Thermal condensation probability increases, the asphalitine component in liquid phase occur on wall pyrocondensation and, deposition probability increase；

4. flow complexity improves, operation difficulty increase.

Because above-mentioned shortcomings be present, independent high pressure hot separator is set and its operation temperature is reaction system The scheme of peak, the first choice not usually in engineering.

Generally, hydrogenation reaction product R10P-X thermal high separation process S1 operation temperature is less than hydrogenation reaction product R10P-X operation temperature, the hydrogen and/or low boiling oil of a large amount of lower temperatures are generally added into hydrogenation reaction product R10P-X Product reduce its temperature, or using setting cold oil mode of washing dedirt and reduce hot high score temperature；Either which kind of mode, heat are high The concentration for the low boiling component divided in oil is above the dense of the low boiling component in hydrogenation reaction product R10P-X balance liquid phase Degree, is more not suitable for as recycle oil using.

Problem above illustrates, for the raw material hydrocarbon of heavy distillat composition of the normal boiling point of middle coalite tar higher than 350 DEG C Problems be present in R10F, the separation of its floating bed hydrogenation product, Liquid product recycle cracking process, prior art：

1. because heavy hydrocarbon floating bed hydrogenation process belongs to liquid-phase hydrogenatin course of reaction, in order to improve reactor liquid phase reactor effect Rate, overall process should not use high hydrogen to oil volume ratio, and therefore, the gas in its product is to light hydrocarbon, the air lift vapour of middle matter hydrocarbon Change function is weaker, and matter hydrocarbon is liquid phase in the major part in floating bed hydrogenation heat cracking reaction product R10P-X, so can not be anti- The relative separation of matter hydrocarbon and heavy hydrocarbon in should partly being formed, if R10P-X balance liquid phase is returned into hydrogenation heat cracking reaction mistake Journey R10, then necessarily cause the inefficient cycle of middle matter hydrocarbon and the negative reactions such as excessive heat cracking occur, increase hydrogen consumption, increase gas, be light Matter Auditory steady-state responses and matter hydrocarbon yield in reducing, i.e., can not form selectivity circulation cracking and can be only formed the circulation inferior of non-selectivity Cracking；

2. in order to realize expected selectivity circulation cracking reaction, first method is by containing a large amount of light hydrocarbons, middle matter Hydrocarbon, the miscella of unconverted oil are hot high score oil, by degassing, fractionation process, complete unconverted oil and light hydrocarbon, middle matter hydrocarbon Separate, then pressurized circulation is reacted into reactor cycles, result in formation of huge circulation logistics capacity, adds correlated process Investment and energy consumption, and in this course, unconverted oil experienced the multi-step Long Time Thermal processing under dehydrogenation condition, must Part thermal condensation so occurs to react and increase pyrocondensation compound production；

3. in order to which the selectively circulation of unconverted oil expected from being realized in course of reaction forms short circulation, a kind of feasible side Method be use hydrogen air lift final reacting product R10P-X liquid phases in most of light hydrocarbon, middle matter hydrocarbon be gas phase, independent Carried out in high pressure hot separator, conventional hot high score device, for the needs of Liquid level, it is necessary to when certain liquid stop is set Between, prolonged stop and low flowing velocity, thermal condensation deposition may be induced；Its flow is complicated, investment is big, difficult operation.

In order to overcome above-mentioned defective workmanship, it is a principal object of the present invention to propose a kind of equilibrium liquid for reducing product R10P-X The easy and effective method for the quantity that light hydrocarbon and/or middle matter hydrocarbon in phase enter in recycle oil, and build corresponding reactor operation System, its primary goal is to form the short circulation of course of reaction, i.e., complete before end productses R10P-X enters high pressure hot separator Into the phase transition behavior of low boiling component.

The present invention basic imagination be：With the hydrocarbon material expanded bed hydrogenation reactor system of air lift hydrogen and liquid collection cups System, suitable for petroleum based heavy fuel oils hydrogenation, coal tar hydrogenating, Coal Liquefaction process end hydrogenation reactor R10ZE inside Middle part product R10ZE-IP processing, using air lift hydrogen BH and liquid collection cups LD, by the product R10ZE-IP liquid phases of middle part At least a portion low boiling hydrocarbon component be vaporizated into gas phase discharge hydrogenation reactor R10ZE, while obtain the master of de- low boiling hydrocarbon To be exported by the collection liquid R10ZE-TL that heavy hydrocarbon forms, collection liquid R10ZE-TL from liquid collection cups as setting boiling point boundary Unconverted oil, form unconverted oil reactive moieties short-circuit cycle hydrogenation pattern；Air lift hydrogen BH passes through horizontally disposed cylinder The dual formula distributor of " nozzle-reflecting plate " composition of formula distributing chamber locular wall is collected with rising cocurrent after material mixes into liquid Cup LD tops take off liquid space.

The end hydrogenation reactor R10ZE of the present invention, liquid collection cups LD and the mixing of air lift Hydrogen distribution is applied in combination Device MG, is a kind of equipment of combination function, and major function has：

1. up flow type expanded bed reactor function；

2. the low boiling component function in air lift hydrogen gasification reaction material；

3. the distributed area of air lift hydrogen, is mixed zone, and hydroconversion reaction zone, and is that the higher hydrogenation of hydrogen partial pressure is anti- Answer area；

4. the de- liquid function of the net product of end reaction product, liquid product and the net product of gas-liquid mixed phase are formed, it is unconverted The high liquid phase of oil concentration is used as recycle oil；

5. the high liquid phase of unconverted oil concentration is used as recycle oil, the circulation hydrogenation of high selectivity unconverted oil is formd, is subtracted The circulation hydrogenation of invalid harmful low boiling hydrocarbon is lacked；

It can further reduce non-targeted heat cracking reaction easily using unconverted oil systemic circulation than operation scheme, carry High liquid yield；

The short-circuit cycle of unconverted oil is realized, " unconverted oil is shortened to greatest extent and enters circulation hydrogenation process No hydrogen adjoint process presence thermal condensation tendency flowing time ", can effectively reduce pyrocondensation compound production；

6. reducing the circulation hydrogenation of invalid harmful low boiling hydrocarbon, reactor target hydrogenation reaction volume effect is improved Rate；The deep hydrofinishing reaction and/or overhydrocracking reaction of high selectivity, the i.e. light oil of hydrogenated products can be performed Yield can significantly improve, hydrogenated products quality can significantly improve, and pyrocondensation compound production can reduce；

7. reducing the circulation hydrogenation of invalid harmful low boiling hydrocarbon, solid catalyst concentration in recycle oil is improved, is carried High reaction efficiency；

8. solid catalyst concentration in recycle oil is improved, beneficial to reduction fresh catalyst addition；

9. reducing fresh catalyst addition, beneficial to dead catalyst discharge capacity is reduced, dead catalyst is discharged beneficial to reducing It is entrained go out mink cell focus quantity；

10. effectively reducing hot high score oil total quantity, the total quantity of particulate matter in hot high score oil is effectively reduced；

Realize the short-circuit cycle of unconverted oil, the technique purpose of hot high score oil product amount be converted into discharge dead catalyst, Thermal condensation product, the use for the few efficient hydrogenation catalyst of dosage create condition, now can only discharge minimal amount of heat High score oil can simplify hot high score oil separation process to discharge minimal amount of dead catalyst, thermal condensation product, it is evident that can be with Significantly slow down the impingment corrosion of hot high score oil pressure-reducing valve because considerably reduce material total amount, reduce solids quantity, Reduce low boiling and easily vaporize composition quantities；The scale of the separation of hot high score oil and/or fractionating section can be greatly lowered, can be with Investment and energy consumption is greatly lowered；

(11) this technique can be used with tandem sequence repeats, i.e., one section of hot high score oil enters secondary hydrogenation reaction system as feedstock oil System；

(12) it can be used for pre-existing reactors to transform, mixed air lift hydrogen access Hydrogen distribution using the existing quenching hydrogen mouth of pipe Device.

Air lift hydrogen BH distribution mixer is arranged on the end of course of reaction in reactor, anti-to main body to reduce as far as possible Answer the reduction of process liquid phase fraction.The present invention is it is not recommended that anterior hydrogenation processes of the air lift hydrogen BH in course of reaction R10 adds Enter, light components, middle matter component can be vaporizated into gas phase too early by this, can reduce the hydrogenation depth of higher boiling raw material hydrocarbon, reason exists In：

1. reducing main body course of reaction liquid phase fraction, reactor volume efficiency is reduced；

2. increasing liquid phase viscosity, the diffusion velocity of high boiling hydrocarbon is reduced；

3. reducing the quantity of the low-boiling hydrocarbon solvent of high boiling hydrocarbon, dissolving hydrogen total amount is reduced, is reduced for activity Hydrogen Energy power, waste the hydrogen supply capacity of lower boiling hydrogen supply hydrocarbon；

4. concentrating high boiling hydrocarbon in advance, the thermal condensation probability of high boiling hydrocarbon particularly gum asphalt, liquid phase are added In asphalitine component occur on pipeline, wall pyrocondensation and, deposition probability increase.

From suppress unconverted oil circulating path thermal condensation angle in terms of, the present invention formed heavy hydrocarbon component unconverted oil it is anti- Partial short circuit circulation process is answered, can " shortening unconverted oil, to be recycled into the no hydrogen before hydrogenation process adjoint to greatest extent The time of the flow process of the presence thermal condensation tendency of process ", therefore, appearance of the invention is inevitable, may refrain from or terminates For unconverted oil thermal condensation reaction, its efficiency highest.

The hydrogenation process R10 of the present invention, as needed, 1 can be used or be used in series 2 or be used in series more Platform hydrogenation reactor, reactor R10XE working method can be any one suitable up-flow reactor form；It is unconverted Oily recycle oil, any one reaction compartment of upstream can be returned to.

The method of the invention has no report.

The present invention, can be with the other technological maheups of combination application.

Therefore, the first object of the present invention is that the hydrocarbon material expansion bed hydroprocessing of proposition air lift hydrogen and liquid collection cups is anti- Device system is answered, hydrocarbon material can be oil and/or coal.

Second purpose of the invention is the coal tar expanded bed hydrogenation reactor system of proposition air lift hydrogen and liquid collection cups System.

3rd purpose of the invention is the coal liquifaction expanded bed hydrogenation reactor system of proposition air lift hydrogen and liquid collection cups System.

4th purpose of the invention is the coal tar expanded bed hydrogenation reactor system of proposition air lift hydrogen and liquid collection cups System, proposes a kind of organization plan of air lift hydrogen BH distribution mixer.

5th purpose of the invention is the hydrocarbon material expanded bed hydrogenation reactor system of proposition air lift hydrogen and liquid collection cups System, constitutes the change hydrogen-oil ratio operator scheme that course of reaction end hydrogen-oil ratio increases considerably suddenly.

The content of the invention

The present invention hydrocarbon material expanded bed hydrogenation reactor system of air lift hydrogen and liquid collection cups, it is characterised in that bag Containing following steps：

(1) in the first hydrogenation process R10, hydrogen, hydrocarbon liquid phase while the mixed phase that there may be solid particle be present Under the conditions of material, the first raw material R10F at least containing carbon and protium enters the first hydrogenation process R10 and carries out the One hydrogenation reaction R10R obtains the first hydrogenation reaction product BASE-R10P；

First raw material R10F, include liquid material R10FL and solid particulate materials R10FS that may be present；

In first hydrogenation process R10, hydrogen, hydrocarbon liquid phase be present while there may be solid particle；

First hydrogenation reaction R10R, at least a portion liquid material R10FL hydrofining reaction is included, may included extremely Few a part of liquid material R10FL hydrocracking reaction, at least a portion solid material R10FS that may be present may be included Hydrogenation heat cracking reaction；

First hydrogenation process R10, catalyst R10C may be used；

First hydrogenation reaction product BASE-R10P, for containing hydrogen, hydrocarbon liquid phase simultaneously may the mixed phase containing solid particle Material；

Material based on the first hydrogenation reaction product BASE-R10P is used as the first hydrogenation reaction effluent R10P-X, and first Hydrogenation reaction effluent R10P-X, occur in the form of 1 tunnel or 2 tunnels or multichannel material, the first hydrogenation reaction effluent R10P-X For gas phase or liquid phase or gas-liquid mixed phase or gas-liquid-solid three-phase logistics；

In the first hydrogenation process R10, the hydrogenation reactor used is up flow type expanded bed hydrogenation reactor, is used At least 1 hydrogenation reactor, least significant end hydrogenation reactor R10ZE carry out product using built-in liquid collection cups LD and take off liquid and liquid Body collects water conservancy diversion and obtains collection liquid R10ZE-TL and gas-liquid mixed phase product R10ZE-P；

In end reaction device R10ZE bottom, R10ZE reaction feed enters expanded bed hydrogenation reactor by charging aperture R10ZE lower reaction zone R10ZE-DZ is flowed up and is passed through R10ZE central reaction zone R10ZE-MZ to turn into middle part product R10ZE-IP, the material based on middle part product R10ZE-IP are entering the de- liquid of logistics separation and liquid on liquid collection cups LD tops Before collection space R10ZE-TZ completes the de- liquid process of logistics, logistics and gas at least partially based on middle part product R10ZE-IP Carrying hydrogen BH and being mixed into mixed material R10ZE-MZP makes at least a portion hydrocarbon liquid phase be vaporizated into gas phase hydrocarbon；In space R10ZE- TZ regions, mixed material R10ZE-MZP carry out de- liquid separation, and at least a portion liquid enters in liquid collection cups LD and along drain Pipe LK flowings turn into collection liquid R10ZE-TL, and remaining product R10P-P discharges reactor R10ZE through product mozzle；

The pressurized step ADP pressurizations of at least a portion collection liquid R10ZE-TL, at least a portion pressurization steps ADP discharges Collection liquid R10ZE-TL returns to the reaction compartment of middle part product R10ZE-IP upstream hydrogenation process as recycle oil R10ZE-RL In；

Heavy hydrocarbon weight concentration in collection liquid R10ZE-TL, the balance liquid phase R10ZE- higher than middle part product R10ZE-IP IP-L heavy hydrocarbon weight concentration；Light hydrocarbon, the total concentration by weight of middle matter hydrocarbon in collection liquid R10ZE-TL, are produced less than in middle part Thing R10ZE-IP balance liquid phase R10ZE-IP-L light hydrocarbon, the total concentration by weight of middle matter hydrocarbon；Middle part product R10ZE-IP takes During band solid particulate matter, the weight ratio for the solid particulate matter that collection liquid R10ZE-TL is carried, higher than middle part product R10ZE-IP's Balance the weight ratio for the solid particulate matter that liquid phase R10ZE-IP-L is carried；

(2) in recovery section S100, the product R10P100 of recovery the first hydrogenation process R10 discharges, product R10P100 comprises at least R10ZE-P.

The present invention, in the first hydrogenation process R10, in end reaction device R10ZE inside, generally, flow through liquid receipts Middle part product R10ZE-IP before collection cup LD outer walls mixes with air lift hydrogen BH；

In end reaction device R10ZE bottom, R10ZE reaction feed enters expanded bed hydrogenation reactor by charging aperture R10ZE lower reaction zone R10ZE-DZ is flowed up and is passed through R10ZE central reaction zone R10ZE-MZ to turn into middle part product R10ZE-IP, middle part product R10ZE-IP and air lift hydrogen BH are mixed into mixed material R10ZE- in mixed zone R10ZE-MZ MZP leaves mixed zone, and mixed zone R10ZE-MZ makes at least a portion hydrocarbon liquid phase in the product R10ZE-IP of middle part be vaporizated into gas phase Hydrocarbon；The top reaction zone R10ZE-UZ that mixed material R10ZE-MZP flows up through R10ZE turns into top product R10ZE- UP, top product R10ZE-UP flow through the runner using liquid collection cups LD at least a portion outside wall surface as runner wall, enter Liquid collection cups LD tops enter the de- liquid of reactor head product separation and liquid collection space R10ZE-TZ, here, part Liquid, which enters in liquid collection cups LD and along catheter LK flowings, turns into collection liquid R10ZE-TL, and remaining product R10P-P is through product Mozzle discharge reactor R10ZE.

The present invention, in the first hydrogenation process R10, in end reaction device R10ZE, at least a portion collection liquid R10ZE- After TL is as the pressurized step ADP pressurizations of recycle oil, adding in the first hydrogenation process R10 the first hydrogenation reactor is returned In hydrogen reaction compartment, or return to the hydrogenation positioned at middle part product R10ZE-IP upstreams in least significant end hydrogenation reactor R10ZE In reaction compartment.

The present invention, the first hydrogenation process R10, a kind or 2 kinds or several of following hydrogenation process can be selected from Combination：

1. the adding using expanded bed of the logistics containing oil product obtained by middle coalite tar or its distillate or its hot procedure Hydrogen process；Hot procedure is selected from coking or catalytic cracking process or catalytic pyrolysis process or hydrogenation process；

2. the hydrogenation using expanded bed of the logistics containing oil product obtained by high temperature coal-tar or its distillate or its hot procedure Process；

3. direct hydrogenation liquefaction of coal liquefaction process uses the hydrogenation process of expanded bed, the coal including the use of hydrogen supply dissolvent oil adds Hydrogen direct liquefaction liquefaction process, oily coal refine process altogether, coal faces hydrogen thermosol liquefaction process；

4. the hydrogenation process using expanded bed of the logistics containing oil product obtained by shale oil or its distillate or its hot procedure；

5. the hydrogenation process using expanded bed of ethylene cracking tar；

6. the hydrogenation process using expanded bed of the logistics containing oil product obtained by petroleum based heavy fuel oils or its hot procedure；

7. the hydrogenation process using expanded bed of the logistics containing oil product obtained by tar sand base heavy oil or its hot procedure；

8. other aromatic hydrocarbons weight contents use expanded bed higher than hydrocarbon ils of 40%, the organic nitrogen weight content higher than 0.10% Hydrogenation process.

The present invention, in the first hydrogenation process R10, existing solid particle, can be in following a kind or several Kind：

1. semicoke particle obtained by direct hydrogenation liquefaction of coal process；

2. catalyst granules；

3. iron rust particle；

4. particles of inorganic material；

5. the solid particle entered caused by coking of coal process in coal tar；

6. the product solid particle from hydro carbons thermal condensation process；

7. the solid particle from shale；

8. the solid particle from oil-sand；

9. other particles being present in the first hydrogenation reaction product BASE-R10P.

The present invention, any hydrogenation reactor that the first hydrogenation process R10 is used, mode of operation can be in following 1 kind or several of combination：

1. suspension bed is slurry bed system；

2. ebullated bed；

3. slight expanded-bed.

The present invention, in the first hydrogenation process R10, in end reaction device R10ZE, air lift hydrogen passes through horizontally disposed Distributor MG spray mixed into mixed zone with middle part product R10ZE-IP；

Generally, distributor MG includes cartridge type distributing chamber, the dual formula distributor spray of " nozzle-reflecting plate " composition of its locular wall The hydrogen gone out enters the de- liquid space in liquid collection cups LD tops with rising cocurrent after material cross-flow mixes；

Generally, the hydrogen stream that the hydrogen nozzle arranged in the vertical walls of cartridge type distributing chamber projects, if hit through fluid Hit opposite reflecting plate and then form specular scattering stream, it is secondary to pass through reaction mass upper up-flow；Air lift hydrogen BH and middle part product Cocurrent enters the de- liquid space in liquid collection cups LD tops after R10ZE-IP completes mixing；

Generally, distributor MG includes 2 layers or multilayer hydrogen circular distribution cylinder, and distributing barrel is setting internal hydrogen communication chamber The concentric drums connected with hydrogen connecting pipe, concentric drums are arranged vertically, and its axle center and reactor axis coinciding, beneficial to anti- Answer device radial section even symmetrical distributing hydrogen；

The function of circular distribution tube wall surface is：Arrange spout, the reflecting plate for serving as Hydrogen Jet Flow, augmentation of heat transfer, rectification with Weaken mixed process radial direction flow distribution unevenness and limit the flowing space scope of fluid；

Generally, distributor MG circular distribution tube wall surface epimere and hypomere reserve one section not opening area be used for Stable distritation The up charging and the flowing of the mixed material of distributor MG tops discharge that device MG bottoms enter, the Hydrogen Jet Flow that spout sprays, Its extended line not spray the spatial dimension i.e. extended line collision opposite reflective wall of cylinder barrel constraint, MG pairs of distributor directly The possibility answered is stripped the reactor shell inwall wall of hydrogen injection contact, sets liner plate or is distributed the lining of air lift hydrogen, Prevent air lift hydrogen from directly spraying contact reactor inwall；

The distance between adjacent distributions cylinder of cartridge type distributor, usually 0.1~1.0 meter, generally 0.15~0.6 meter, Preferably 0.25~0.40 meter

Nozzle hydrogen flow rate, usually 0.5~30 meter per second, generally 1.0~15 meter per seconds, be preferably 2.0~10 meters/ Second.

Spout horizontal dispersion angle, usually 0.0~30 °, generally 0.0~20 °, preferably 0.0~15 °.

The present invention, in the first hydrogenation process R10, in end reaction device R10ZE, the collection liquid of catheter LK discharges Normal boiling point is higher than the weight concentration of 300 DEG C of hydrocarbon component in total hydrocarbon component in R10ZE-TL：Typically larger than 65%, generally higher than 75%th, more preferably greater than 85%.

The present invention, in the first hydrogenation process R10, in end reaction device R10ZE, the air lift hydrogen BH used mark The ratio of 20 DEG C of volume amounts of the conventional liquid phase hydrocarbon in quasi- state volume flow BH-V and fresh feed R10F is K900, K900 Usual 300~3000,500~2000 are generally.

The present invention, in the first hydrogenation process R10, floating bed hydrogenation reactor can be used, operating condition is usually： Reaction temperature is 320~480 DEG C, 6~30MPa of reaction pressure, 0.2~5.0h of volume space velocity of reaction compartment^-1, hydrogen to oil volume ratio 200~3000, operating condition is generally：Reaction temperature is 360~460 DEG C, 12~25MPa of reaction pressure, the body of reaction compartment 0.2~5.0h of product air speed^-1, hydrogen to oil volume ratio 200~1500.

The present invention, the first hydrogenation process R10, using boiling bed hydrogenation reactor, operating condition is usually：Reaction temperature Spend for 320~480 DEG C, 6~30MPa of reaction pressure, reaction compartment 0.2~5.0h of volume space velocity^-1, hydrogen to oil volume ratio 200~ 3000, operating condition is generally：Reaction temperature is 360~460 DEG C, 12~25MPa of reaction pressure, the volume space velocity of reaction compartment 0.2~5.0h^-1, hydrogen to oil volume ratio 200~1500.

The present invention, in the first hydrogenation process R10, raw material R10F is from coal tar and is mainly higher than by normal boiling point During 400 DEG C of hydrocarbon component HD compositions, raw material R10F Unit Weight hydrogen consumption is usually 0.05~7.0%.

The present invention, in the first hydrogenation process R10, when raw material R10F is coal dust R10FS and hydrogen supply dissolvent R10FL, coal Powder R10FS Unit Weight hydrogen consumption is usually 2.5~10.0%.

The present invention, in the first hydrogenation process R10, when raw material R10F comes from coal tar, the hydrogenation catalyst that uses R10C, it can be a kind of compound coal tar hydrogenation catalyst, include high-activity component and low activity component；The high activity group It is 1: 10 to 10: 1 that parting, which belongs to the weight ratio of low activity component metals,；The high-activity component is the water soluble salt chemical combination of molybdenum Thing or its mixture；The low activity component is ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, catalyst R10C water content are less than 2wt%；R10C particle diameters are 1~100 μm of powdered granule.

The present invention, in the first hydrogenation process R10, when raw material R10F comes from coal tar, the hydrogenation catalyst that uses R10C, can comprise at least Mo elements, and Mo is M in the first hydrogenation process R10 body of work form₀S₂In, hydrogenation catalyst Agent R10C is 1~100 μm of powdered granule.

The present invention, when raw material R10F comes from coal tar, the first hydrogenation process R10 operating condition is usually：Temperature For 300~480 DEG C, pressure be 6.0~30.0MPa, hydrogen/feedstock oil volume ratio is 0.01: 1~4000: 1, hydrogenation catalyst R10C addition weight is the 0.001~8.0% of raw material R10F weight, reaction compartment volume space velocity is 0.1~10.0hr^-1；Raw material R10F weight chemistry hydrogen consumption is 0.05~7.0%, and the first hydrogenation process R10 operating condition is generally：Temperature is 350~460 DEG C, pressure be 12.0~25.0MPa, hydrogen/feedstock oil volume ratio is 50: 1~1200: 1, hydrogenation catalyst R10C Addition weight is the 0.5~5.0% of HDS weight, volume space velocity is 0.2~2.0hr^-1；Raw material R10F weight chemistry hydrogen consumption For 0.50~5.5%.

The present invention, the first hydrogenation process R10, usually using 1~4 hydrogenation reactor, typically added using 2~3 Hydrogen reactor.

The present invention, hydrogen supply hydrocarbon material can be included in the first hydrogenation process R10, raw material R10F.

Brief description of the drawings

Fig. 1 is the principle work(of the hydrocarbon material expanded bed hydrogenation reactor system of present invention air lift hydrogen and liquid collection cups Can schematic diagram.

As shown in figure 1, the reaction combined feed R11TF comprising liquid hydrocarbon, hydrogen enters hydrogenation process R10, show in figure What is gone out is situations of the hydrogenation process R10 using up flow type hydrogenation reactor R11, R12 of 2 serial operations, and first is hydrogenated with Reactor R11 is empty cartridge type suspension bed or the hydrogenation reactor for setting the liquid product circulatory system, the second hydrogenation reactor R12 are The floating bed hydrogenation reactor of the liquid product circulatory system is set, and final reacting product R100P enters thermal high point through pipeline 130 The air heat gas separated by high pressure separator S1V discharged along pipeline 201 and the hot high score oil S1L of liquid discharged along pipeline 202 are separated into from part S1 (containing solid particle).

As shown in figure 1, the feedstock hydrocarbon R11CF conveyed through pipeline 101, the hydrogen logistics R11HF conveyed with pipeline 102 After mixing, the combined feed R11TF as the first hydrogenation process R10 enters the first hydrogenation reactor R11 through road 105 and carries out the One hydrogenation reaction obtains reaction product R11P；R11P enters the second hydrogenation reaction of the second hydrogenation reactor R12 progress through road 107 and obtained To reaction product R12P and it is used as final reacting product R100P.

As shown in figure 1, the second hydrogenation reactor R12 is the floating bed hydrogenation reactor for setting the liquid product circulatory system, Liquid collection cups LD, catheter LK are provided with, the liquid R12-RL of liquid collection cups LD discharges enters circulation by catheter LK It is divided into 2 tunnels after pump PP pressurizations, first via liquid PPLA is as the second hydrogenation reactor R12 repeats itselfs oil, through pipeline 120 and warp After the reaction product R11P mixing that pipeline 107 conveys, the combined feed R12TF as the second hydrogenation reactor R12 enters through road 108 Second hydrogenation reactor R12 carries out the second hydrogenation reaction and obtains reaction product R12P.

As shown in figure 1, when hydrogenation process R10 performs coal liquifaction hydrogenation reaction, feedstock hydrocarbon R11CF is to include coal The coal of the raw materials such as powder, hydrogen supply dissolvent, circulation slurry oil, catalyst, vulcanizing agent, the first hydrogenation reactor R11 carry out coal swelling With either shallow coal liquefaction hydrogenation reaction, the first hydrogenation reactor R11 can be to set the floating bed hydrogenation of the liquid product circulatory system anti- Answer device；Second hydrogenation reactor R12 carries out depth coal liquefaction hydrogenation reaction, and the second hydrogenation reactor R12 is setting liquid product The floating bed hydrogenation reactor of the circulatory system, light oil, middle matter oil and mink cell focus and not retortable are contained in reaction product R12P Thing such as catalyst, ash content, liquefaction semicoke, asphaltene, preasphaltene etc., are ensureing thermal high separate section operability premise Under, recycle oil R12-RL hydrocarbon component caused by the second hydrogenation reactor R12 preferably deviates from light oil and at least a portion The high boiling hydrocarbon of middle matter oil, to avoid unhelpful harmful circulation thermal cracking of light oil, middle matter oil.

As shown in figure 1, when hydrogenation process R1 performs coal tar hydrogenating reaction, feedstock hydrocarbon R11CF is to include coal Tar, catalyst, the coal of vulcanizing agent, feedstock hydrocarbon R11CF are also possible that circulation slurry oil, hydrogen supply dissolvent, pyrolysis or dry Semicoke dust of process etc. is evaporated, the first hydrogenation reactor R11 carries out the hydrofining reaction of coal tar and/or either shallow is hydrocracked Reaction, the first hydrogenation reactor R11 can be empty cartridge type suspension bed or the hydrogenation reactor for setting the liquid product circulatory system；Second Hydrogenation reactor R12 carries out coal tar overhydrocracking reaction, and the second hydrogenation reactor R12 is setting liquid product cyclic system The floating bed hydrogenation reactor of system, in reaction product R12P containing light oil, middle matter oil and mink cell focus and can not distillation such as urge Agent, ash content, semicoke, asphalitine etc., under the premise of thermal high separate section operability is ensured, the second hydrogenation reactor R12 Caused recycle oil R12-RL hydrocarbon component is preferably to deviate from the high boiling hydrocarbon of matter oil in light oil and major part, light to avoid Unhelpful harmful circulation thermal cracking of oily, the middle matter oil of matter.

As shown in figure 1, when hydrogenation process R1 performs the reaction of high temperature coal-tar deep hydrofinishing, feedstock hydrocarbon R11CF be comprising high temperature coal-tar, catalyst, vulcanizing agent coal, feedstock hydrocarbon R11CF be also possible that circulation slurry oil, Semicoke dust of hydrogen supply dissolvent, pyrolysis or retort process etc., the first hydrogenation reactor R11 carry out the hydrofining reaction of coal tar And/or either shallow coal hydrogenation cracking reaction, the first hydrogenation reactor R11 can be empty cartridge type suspension bed or set liquid product cyclic system The hydrogenation reactor of system；Second hydrogenation reactor R12 carries out the reaction of coal tar deep refining and/or either shallow hydrocracking reaction, the Two hydrogenation reactor R12 are the floating bed hydrogenation reactor for setting the liquid product circulatory system, are contained in reaction product R12P light Matter is oily, middle matter oil and mink cell focus and can not distillation such as catalyst, ash content, semicoke, asphalitine etc., ensureing thermal high separation unit Divide under the premise of operability, recycle oil R12-RL hydrocarbon component caused by the second hydrogenation reactor R12 preferably deviates from light oil And the oily high boiling hydrocarbon of matter in major part, to avoid the inefficient cycle of light oil, middle matter oil from being hydrogenated with.

As shown in figure 1, as needed, recycle oil R12-RL is divided into 2 tunnels, first via liquid after circulating pump PP pressurizations PPLA, the second road liquid PPLB, the second road liquid PPLB is as the first hydrogenation reactor R11 recycle oils, through pipeline 121 and through pipe Road 101 convey feedstock hydrocarbon R11CF mixing after, as the first hydrogenation reactor R11 combined feed R12TF a part through road 105 carry out circulation hydrogenation into the first hydrogenation reactor R11.

Fig. 2 is the distributor of the hydrocarbon material expanded bed hydrogenation reactor system of present invention air lift hydrogen and liquid collection cups A kind of schematic diagram of MG structure type.

As shown in Figure 1 and Figure 2, the top of the second hydrogenation reactor R12 main body reaction compartment, is provided with air lift hydrogen Distributor MG blenders of air lift hydrogen and reaction mass in other words, in this Mixed Zone, air lift hydrogen spray with vertically upward The reaction mass cross-flow mixing of flowing, hydrogen stream smash air pocket and big liquid bolus in reaction mass；Air lift hydrogen Best level sprays.The reacted device wall opening 501 of hydrogen enters cartridge type distributing chamber 503 through passage 502.

As shown in Figure 1 and Figure 2, in the second hydrogenation reactor R12 air lift hydrogen and the mixed zone of reaction mass, water is set The distributor MG that plain cloth is put, distributor MG are cartridge type distributing chamber, the dual formula distributor of " nozzle-reflecting plate " composition of its locular wall Enter the de- liquid space in liquid collection cups LD tops with rising cocurrent after material mixes.

As shown in Fig. 2 the hydrogen stream that distributor MG distribution nozzles project, if through fluid impact opposite reflecting plate Specular scattering stream is formed, secondary to pass through reaction mass upper up-flow, air lift hydrogen completes cocurrent after mixing with reaction mass and enters liquid Body collection cups LD tops take off liquid space.The hydrogen stream that distribution nozzles project, also rinse the possibility deposit of opposite reflecting plate Effect.Distributor MG hydrogen nozzle, generally horizontal arrangement is to produce hydrogen stream of the exit as horizonally projected jet.

Hydrogen distribution cylinder 503 can arrange hydrogen spout or 2 sides arrangement hydrogen spout with 1 side.

As shown in Fig. 2 distributor MG includes 3 layers of Hydrogen distribution cylinder 503, distributing barrel is the use for setting internal hydrogen communication chamber The concentric drums that hydrogen communicating pipe 502 connects, concentric drums are arranged vertically, and its axle center and reactor axis coinciding, are beneficial to Reactor radial section even symmetrical distributing hydrogen；The major function of cylinder wall 505 is：Arrangement spout 600, serve as Hydrogen Jet Flow Reflecting plate, augmentation of heat transfer, rectification with weaken mixed process radial direction flow distribution unevenness and limit fluid the flowing space Scope；The epimere of cylinder wall 505 and hypomere reserve one section of upper traveling that opening area does not enter for Stable distritation device MG bottoms The flowing of material and the mixed material of distributor MG tops discharge, the Hydrogen Jet Flow that spout sprays, its extended line had better not be direct Spray the spatial dimension of cylinder barrel constraint；It may be stripped corresponding to distributor MG in the reactor cylinder body of hydrogen injection contact Wall wall, center catheter LK outer wall walls, liner plate is set or is distributed the lining of air lift hydrogen, prevents air lift hydrogen from directly spraying Contact the wall.

The distance between cartridge type distributor MG adjacent distributions cylinder 503, usually 0.1~1.0 meter, generally 0.15~ 0.6 meter, preferably 0.25~0.40 meter.

Hydrogen flow rate at spout 600, usually 0.5~30 meter per second, generally 1.0~15 meter per seconds, be preferably 2.0~10 Meter per second.

The horizontal dispersion angle of spout 600, usually 0.0~30 °, generally 0.0~20 °, preferably 0.0~15 °.

Distributor MG, in addition to charging aperture, hydrogen spout, bottom can set a small amount of tear is empty to be used for discharge opeing of stopping work, normal behaviour Make drain hole jet amount during operating mode, be advisable with 1% less than air lift hydrogen total amount.

Gas hydrogen opening in wall of reactor, connected by hydrogen distribution pipe and distributor MG 3 layers of Hydrogen distribution cylinder Connect, distribution pipe plays the role of certain distribution gas flow, and pressure drop elements such as one section of minor diameter can be set inside distribution pipe Pipe.

Percent opening on Hydrogen distribution tube wall surface, with few, more away from hydrogen inlet pipe position close to hydrogen inlet pipe position Principle distribution, to be evenly distributed hydrogen as far as possible.

The fixed form of distributor MG, Hydrogen distribution cylinder, hydrogen distribution pipe in reactor, can be any appropriate side Formula, for example fix Hydrogen distribution cylinder using the mode of bottom support beam.

Embodiment

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 material under an atmospheric pressure, liquid equilibrium temperature.

Conventional boiling range of the present invention refers to the normal boiling point scope of cut.

Proportion 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 weight basis unless stated otherwise Value.

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

Conventional liq hydrocarbon of the present invention, refer 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, refer to hydro-conversion thing such as water, ammonia, the vulcanization of non-hydrocarbon component in feedstock oil Hydrogen, hydrogen chloride etc..

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

Middle matter hydrocarbon of the present invention, is diesel component, refers to the hydro carbons that normal boiling point is 200~330 DEG C.

Wax oil component of the present invention refers to the hydro carbons that normal boiling point is 330~530 DEG C.

Heavy hydrocarbon of the present invention, refer to that normal boiling point is higher than 330 DEG C of hydro carbons.

Hydrogen to oil volume ratio of the present invention, refer to the standard state volume flow of hydrogen with specifying the normal of oily logistics The ratio of pressure, 20 DEG C of volume flow.

The weight ratio for the solid particulate matter that collection liquid R10ZE-TL is carried, refer to the solid that collection liquid R10ZE-TL is carried The ratio of the weight of particulate matter and the weight of pure liquid phase material.

Hydrogenation reaction space, refer to occurring the fluid circulation space of the hydrogenation reaction, can be reaction in space such as Empty barrel reactor area, air lift hydrogen mixed zone, liquid collection cups upper space region etc., can be the reactor external space such as pipelines Space in interior space, valve, space in blender, space etc. in pump.

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

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

The present invention described in detail below.

Coal tar and coal tar hydrogenating process are described below.

Coal tar of the present invention, refer to from pyrolysis of coal or coking of coal or the dry distillation of coal or the pyrolysis of coal generating gas process step The coal tar of process or its cut such as rapid, can be accessory substance coalite tar or its cut or the coal refining of coal generating gas Coking coal pyrolytic process (including semicoke, medium temperature coking, high-temperature coking process) accessory substance coal tar or its cut, institute of the present invention State the miscella that coal tar can also be above-mentioned coal tar.Coal tar of the present invention, including low temperature tar, middle temperature tar, height Temperature tar, the miscella of different coal tar, the distillate of coal tar.

High-temperature coking belongs to coal high temperature pyrolysis process, and the final temperature of pyrolytic process is generally higher than 900 DEG C, generally 1000 Between~1400 DEG C.The high temperature coal-tar refers to that coal high temperature pyrolysis produces the pair of coke and/or the production of town gas process Product crude tar oil.High temperature coal-tar generally produces following product in primary distillation process：Light oil (topping tar), carbolic oil, naphthalene The product such as oil, lightweight washing oil, heavy wash oil, lightweight carbolineum, heavy carbolineum, pitch, carbolic oil can be further separated into crude phenols and take off Carbolic oil, naphtalene oil can be further separated into thick naphthalene and de- naphtalene oil.High temperature coal-tar light fraction of the present invention refers to：Carbolineum, wash Oil, naphtalene oil, de- naphtalene oil, carbolic oil, dephenolize oil, light oil and its miscella.

Because raw coal property and coking or gas-making process condition change within the specific limits, the property of coal tar is also one Determine to change in scope.The process conditions and product requirement of coal tar primary distillation process also change within the specific limits, therefore coal tar The property of oily light fraction also changes within the specific limits.The property of coal tar light fraction, proportion are usually 0.92~1.25, conventional It is usually 120~460 DEG C that boiling point, which is generally 60~500 DEG C, usual tenor is 5~80PPm, sulfur content be 0.4~ 0.8%th, nitrogen content be 0.6~1.4%, oxygen content be 0.4~9.0%, usual water content be 0.2~5.0%, carbon residue content leads to It is often 0.5~13%.

Medium temperature coal tar of the present invention, it is that 120~450 DEG C of hydrocarbon components and normal boiling point are high typically comprising conventional boiling range In the mixture of 450 DEG C of hydrocarbon components, the light fraction FD1 that the conventional boiling range for generally comprising 10~20% is 120~260 DEG C is (containing double Cyclophane hydrocarbon-fraction), to generally comprise 30~40% conventional boiling range be that 260~370 DEG C of middle cut FD2 (contains bicyclic, thrcylic aromatic hydrocarbon Cut), include the heavy distillat FD3 (containing bicyclic to Fourth Ring aromatic fraction) and 8 that 20~35% conventional boiling range is 370~450 DEG C ~20% conventional boiling range is higher than 450 DEG C of residue oil fraction FD4 (i.e. coal tar pitch cut).Table 1 be in typical medium temperature coal tar not With boiling fraction content statistical form.

Different boiling ranges ends content statistical form in 1 typical medium temperature coal tar of table

Middle coalite tar, the foreign metal overwhelming majority concentrate on normal boiling point and 450 DEG C are especially greater than higher than 350 DEG C In cut, and generally using hydrogenolysis-prone metal component iron, calcium, magnesium as key component, typically oil soluble metal compound such as cycloalkanes Sour iron, calcium naphthenate etc., these hydrogenolysis-prone metal components can be quickly sent out at certain high temperature and hydrogen existence condition Raw hydrogenolysis is converted into sulfide such as iron sulfide, calcium sulfide, and can form granular precipitates or co-precipitate, certain Under the conditions of, particle size can grow up.Experimental study and commercial plant operating show, in the hydrogenation reaction of middle coalite tar During, raw material different component reaction temperature according to be divided into from low to high following steps substantially meet it is actual：Hydrogenolysis-prone gold Category thermal decomposition ＜ high activity condensed-nuclei aromatics thermal condensations and the rudimentary sulphur compound hydrodesulfurizations of hydrogenation saturation ＜, metal-organic complex Catalytic hydrogenolysis, rudimentary organic phenol catalytic deoxidation, polycyclic aromatic hydrocarbon take off carbon residue, said temperature be generally in the range of 170~350 DEG C, it is general For 210~330 DEG C, it is evident that this is the reaction temperature section of a wide scope, and the light fraction for middle coalite tar is preferably controlled First, second, third step of different temperatures section is made as according to carrying out stage by stage from low to high, beneficial to reducing metal sulfide life Into speed, reduction pyrocondensation compound formation speed, prevent from forming superposition peak value, realize hydrogenolysis-prone metal deposit in beds Depth profiles, improve the controllability of deposition reaction.

The olefin(e) centent height of cut of the coalite tar light fraction such as normal boiling point less than 350 DEG C, phenol content in generally High, gum level height simultaneously contains the more component easily reacted under the conditions of mitigation, therefore, the pre-add of described coal tar light fraction Hydrogen process, usually using hydrogenation protecting agent, olefins hydrogenation agent, hydrogenation deoxidation agent, removal of ccr by hydrotreating agent, hydrogen desulfurization agent etc. Single dose or the tandem compound or mixed loading combination of double agent or multi-agent, usually using down-flow fixed bed hydrogenation reactor.The present invention The middle coalite tar light fraction oil, refers to that normal boiling point is generally 60~480 DEG C, usually 60~450 DEG C of coal Tar cuts oil, can generally fixed bed hydrogenation technology be used to carry out hydro-upgrading.

Residue oil fraction FD4 is generally difficult to realize long period using conventional bed technology, is hydrogenated with lighting in high yield therefore adopts With up flow type expanded bed such as suspension bed or boiling bed hydrogenation technical transform it, it is unnecessary in order to prevent from gum asphalt from reuniting triggering Coking reaction, it is often necessary to it is dissolved using the solvent hydro carbons for having good ability of dissolving each other with cinder oil distillate and scattered forms glue The weak solution of matter asphalitine, solvent hydro carbons can be the heavy distillat FD3 or heavy distillat that conventional boiling range is 370~450 DEG C The FD3 and residue oil fraction FD4 conversion product of hydrogenation aromatic moiety saturation or middle cut FD2 hydrogenation aromatic moiety is satisfied The conversion product of sum.The conversion product of middle cut FD2 hydrogenation aromatic moiety saturation belongs to excellent hydrogen supply dissolvent, rich in hydrogen supply hydrocarbon.

Heavy distillat of the normal boiling point of middle coalite tar higher than 350 DEG C includes coal tar pitch, and its suitable method of hydrotreating is Using the hydrogenation thermal cracking process of up flow type expanded bed, following process as needed can be with supporting hydro-upgrading process.

Middle coalite tar heavy fraction of oil of the present invention, refer to that normal boiling point is usually above 370 DEG C, is generally greater than 400 DEG C of middle coalite tar cut, their hydrogenation thermal cracking process, refer to that at least a portion hydrocracking reaction occurs The process that molecular weight is less than cracked stock molecular weight is produced, the process generally comprises parallel HDM, hydrofinishing, added Hydrogen heat cracking reaction.In generally coalite tar heavy distillat such as normal boiling point higher than 350 DEG C and containing low in coal tar pitch Warm coal tar fraction, its tenor is high, gum level is high, asphalt content is high, contains solid particulate matter, therefore, described The hydrogenation thermal cracking process of coal tar heavy fractioning, usually using the up flow type expanded bed such as hydrogenation reaction such as ebullated bed, suspension bed Device, so as in fast online replacement reaction zone because of metal deposit and/or green coke the hydrogenation catalyst of rapid deactivation, protect simultaneously Card reaction stream has been developed that varied by the beds of reaction zone, its catalyst used, auxiliary agent unobstructedly Complex function catalyst, auxiliary agent.The hydrogenation heat cracking reaction area of the middle coalite tar heavy fraction of oil, catalyst bed Layer working method is usually up-flow reactor, a kind or several of the combination in following：

1. suspension bed is slurry bed system；

2. ebullated bed；

3. up flow type moving bed；

4. up flow type slight expanded-bed.

On hydrocarbon material hydrogen addition technology, prior art can be used or be used cooperatively with reasonable selection, had a variety of Method or scheme, suspension bed or boiling bed hydrogenation method described as follows：

A kind of 1. hydrogenation method for coal tar suspension bed of heterogeneous catalysis of Chinese patent ZL201010217358.1；

Applicant：China Coal Research Institute；

Slurry-bed hydrocracking process feedstock oil：Coal tar heavy fractioning more than 370 DEG C；

Product：Floating bed hydrocracking generation oil is by hydrogenation grading process, production high-quality diesel component, naphtha group Point；

Reactor types：Suspension bed, structure type are unrestricted；

Catalyst type：The grain of monometallic active component or compound more metal active constituents containing molybdenum, nickel, cobalt, tungsten or iron The coal tar suspension bed hydrogenation catalyst of powdered granule of a diameter of 1~100 micron of son；Suspension bed hydrogenation catalyst dosage is with activity Component metals gross mass is calculated as the 0.1~4% of floating bed raw material coal tar；

2. a kind of full fraction of coal tar floating bed hydrocrackings of Chinese patent application CN104946306A and fixed bed hydrogenation Modification combined method.

Applicant：China Petroleum Univ. (East-China)；

Slurry-bed hydrocracking process feedstock oil：Coal tar normal pressure fractionation gained reduced crude；

Product：Floating bed hydrocracking generation oil passes through fixed bed hydrogenation grading process, production high-quality diesel component, stone Cerebrol component；

Reactor types：Suspension bed, structure type are unrestricted；

Catalyst type：Oil-soluble complexing agent, including two components or three component oil soluble metal catalyst, vulcanizing agent and suppression Burnt agent；Oil soluble metal catalyst is two kinds or three kinds of mixture in molybdenum naphthenate, nickel naphthenate and cobalt naphthenate, is suspended Bed hydrogenation catalyst dosage is calculated as 40~1000PPm of full fraction of coal tar with total metal mass；

3. a kind of coal tar suspension bed hydrocracking unit optimization chargings of Chinese patent ZL201310447621.X is supporting Process；

Applicant：Beijing petroleum chemical engineering Co., Ltd；

Slurry-bed hydrocracking process feedstock oil：Boiling range obtained by vacuum fractionation is 320~565 DEG C of wax oil cuts and taken off Except the boiling point more than 25 microns of solid particles is more than 565 DEG C of decompression residuum；

Reactor types：Suspension bed, structure type are unrestricted；

Catalyst type：Unrestrictedly；

A kind of 4. full fraction of coal tar hydroprocessing techniques of Chinese patent ZL200410050747.4；

Applicant：China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute；

Slurry-bed hydrocracking process feedstock oil：Full fraction of coal tar；

Reactor types：Suspension bed, structure type are unrestricted；

Catalyst type：Homogeneous catalyst, it is one or more metals of periodic table of elements vib and group VIII The compound of (such as Mo, Ni, Co, W, Cr, Fe) or its aqueous solution, suspension bed hydrogenation catalyst dosage are calculated as with total metal mass 50~200PPm of full fraction of coal tar；

5. Chinese patent ZL201010222021.X a kind of floating bed hydrogenation reactor and technique with high-pressure separator；

Slurry-bed hydrocracking process feedstock oil：Poor oil；

Reactor types：Floating bed hydrogenation reactor with high-pressure separator；

Catalyst type：Unrestrictedly；

6. the DCL/Direct coal liquefaction side of a kind of adverse currents of Chinese patent ZL03102672.9, circulation, online hydrogenation reactor series connection Method；

Applicant：Beijing Coal Chemistry Inst., Coal Sciences General Inst.；

Circulation circulation flow reactor slurry-bed hydrocracking process raw material in second segment：Coal slurry first paragraph counter-current reactor Bottom liquid discharges material admittedly；

Product：DCL/Direct coal liquefaction generation oil completes hydrogenation grading process by online hydrogenation reactor, produces high quality bavin Oil ingredient, gasoline component；

Reactor types：Interior circulation circulation pattern floating bed hydrogenation reactor；

Catalyst type：Unrestrictedly；

A kind of 7. floating bed hydrogenation reactors of Chinese patent application CN102451650A；

Reactor types：2 or multiple inner circulation zones are set in device；

A kind of 8. fluidized bed reactors of Chinese patent application ZL200710012680.9；

Reactor types：Middle and upper part sets at least one inner circulation zone in device；

A kind of 9. Multi-stage boiling bed hydrogenation process devices of Chinese patent application ZL201010522203.9；

Reactor types：Middle and upper part sets at least two inner circulation zone in device；

A kind of 10. methods of coal tar oil boiling bed hydrogenation of Chinese patent CN104593060A；

Slurry-bed hydrocracking process feedstock oil：The dehydration of coal tar or coal tar oil boiling bed hydrogenation modification generation oil Oil；

Product：Floating bed hydrogenation refined oil；

Reactor types：Boiling bed hydrogenation reactor；

Catalyst type：Using cheap FeOOH as active metal component catalyst for hydro-upgrading and Hydrobon catalyst grading uses.

Hydrogen supply hydrocarbon is described below.

Hydrogen supply hydrocarbon described herein, refer to that the high-temperature hydrogenation thermal cracking in low hydrogen content hydrocarbon ils such as residue oil fraction FD4 is anti- There is the hydrocarbon component of hydrogen supply function during answering, hydrogen supply hydrocarbon includes double ring arene, the polycyclic aromatic hydrocarbon of fractional saturation of fractional saturation, The species and function of the hydrogen supply hydrocarbon used with coal liquefaction are same or like.In hydrogen supply hydrocarbon, the hydrogen supply speed of dihydro body is all higher than four Hydrogen body, the dihydro body of thrcylic aromatic hydrocarbon and the dihydro body phase ratio of double ring arene, it is low that its hydrogen supply speed has height to have；Experiment it has been proved that Although polycyclic aromatic hydrocarbon has the ability for transmitting hydrogen without hydrogen supply capacity.At 400 DEG C, the relative hydrogen supply speed of following component is as follows：

DCL/Direct coal liquefaction process is described below.

DCL/Direct coal liquefaction process of the present invention, refer to the side for making coal liquefaction by hydrogenation under solvent naphtha existence condition Method, according to the difference of the difference of solvent naphtha and catalyst, the difference of pyrolysis way and hydrogenation mode and process conditions, Ke Yifen For following several techniques：

1. dissolving pyrolysis liquefaction process：Low-ash extract can be made to pyrolysis of coal extracting using heavy solvent, and (Japan claims Swelling charcoal)；Extract the available oils based on mink cell focus at supercritical conditions using light solvent.This method does not have to hydrogen, Though former process yield is high but product is still solid, latter technique such as supercritical extraction (extraction) method (SCE) extract content is not It is too high；

2. solvent hydrogenation extracting liquefaction process：If any solvent refined coal process l and II (SRC-1 and SRC-II), Exxon donor solvent process EDS, Japanese New Energy Development Organization liquefaction process (NEDOL) etc., using hydrogen, but pressure is less high, and solvent naphtha has obvious work With；

3. Hydrogenation method：Such as the old and new's liquefaction process (IG and NewlG) of Germany and the H coal process (H- in the U.S. ) etc. Coal it is a kind of to belong to this；

4. coal and residual oil joint processing method (C0processing)：Using residual oil as solvent naphtha together with coal once by anti- Device is answered, without recycle oil.Hydrocracking occurs is converted into light oil to residual oil simultaneously.The U.S., Canada, Germany and former Soviet Union etc. are each There is different technique；

5. destructive distillation liquefaction process：Coal is first pyrolyzed to obtain tar, then carries out hydrocracking and upgrading to tar；

6. underground liquefaction process：Solvent is injected into subterranean coal, makes coal depolymerization and dissolving, collapses coal plus the impulsive force of fluid Dissipate, the coal not being completely dissolved is then suspended in solvent, is extracted solution out with pump and is separated processing.

In coal direct liquefaction method, majority belongs to direct hydrogenation liquefaction of coal liquefaction process, and no matter which kind of coal faces the direct liquid of hydrogen Change process, its target are to obtain oil product, and the function of pursuit is " coal turns oil ", it is necessary to which existing chemical change is that " coal adds Hydrogen ", the common trait of current such technology is to use solvent naphtha and catalyst, and the conventional boiling range of solvent naphtha is generally 200~450 DEG C, it is most be 200~400 DEG C, solvent naphtha majority be distilled oil, and contained aromatic hydrocarbons majority is the aromatic hydrocarbons of 2~4 ring structures.Therefore, Either which kind of coal faces hydrogen direct liquefaction process, outer oil extraction caused by it or liquefied coal coil (being usually coal liquefaction light oil) or coal liquid Carburetion modified oil, as long as its composition possesses raw material compositing characteristic of the present invention, it can be processed using the inventive method.

A kind of thermally dissolving and catalytic with lignite preparing liquid fuel that patent CN100547055C states clearly is owned by France to press in lignite It is hydrogenated with direct liquefaction process, including Coal liquefaction process and liquefied coal coil hydrogenation modification process totally two processes.In order to improve The conversion ratio of coal direct liquefaction and realize that coal feedstock enters reactor, coal enters usual before reactor Coal dust is made, is made into coal with possessing the solvent naphtha of good hydrogen supply capacity, coal is pressurized, it is anti-to enter coal liquefaction after heating Answer device.

Coal liquefaction process of the present invention, refer to using coal and molecule hydrogen that may be present as raw material, with spy Fixed oil product (being usually the hydrogenation modification oil of liquefied coal coil) is hydrogen supply dissolvent oil, certain operating condition (such as operation temperature, Operating pressure, solvent naphtha/coal weight ratio, hydrogen/solvent naphtha volume ratio and suitable hydrogenation catalyst) under, carbon directly occurs for coal The thermal cracking of carbon key, the course of reaction of hydrogenation liquefaction.

Liquefied coal coil of the present invention, oil product caused by the Coal liquefaction process is referred to, it is present in coal hydrogenation It is the combined reaction product based on hydrogen supply dissolvent oil, reaction consumption coal and reaction transfer hydrogen in liquefaction reaction effluent.

After Coal liquefaction process works well, the self-produced coal liquid of hydrogen supply dissolvent oil generally use Coal liquefaction process The hydrogenation modification oil of carburetion (being usually that conventional boiling range is higher than 165 DEG C of distillate), liquefied coal coil hydrogenation modification process it is main Target is production Coal liquefaction process solvent naphtha, is exactly specifically to improve in oil product " to have the group of good hydrogen supply function Point " content, for example improve cycloalkyl benzene class, the content of bicyclic alkyl benzene class component, contained based on liquefied coal coil a large amount of bicyclic The fact that aromatic hydrocarbons and a large amount of thrcylic aromatic hydrocarbons, liquefied coal coil hydrogenation modification process are the hydrogenation of one " appropriate aromatic hydrocarbons saturation " Journey.

The final goal of Coal liquefaction process is the outer oil product supplied of production, and usual liquefied coal coil hydrogenation modification process produces Hydrogenation modification oil be two parts：A part is used as Coal liquefaction process hydrogen supply dissolvent oil, and a part is used as coal liquefaction The outer oil extraction of liquefaction process.Generally, at least a portion coal liquefaction light oil caused by Coal liquefaction process is used as outside coal liquifaction process Oil extraction A, it is molten that remaining liquefied coal coil is used as liquefied coal coil hydrogenation modification process feedstock oil production Coal liquefaction process hydrogen supply The oily and outer oil extraction B of agent, the outer oil extraction of A and B two-way now be present, the final whereabouts of the outer oil extraction of A and B two-way is typically each by depth It is hydrogenated with grading process and produces high-quality oil product such as diesel oil distillate, naphtha cut.

The present invention is described in detail below in conjunction with accompanying drawing, accompanying drawing is drawn to describe the present invention, but it can not be limited The application of the fixed present invention.

Up flow type expanded bed hydrogenation reactor R10ZE of the present invention, the basic element of character generally have：

1. reactor shell R10ZES；

2. the opening (or being adapter) on reactor shell R10ZES；

3. being arranged in the up flow type hydrogenation main reaction space of middle hypomere in reactor shell R2ES, generally make during working condition With catalyst, it is used to be uniformly distributed charging usually using charging distributed component；

4. it is arranged in the air lift Hydrogen distribution device MG of epimere or middle epimere in reactor shell R10ZES；

5. it is arranged in the liquid collection cups LD and liquid conduits LK of epimere or middle epimere in reactor shell R10ZES；

6. reactor intermediate feed distributor (or distributor), such as blender of catalyst bed interlayer, 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：The temperature-measuring part such as thermocouple of reaction bed temperature is tested, measures reactor The pressure gauge of system specific location pressure, measure liquid level instrument such as glass plate, floating drum, double flange difference gauges, the guided wave of liquid level Radar, ray level-sensing device etc.；

Up-flow reactor of the present invention, accessory are external insulation material, support member (skirt or journal stirrup), base Plinth, ladder, operating platform and fire-fighting accessory that may be present such as steam smothering ring.According to the conditions such as ground geology, meteorology are built, tie The conditions such as weight of equipment, height are closed, up-flow reactor of the present invention needs piling to control as needed under its basis Its basic sinking speed.

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

1. floating bed hydrogenation reactor；

2. boiling bed hydrogenation reactor, generally draw off the decreased catalysis of activity from bed bottom in an intermittent fashion Agent, fill into fresh catalyst from bed top in an intermittent fashion and maintain bed catalyst reserve；

3. slight expanded-bed.

The characteristic of the present invention is described below.

First hydrogenation process R10, catalyst R10C may be used；

5. the hydrogenation process using expanded bed of ethylene cracking tar；

2. catalyst granules；

3. iron rust particle；

4. particles of inorganic material；

5. the solid particle entered caused by coking of coal process in coal tar；

7. the solid particle from shale；

8. the solid particle from oil-sand；

1. suspension bed is slurry bed system；

2. ebullated bed；

3. slight expanded-bed.

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 any hydrogenation process, but is typically incorporated into most upstream Hydrogenation process entrance, to ensure course of reaction necessary minimum concentration of hydrogen sulfide such as 500PPm (v) or 1000PPm (v) or setting is expected, to ensure that the necessary hydrogen sulfide sectional pressure of catalyst is not less than minimum setting.Described supplement sulphur can Be sulfide hydrogen or can be converted into hydrogen sulfide to material of the hydroconversion process without ill-effect, it is such as hydrogen sulfide containing Gas or oil product, or generate molten sulfur or carbon disulfide or DMDS of hydrogen sulfide etc. after being contacted with high-temperature hydrogen.

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 Oil density big (for example being approached with water density) or viscosity are big or when being difficult to separate with water emulsification, it is also necessary to set operation temperature usual For 150~450 DEG C of high pressure hot separator, now hydrogenation reaction effluent is separated into one in volume into high pressure hot separator On the hot gas separated by high pressure separator gas that is mainly made up of hydrogen and one be mainly made up of conventional liq hydrocarbon and solid that may be present Hot high score fluid body, hot gas separated by high pressure separator enter operation temperature be usually 20~80 DEG C of cold high pressure separator be separated into cold high score oil and Cold gas separated by high pressure separator, because a large amount of high boiling components enter in hot high score fluid body, realize following target：Cold high score oil density diminishes Or viscosity diminishes or is easily isolated with water.The high pressure separation process of hydrogenation reaction effluent sets high pressure hot separator, is also equipped with The advantages of reducing thermal loss because hot high score fluid body can avoid hot gas separated by high pressure separator experience using air cooler or water cooler Cool process.Meanwhile the hydrogenation process that the hot high score fluid body in part can be returned to upstream recycles, to improve The overall raw material property of the hydrogenation process of the recycle oil is received, or circulation hydrogenation is carried out to the recycle oil.

Hydrogenation reaction effluent or hot gas separated by high pressure separator enter before cold anticyclone separate section, generally first reduce temperature and (are 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 generally thereto inject washings formed water filling back end hydrogenation reaction effluent, washings be used 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 is separated into：One cold gas separated by high pressure separator being mainly made up of in volume hydrogen, a master Will by cold high score that conventional liq hydrocarbon and dissolved hydrogen form oil, one it is being mainly made up of water and dissolved with ammonia, hydrogen sulfide it is cold High score water.The cold high score water, the content of wherein ammonia are generally 0.5~15% (w), preferably 1~8% (w).Note washings One purpose is to absorb the ammonia and hydrogen sulfide in hydrogenation reaction effluent, prevents that to form sulphur hydrogenation ammonia or more sulphur ammonia Crystallization Pluggings changes Hot device passage, increase system pressure drop.The injection rate of the washings, it should be determined according to following principles：On the one hand, washings are noted It is divided into vapour phase water and liquid phase water after entering hydrogenation reaction effluent, liquid phase water have to be larger than zero, preferably wash water inventory 30% or more；Another further aspect, washings are used to absorb the ammonia in hydrogenation reaction effluent, prevent the ammonia density of gas separated by high pressure separator too Height, catalyst activity is reduced, the ammonia volumetric concentration of usual gas separated by high pressure separator is more low better, generally no greater than 200PPm (v), preferably less In 50PPm (v).Described 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 too high, generally 0.35~3.2MPa, be usually 0.5~1.5MPa.The hydrogen volume concentration value of described cold gas separated by high pressure separator, should not too low (cause device operating pressure rise), one As should be 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 gas separated by high pressure separator returns to be recycled in hydrogenation reaction part, to provide hydrogenation reaction part necessary amounts of hydrogen And hydrogen concentration；In order to improve plant investment efficiency, it is necessary to assure circulation hydrogen concentration is not less than foregoing lower limit value, therefore, according to Specific feedstock property, reaction condition, product distribution, can exclude a part of cold gas separated by high pressure separator to exclude to react caused first Alkane, ethane.For the cold gas separated by high pressure separator of discharge, conventional membrane separation process or pressure swing adsorption technique or oil wash technique can be used real Existing hydrogen and the separation of non-hydrogen gas component, and the hydrogen of recovery is used as new hydrogen.

New hydrogen enters hydrogenation part to supplement the hydrogen of hydrogenation process consumption, and new hydrogen hydrogen concentration is the higher the better, typically Not preferably less than 95% (v), preferably not below 99% (v).All new hydrogen can be introduced any hydrogenation reaction parts, be preferably introduced the One hydrogenation reactor.

The present invention, in the first hydrogenation process R10, in end reaction device R10ZE inside, generally, air lift hydrogen BH With middle part product R10ZE-IP with mixing after flow through liquid collection cups LD outer walls into reactor R10ZE top product separate it is de- Liquid and liquid collection space R10ZE-TZ；The position of air lift hydrogen BH injection mixed zone, does not recommend on the outside of liquid collection cups LD Same level height region, the de- liquid of product separation and liquid collection space R10ZE-TZ are not recommended, because mixing hydrogen and liquid phase yet The time that vaporescence needs can not ensure, can influence the continuous and stable of logistics composition, can also influence liquid collection cups LD Stabilization of equipment performance.

Compared with the system that up-flow reactor, air lift separator, high pressure hot separator form, combination function of the present invention is anti- Answer device R10ZE, major advantage is as follows：

1. avoid air lift front middle part product R10ZE-IP acceleration flowing and liquid phase is reunited, separated into thermal high air lift Deceleration flowing inside device is separated and space quadratic distribution process, and big, gas-liquid mixed phase reaction product is accumulated using reactor cross section The characteristics of up flow velocity very low (being usually the 1/50~1/200 of pipe flow speed), efficiently complete R10ZE-IP and air lift hydrogen Mixing, vaporization, gas-liquid separation, reduce idle space, improve space availability ratio；

2. at the top of reactor R10ZE, make full use of upper cover space, set de- liquid separate section obtain liquid phase material, Gas-liquid mixed phase material, can utilization space to greatest extent；

3. eliminating the high-pressure material pipeline system between reactor R10ZE, mixing vaporizer, separator, avoid The pipeline problem of high viscosity, easily condensation hydrocarbon ils；

4. constituting combination type reactor, mixing vaporizer and high pressure hot separator, reduce high-pressure system volume, reduce High-pressure system liquid storage amount；

5. functions of the equipments are compact, device structure is enormously simplify, saves a large amount of alloy steel materials.

Reference examples

Coal tar hydrogenating unit, 37.5 tons of initial coal tar/when, property is shown in Table 2, table 3, table 4.

Table 2 is full cut medium temperature coal tar, fraction A (medium temperature coal tar light oil), fraction B (medium temperature coal tar heavy oil) analysis Data, table 3 are cut C (coal tar pitch) analyze data of medium temperature coal tar, and table 4 is medium temperature coal tar distillation fraction yield table.

From table 2 it can be seen that the characteristics of fraction B (medium temperature coal tar heavy oil) is that content of heteroatoms is high, hydrogen content is low, density Greatly, aromatic hydrocarbons, gum level 83.5%, it is non-covalent because the colloid in medium temperature coal tar belongs to molecular association complex in large quantities Key, the structure of these colloids are easily disintegrated, and its carbon residue content can not use the concept Equivalent Analysis of black petroleum products.

From table 3 it can be seen that the characteristics of cut C (coal tar pitch) is that content of heteroatoms is high, hydrogen content is extremely low, aromatic hydrocarbons, colloid, Asphalitine, insoluble matter are up to 99.34%, carbon residue 37.8%, because the gum asphalt in medium temperature coal tar belongs to point in large quantities Sub- associated matter and non-covalent bond, the structure of these gum asphalts are easily disintegrated, its carbon residue content can not use black petroleum products Concept Equivalent Analysis, its coking test shows, coking yield is 64~68%.

Full cut medium temperature coal tar is filtered, is dehydrated, depth distillation, is separated into one section that normal boiling point is less than 230 DEG C Cut, the three sections of cuts of two sections of cuts, conventional boiling range more than 430 DEG C that conventional boiling range is 230~430 DEG C are coal tar heavy oil.

Using two sections of cuts as hydrogen supply hydrocarbon precursor by fixed bed hydrogenation process R00 productions aromatic carbon rate fa between 50~ 55% hydrogen supply dissolvent oil, hydrogenation process R00 products are separated into gas separated by high pressure separator and mainly by routine by HTHP separation process The hot high score oil of higher than 250 DEG C hydrocarbon compositions of boiling point, hot high score oil are coal tar heavy oil, urged as hydrogen supply dissolvent oil with three sections of cuts Agent, vulcanizing agent are mixed into mixing slurry oil and carry out floating bed hydrogenation thermal cracking；Hot cracked product passes through high pressure hot separator S1 It is separated into hot gas separated by high pressure separator S1V, hot high score oil S1L；Hot gas separated by high pressure separator S1V cools by heat exchange, water filling is washed, it is laggard to be cooled to 45 DEG C Enter cold high pressure separator and be separated into that cold gas separated by high pressure separator, cold high score be oily, cold high score water；Hot high score oil S1L is decompressed to 4.0MPa and is separated into Low point of oil of hot low point of air and heat；Hot low point of air cooling to the cold high score oil after after 45 DEG C, and after decompression is mixed into cold low separation Device is separated into cold low point of gas, cold low point of oil, cold low point of water；It is gas that cold low point of oil and hot low point of oil enter fractionating system fractionation in the lump Body, liquefied gas, normal boiling point be oily less than 200 DEG C of No.1, conventional boiling range is 200~300 DEG C No. two oil, conventional boiling range are 300~380 DEG C of No. three oil, No. four oil (containing catalyst granules) that conventional boiling range is 380~450 DEG C, conventional boiling range be 450~ 530 DEG C of the dregs of fat containing catalyst of No. five oil (containing catalyst granules), normal boiling point more than 530 DEG C.

Normal boiling point is oily less than 200 DEG C of No.1, conventional boiling range is 200~300 DEG C No. two oil, Part I routinely boil Journey is 300~380 DEG C of No. three oil, and the fixed bed hydrogenation grading process R7000 at rear portion is removed as product.

Another part routine boiling range is that 300~380 DEG C of No. three oil enter hydrogenation process R00 as hydrogen supply hydrocarbon precursor Prepare hydrogen supply agent.

No. four oil (containing catalyst granules) that conventional boiling range is 380~450 DEG C, No. five that conventional boiling range is 450~530 DEG C Oily (contain catalyst granules) is completely used as recycle oil, after mix with suspension bed hydrogenation catalyst, then it is oily and three sections with hydrogen supply dissolvent Cut is coal tar heavy oil mixing, into floating bed hydrogenation course of reaction；

Mixed material slurry oil and hydrogen mix, after heating furnace preheats, and enter first after the mixing of surplus stock hydrogen Floating bed hydrogenation reactor R11 is converted into the first floating bed hydrogenation reaction product R11P, the first floating bed hydrogenation reactor R11 Empty barrel reactor, liquid-phase hydrogenatin reaction include hydrogen supply dissolvent molecule and provide reactive hydrogen to coal tar heavy duty oil molecule or building stone The hydrogen aromatic carbon rate that liquid phase hydrogen transfer reactions, i.e. hydrogen supply dissolvent molecule loses activity improves, coal tar heavy duty oil molecule or building stone knot Closing reactive hydrogen aromatic carbon rate reduces the de- carbon residue reaction of i.e. formation hydrogenation.

First floating bed hydrogenation reactor R11, operation temperature is relatively low, to suppress thermal condensation reaction, with hydrofining reaction Reacted for main target.

Second floating bed hydrogenation reactor R12, to set the floating bed hydrogenation of the carrying liqs product circulation of liquid collection cups Reactor, the first floating bed hydrogenation reaction product R11P are converted into the second floating bed hydrogenation reaction product R12P in R12, and circulation adds Work product liquid.Second floating bed hydrogenation reactor R12, using systemic circulation than backmixing of liquid phase recycle cracking operation mode, circulation Weight of oil is 4~6 than R12-RLK to the weight of fresh feed, and the operating point R12-RLK values in this example are 5；Second suspension bed The recycle oil of hydrogenation reactor R12 discharges returns to the first floating bed hydrogenation reactor R11 entrances.

Second floating bed hydrogenation reactor R12, operation temperature is higher, is reacted by main target of either shallow hydrocracking reaction.

3rd floating bed hydrogenation reactor R13, to set the floating bed hydrogenation of the carrying liqs product circulation of liquid collection cups Reactor, the second floating bed hydrogenation reaction product R12P are converted into the 3rd floating bed hydrogenation reaction product R13P in R13, and circulation adds Work product liquid.3rd floating bed hydrogenation reactor R13, using systemic circulation than backmixing of liquid phase recycle cracking operation mode, circulation Weight of oil is 4~6 than R13-RLK to the weight of fresh feed, and the operating point R13-RLK values in this example are 5；3rd suspension bed The recycle oil of hydrogenation reactor R13 discharges returns to the 3rd floating bed hydrogenation reactor R11 entrances.

3rd floating bed hydrogenation reactor R13, operation temperature highest, reacted by main target of overhydrocracking reaction.

Suspension bed hydrogenation catalyst used is a kind of compound suspension bed hydrogenation catalyst of molybdenum-iron, and used catalyst includes height Active metal component molybdenum and low activity metal component iron, wherein high-activity component metal molybdenum and the weight of low activity component metals iron Than for 1: 500, catalyst water content is less than 0.5wt%, and particle diameter is 1~100 μm of powdered granule.The catalyst is to contain iron Measure and be ground into powdered granule less than 100 μm for 58wt% bloodstone (Main Ingredients and Appearance Fe203), then by 10% ammonium molybdate The aqueous solution is equably sprayed on particle, and spray flux is about molybdenum: iron weight ratio is equal to 1: 500, through being dried 1 hour at 100 DEG C, Obtain the powdered granule catalyst that water content is less than 0.5wt%.

Table 5 is the first hydrogenation process R10 reaction conditions.

It is conventional in balance gas phase R13P-V, balance liquid phase R13P-L that table 6 is the 3rd floating bed hydrogenation reaction product R13P The quantity and ASTM-D86 data of liquid hydrocarbon.

Balance gas phase R13P- under material composition and operating condition that table 7 is the 3rd floating bed hydrogenation reaction product R13P V, liquid phase R13P-L composition is balanced.

As can be seen from Table 6, low boiling hydrocarbon 42.2% of the normal boiling point less than 330 DEG C, conventional boiling are contained in hydrocarbon liquid phase High boiling hydrocarbon about 57.8% of the point higher than 330 DEG C, low boiling hydrocarbon are 0.73: 1 with high boiling hydrocarbon weight ratio；Recycle oil, which carries, urges Agent, other solid particles, it is evident that about 42.2% low boiling hydrocarbon contained in recycle oil is warm with the depth of round of recycle oil Cracking reaction process, a large amount of excessive heat cracking reactions necessarily occur.

The full cut medium temperature coal tar of table 2, fraction A, fraction B analyze data

The cut C analyze datas of the medium temperature coal tar of table 3

Sequence number	Project	Cut C
			1	Sulphur, %	0.40
2	Nitrogen, %	0.8519
			3	C/H, %	89.1/5.90
4	Carbon residue, %	37.8
			5	Softening point (ring and ball method)/DEG C	106
6	Ductility (25 DEG C)/cm	0
			7	Needle penetration (25 DEG C)/mm	3
8	Four components, %
				Saturation point/fragrance point	0.66/7.03
	Colloid/asphalitine	14.82/44.04
			9	Insoluble matter	33.45

The medium temperature coal tar distillation fraction yield table of table 4

Sequence number	Fraction section	Cut, DEG C	Yield, %
				1	Water	Water	4.22
2	Fraction A	＜ 310	36.10
				3	Fraction B	310~500	47.65
4	Cut C	＞ 500	12.03
				5		It is total	100.00

Table 5 the first hydrogenation process of reference examples (hydrogenation thermal cracking process) R10 reaction condition process conditions

The floating bed hydrogenation reaction product R13P of table 6 the 3rd material composition and operating condition under balance gas phase R13P-V, Balance liquid phase R13P-L composition

The product phase state analysis of table 7 (the non-row solids of stream components flow rate)

Explanation：NBP48 is pseudocomponent title, and the normal boiling point for representing pseudocomponent is 48 DEG C, other to analogize.

Embodiment

Embodiment one

Based on reference examples, in order to improve the selectivity of the 3rd floating bed hydrogenation reactor R13 hydrogenation heat cracking reaction, adopt With the present invention, the 3rd floating bed hydrogenation reactor R13 sets hydrogen stripping section, is carried out in the end of the 3rd hydrogenation process light The air lift of matter hydrocarbon and middle matter hydrocarbon vaporizes, to obtain the recycle oil being mainly made up of high boiling hydrocarbon of the normal boiling point higher than 300 DEG C.

3rd floating bed hydrogenation reactor R13, the gas hydrogen BH used is 29497 standard cubes m/hour, with fresh original The ratio for expecting 20 DEG C of 26.7 cubes ms/hour of volume amounts of " coal tar heavy oil, the hydrogen supply agent " in R10F is 1105..

It is conventional in balance gas phase R13P-V, balance liquid phase R13P-L that table 8 is the 3rd floating bed hydrogenation reaction product R13P The quantity and ASTM-D86 data of liquid hydrocarbon.

Balance gas phase R13P- under material composition and operating condition that table 9 is the 3rd floating bed hydrogenation reaction product R13P V, liquid phase R13P-L composition is balanced.

As can be seen from Table 8, in liquid phase normal boiling point less than 330 DEG C of low boiling hydrocarbon quantity by 12.1 tons/when drop As little as 6.8 tons/when, reduce to about the 56% of reference examples.

As can be seen from Table 8, in liquid phase normal boiling point higher than 330 DEG C of high boiling hydrocarbon quantity by 16.6 tons/when drop As little as 15.1 tons/when, reduce to about the 91% of reference examples；The weight of low boiling hydrocarbon of the normal boiling point less than 330 DEG C is dense in liquid phase Degree brings up to 68.6% by 57.8%, and low boiling hydrocarbon is 0.46: 1 with high boiling hydrocarbon weight ratio；Ensureing unconverted oil internal circulating load On the premise of constant, what recycle oil quantity can be reduced to reference examples 83.8% can reduce recycle oil 16.2%.

Meanwhile balance liquid phase total amount by 28.7 tons/when be reduced to 21.96 tons/when, be reduced to about the 76.5% of reference examples, The concentration of catalyst has brought up to about the 131% of reference examples so in liquid phase.

Beneficial effect is shown as：

1. the excessive heat cracking reaction of recycle oil circulation cracking process, light hydrocarbon and middle matter hydrocarbon is greatly lowered

Low boiling hydrocarbon quantity in apparent recycle oil is reduced to about the 56% of reference examples, the depth of round hot tearing of recycle oil Change course of reaction, the excessive heat cracking reaction amount of the low boiling hydrocarbon of generation is greatly reduced, reduced to about the 56% of reference examples；

Therefore, under thermal cracking conversion reaction amount permanence condition, hydrogen consumption can be reduced, reduce gas or small molecule yield, Improve the macromolecular hydrocarbon liquid yield in light hydrocarbon and middle matter hydrocarbon；

2. recycle oil quantity is greatly lowered, reactor volume can be reduced or improve thermal cracking conversion ratio

With being greatly lowered for the light hydrocarbon in recycle oil and middle matter hydrocarbon quantity, in the bar that unconverted oil internal circulating load is constant Under part, recycle oil absolute quantity can reduce 16.2%, therefore, can be reduced under thermal cracking conversion reaction amount permanence condition anti- Answer body to accumulate, or thermal cracking conversion ratio can be improved under reactor volume permanence condition；

3. the 3rd floating bed hydrogenation reactor R13 cumulative volume, hardly increase can even be reduced

3rd floating bed hydrogenation reactor R13, the air lift hydrogen blender of setting occupy segment space, but the space A high efficiency reaction core can be turned on the contrary, the reduction of recycle oil quantity in addition is beneficial to reduce reactor cumulative volume, anti-for offsetting Answer device top product to take off the growth of liquid space, in a word, the 3rd hydrogenation reactor AR3 cumulative volume, be increased without substantially；

The density of hydrogen of gas phase is balanced, is increased to 82.2% by 70.0%, hydrogen partial pressure is increased to by 15.10MPa 17.76MPa, that is, raise 26.6MPa；

4. because equilibrium liquid phase transformation weight, balance amount of liquid phase by 28.7 tons/when be reduced to 21.96 tons/when, be reduced to control About the 76.5% of example, the hot high score oil total amount of the 3rd floating bed hydrogenation reactor R13 products isothermal equilibrium flash distillation gained will decrease to About the 76.5% of reference examples can reduce by 23.5% quantity；

5. because equilibrium liquid phase transformation weight, beneficial to reactive moieties recycle oil quantity is increased, higher overall single pass cracking is realized Rate, if it is considered that this Beneficial Effect, then hot high score oil total amount is changed and can further reduced；

Hot high score oil total amount is present to be limited under one, by dead catalyst amount, thermal condensation object amount is discharged, is given up and is urged in hot high score oil The restriction of agent amount, the concentration of thermal condensation object amount；

In this example, catalyst weight addition is the 1% of total liquid hydrocarbon material, semicoke particle and ash content are total liquid hydrocarbon material 1%, consideration thermal condensation green coke weight is the 1.5% of total liquid hydrocarbon material, the 3.5% of total liquid hydrocarbon material is added up to, according to hot high score Solid particle weight content is 15% calculating in oil, and hot high score oil total amount lower limit is the 23.3% of total liquid hydrocarbon material, about 9.5 Ton/when；

It is thus possible to increase cracked cycle oil quantity, improves overall cracking per pass, hot high score oil total amount is further reduced And solid flow, to reduce hot high score oil system of processing, (high-pressure separator S1, hot high score oil SIL are depressured valve system, hot high score oil SIL separate or fractionating system) scale create condition, can be greatly lowered investment and energy consumption, and can reduce asphalitine condensation Produce amount, improve processing safety.

The floating bed hydrogenation reaction product R13P of table 8 the 3rd material composition and operating condition under balance gas phase R13P-V, Balance liquid phase R13P-L composition

The product phase state analysis of table 9 (the non-row solids of stream components flow rate)

Embodiment two

Coal Liquefaction process, its last floating bed hydrogenation reactor R10ZE, the discharge of the liquid collection cups of setting Liquid is through the direct Returning reactor R10ZE itself of pump circulation, using mode of the present invention, using air lift hydrogen by liquid product Part normal boiling point is that 250~330 DEG C of middle matter hydrocarbon is vaporizated into gas phase, and improving normal boiling point in cycling hot cracked cycle oil is The concentration of mink cell focus more than 330 DEG C, optimize operation.

Claims

1. with the hydrocarbon material expanded bed hydrogenation reactor system of air lift hydrogen and liquid collection cups, it is characterised in that include following step Suddenly：

(1) in the first hydrogenation process R10, hydrogen, hydrocarbon liquid phase while the mixed phase material that there may be solid particle be present Under the conditions of, the first raw material R10F at least containing carbon and protium enters the first hydrogenation process R10 progress first and added Hydrogen reaction R10R obtains the first hydrogenation reaction product BASE-R10P；

First hydrogenation reaction R10R, at least a portion liquid material R10FL hydrofining reaction is included, at least one may be included Operative liquid raw material R10FL hydrocracking reaction, adding at least a portion solid material R10FS that may be present may be included Hydrogen heat cracking reaction；

First hydrogenation process R10, catalyst R10C may be used；

First hydrogenation reaction product BASE-R10P, for containing hydrogen, hydrocarbon liquid phase simultaneously may be containing solid particle mixed phase thing Material；

Material based on the first hydrogenation reaction product BASE-R10P is used as the first hydrogenation reaction effluent R10P-X, the first hydrogenation Reaction effluent R10P-X, occur in the form of 1 tunnel or 2 tunnels or multichannel material, the first hydrogenation reaction effluent R10P-X is gas Phase or liquid phase or gas-liquid mixed phase or gas-liquid-solid three-phase logistics；

In the first hydrogenation process R10, the hydrogenation reactor used is up flow type expanded bed hydrogenation reactor, using at least 1 hydrogenation reactor, least significant end hydrogenation reactor R10ZE carry out product using built-in liquid collection cups LD and take off liquid and liquid receipts Collect water conservancy diversion and obtain collection liquid R10ZE-TL and gas-liquid mixed phase product R10ZE-P；

The pressurized step ADP pressurizations of at least a portion collection liquid R10ZE-TL, the collection of at least a portion pressurization steps ADP discharges Liquid R10ZE-TL is returned as recycle oil R10ZE-RL in the reaction compartment of middle part product R10ZE-IP upstream hydrogenation process；

Heavy hydrocarbon weight concentration in collection liquid R10ZE-TL, the balance liquid phase R10ZE-IP-L higher than middle part product R10ZE-IP Heavy hydrocarbon weight concentration；Light hydrocarbon, the total concentration by weight of middle matter hydrocarbon in collection liquid R10ZE-TL, less than in middle part product R10ZE-IP balance liquid phase R10ZE-IP-L light hydrocarbon, the total concentration by weight of middle matter hydrocarbon；Middle part product R10ZE-IP is carried During solid particulate matter, the weight ratio for the solid particulate matter that collection liquid R10ZE-TL is carried is flat higher than middle part product R10ZE-IP The weight ratio for the solid particulate matter that the liquid phase that weighs R10ZE-IP-L is carried；

(2) in recovery section S100, the product R10P100 of recovery the first hydrogenation process R10 discharges, product R10P100 is extremely Include R10ZE-P less.

2. expanded bed hydrogenation reactor system according to claim 1, it is characterised in that：

(1) in the first hydrogenation process R10, in end reaction device R10ZE inside, before flowing through liquid collection cups LD outer walls Middle part product R10ZE-IP mixed with air lift hydrogen BH；

3. expanded bed hydrogenation reactor system according to claim 1, it is characterised in that：

(1) in the first hydrogenation process R10, it is used as and follows in end reaction device R10ZE, at least a portion collection liquid R10ZE-TL The hydrogenation reaction returned after the pressurized step ADP pressurizations of ring oil in the first hydrogenation process R10 the first hydrogenation reactor is empty Between in.

4. expanded bed hydrogenation reactor system according to claim 1, it is characterised in that：

(1) in the first hydrogenation process R10, it is used as and follows in end reaction device R10ZE, at least a portion collection liquid R10ZE-T Returned after the pressurized step ADP pressurizations of ring oil in least significant end hydrogenation reactor R10ZE and be located at middle part product R10ZE-IP upstreams Hydrogenation reaction space in.

5. expanded bed hydrogenation reactor system according to claim 1, it is characterised in that：

(1) first hydrogenation process R10, a kind or 2 kinds or several of combination selected from following hydrogenation process：

1. the hydrogenation using expanded bed of the logistics containing oil product obtained by middle coalite tar or its distillate or its hot procedure Journey；Hot procedure is selected from coking or catalytic cracking process or catalytic pyrolysis process or hydrogenation process；

2. the hydrogenation process using expanded bed of the logistics containing oil product obtained by high temperature coal-tar or its distillate or its hot procedure；

3. direct hydrogenation liquefaction of coal liquefaction process uses the hydrogenation process of expanded bed, the coal hydrogenation including the use of hydrogen supply dissolvent oil is straight Connect liquefaction liquefaction process, oily coal refines process altogether, coal faces hydrogen thermosol liquefaction process；

5. the hydrogenation process using expanded bed of ethylene cracking tar；

8. other aromatic hydrocarbons weight contents are higher than the adding using expanded bed of hydrocarbon ils of 40%, the organic nitrogen weight content higher than 0.10% Hydrogen process.

6. expanded bed hydrogenation reactor system according to claim 1, it is characterised in that：

(1) in the first hydrogenation process R10, a kind or several in following of existing solid particle：

2. catalyst granules；

3. iron rust particle；

4. particles of inorganic material；

5. the solid particle entered caused by coking of coal process in coal tar；

7. the solid particle from shale；

8. the solid particle from oil-sand；

7. expanded bed hydrogenation reactor system according to claim 1, it is characterised in that：

Any hydrogenation reactor that (1) first hydrogenation process R10 is used, a kind or several in following of mode of operation Combination：

1. suspension bed is slurry bed system；

2. ebullated bed；

3. slight expanded-bed.

8. expanded bed hydrogenation reactor system according to claim 2, it is characterised in that：

(1) in the first hydrogenation process R10, in end reaction device R10ZE, air lift hydrogen passes through horizontally disposed distributor MG sprays to be mixed into mixed zone with middle part product R10ZE-IP.

9. expanded bed hydrogenation reactor system according to claim 2, it is characterised in that：

(1) in the first hydrogenation process R10, in end reaction device R10ZE, air lift hydrogen passes through horizontally disposed distributor MG sprays to be mixed into mixed zone with middle part product R10ZE-IP；

Distributor MG includes cartridge type distributing chamber, the hydrogen of the dual formula distributor ejection of " nozzle-reflecting plate " composition of its locular wall Enter the de- liquid space in liquid collection cups LD tops with rising cocurrent after material cross-flow mixes；

The hydrogen stream that the hydrogen nozzle arranged in the vertical walls of cartridge type distributing chamber projects, if reflected through fluid impact opposite Plate then forms specular scattering stream, secondary to pass through reaction mass upper up-flow；Air lift hydrogen BH and middle part product R10ZE-IP completes mixed Cocurrent enters the de- liquid space in liquid collection cups LD tops after conjunction.

10. expanded bed hydrogenation reactor system according to claim 9, it is characterised in that：

Distributor MG includes 2 layers or multilayer hydrogen circular distribution cylinder, and distributing barrel is connected for setting internal hydrogen communication chamber with hydrogen Thread a pipe the concentric drums of connection, concentric drums are arranged vertically, and its axle center and reactor axis coinciding, beneficial to reactor radially Section even symmetrical distributing hydrogen；

The function of circular distribution tube wall surface is：Arrangement spout, the reflecting plate for serving as Hydrogen Jet Flow, augmentation of heat transfer, rectification are to weaken Mixed process radial direction flow distribution unevenness and the flowing space scope for limiting fluid.

11. expanded bed hydrogenation reactor system according to claim 10, it is characterised in that：

Distributor MG circular distribution tube wall surface epimere and hypomere reserve one section not opening area be used for Stable distritation device MG bottoms The flowing of the mixed material of the up charging entered and the discharge of distributor MG tops, the Hydrogen Jet Flow that spout sprays, its extended line The spatial dimension i.e. extended line collision opposite reflective wall of cylinder barrel constraint is not sprayed directly, may corresponding to distributor MG The reactor shell inwall wall of hydrogen injection contact is stripped, liner plate is set or is distributed the lining of air lift hydrogen, prevents air lift Hydrogen directly sprays contact reactor inwall.

12. expanded bed hydrogenation reactor system according to claim 9, it is characterised in that：

The distance between adjacent distributions cylinder of cartridge type distributor, it is 0.1~1.0 meter；

Nozzle hydrogen flow rate, it is 0.5~30 meter per second；

Spout horizontal dispersion angle, it is 0.0~30 °.

13. expanded bed hydrogenation reactor system according to claim 9, it is characterised in that：

The distance between adjacent distributions cylinder of cartridge type distributor, it is 0.15~0.6 meter；

Nozzle hydrogen flow rate, it is 1.0~15 meter per seconds；

Spout horizontal dispersion angle, it is 0.0~20 °.

14. expanded bed hydrogenation reactor system according to claim 9, it is characterised in that：

The distance between adjacent distributions cylinder of cartridge type distributor, it is 0.25~0.40 meter

Nozzle hydrogen flow rate, it is 2.0~10 meter per seconds；

Spout horizontal dispersion angle, it is 0.0~15 °.

15. according to the expanded bed hydrogenation reaction described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 Device system, it is characterised in that：

(1) in the first hydrogenation process R10, in end reaction device R10ZE, the collection liquid R10ZE-TL of catheter LK discharges The weight concentration of hydrocarbon component of the normal boiling point higher than 300 DEG C is more than 65% in middle total hydrocarbon component.

16. expanded bed hydrogenation reactor system according to claim 15, it is characterised in that：

(1) in the first hydrogenation process R10, in end reaction device R10ZE, the collection liquid R10ZE-TL of catheter LK discharges The weight concentration of hydrocarbon component of the normal boiling point higher than 300 DEG C is more than 75% in middle total hydrocarbon component.

17. expanded bed hydrogenation reactor system according to claim 15, it is characterised in that：

(1) in the first hydrogenation process R10, in end reaction device R10ZE, the collection liquid R10ZE-TL of catheter LK discharges The weight concentration of hydrocarbon component of the normal boiling point higher than 300 DEG C is more than 85% in middle total hydrocarbon component.

18. according to the expanded bed hydrogenation reaction described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 Device system, it is characterised in that：

(1) in the first hydrogenation process R10, in end reaction device R10ZE, the air lift hydrogen BH used standard state body The ratio of 20 DEG C of volume amounts of the conventional liquid phase hydrocarbon in product flow BH-V and fresh feed R10F be K900, K900 for 300~ 3000。

19. expanded bed hydrogenation reactor system according to claim 18, it is characterised in that：

(1) in the first hydrogenation process R10, in end reaction device R10ZE, K900 is 500~2000.

20. according to the expanded bed hydrogenation reaction described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 Device system, it is characterised in that：

(1) first hydrogenation process R10, using floating bed hydrogenation reactor, operating condition is：Reaction temperature is 320~480 DEG C, 0.2~5.0h of volume space velocity of 6~30MPa of reaction pressure, reaction compartment^-1, hydrogen to oil volume ratio 200~3000.

21. expanded bed hydrogenation reactor system according to claim 20, it is characterised in that：

(1) first hydrogenation process R10, using floating bed hydrogenation reactor, operating condition is：Reaction temperature is 360~460 DEG C, 0.2~5.0h of volume space velocity of 12~25MPa of reaction pressure, reaction compartment^-1, hydrogen to oil volume ratio 200~1500.

22. according to the expanded bed hydrogenation reaction described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 Device system, it is characterised in that：

(1) first hydrogenation process R10, using boiling bed hydrogenation reactor, operating condition is：Reaction temperature is 320~480 DEG C, 0.2~5.0h of volume space velocity of 6~30MPa of reaction pressure, reaction compartment^-1, hydrogen to oil volume ratio 200~3000.

23. expanded bed hydrogenation reactor system according to claim 22, it is characterised in that：

(1) first hydrogenation process R10, using boiling bed hydrogenation reactor, operating condition is：Reaction temperature is 360~460 DEG C, 0.2~5.0h of volume space velocity of 12~25MPa of reaction pressure, reaction compartment^-1, hydrogen to oil volume ratio 200~1500.

24. according to the expanded bed hydrogenation reaction described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 Device system, it is characterised in that：

(1) in the first hydrogenation process R10, raw material R10F is from coal tar and is mainly higher than 400 DEG C of hydrocarbon groups by normal boiling point Divide HD compositions, raw material R10F Unit Weight hydrogen consumption is 0.05~7.0%.

25. according to the expanded bed hydrogenation reaction described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 Device system, it is characterised in that：

(1) in the first hydrogenation process R10, raw material R10F is coal dust R10FS and hydrogen supply dissolvent R10FL, coal dust R10FS list Position weight hydrogen consumption is 2.5~10.0%.

26. according to the expanded bed hydrogenation reaction described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 Device system, it is characterised in that：

(1) coal tar is come from the first hydrogenation process R10, raw material R10F；The hydrogenation catalyst R10C used, it is a kind of multiple Mould assembly coal tar hydrogenation catalyst, include high-activity component and low activity component；The high-activity component metal and low activity group The weight ratio of parting category is 1: 10 to 10: 1；The high-activity component is the water soluble salt compound or its mixture of molybdenum；Institute It is ferric oxide ore or iron sulfide ore to state low activity component, and wherein iron in ore content is not less than 40wt%, catalyst R10C Water content is less than 2wt%；R10C particle diameters are 1~100 μm of powdered granule.

27. according to the expanded bed hydrogenation reaction described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 Device system, it is characterised in that：

(1) coal tar is come from the first hydrogenation process R10, raw material R10F, the hydrogenation catalyst R10C used, comprised at least Mo elements, Mo are M in the first hydrogenation process R10 body of work form₀S₂In, hydrogenation catalyst R10C is 1~100 μm Powdered granule.

28. according to the expanded bed hydrogenation reaction described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 Device system, it is characterised in that：

(1) raw material R10F comes from coal tar, and the first hydrogenation process R10 operating condition is：Temperature is 300~480 DEG C, pressure Power is 6.0~30.0MPa, hydrogen/feedstock oil volume ratio is 0.01: 1~4000: 1, hydrogenation catalyst R10C adds weight as original Expect that the 0.001~8.0% of R10F weight, reaction compartment volume space velocity is 0.1~10.0hr^-1；Raw material R10F weight chemistry hydrogen Consumption is 0.05~7.0%.

29. expanded bed hydrogenation reactor system according to claim 28, it is characterised in that：

(1) raw material R10F comes from coal tar, and the first hydrogenation process R10 operating condition is：Temperature is 350~460 DEG C, pressure Power is 12.0~25.0MPa, hydrogen/feedstock oil volume ratio is 50: 1~1200: 1, hydrogenation catalyst R10C addition weight is HDS Weight 0.5~5.0%, volume space velocity be 0.2~2.0hr^-1；Raw material R10F weight chemistry hydrogen consumption is 0.50~5.5%.

30. expanded bed hydrogenation reactor system according to claim 1, it is characterised in that：

(1) in the first hydrogenation process R10,1~4 hydrogenation reactor is used.

31. expanded bed hydrogenation reactor system according to claim 1, it is characterised in that：

(1) in the first hydrogenation process R10,2~3 hydrogenation reactors are used.

32. expanded bed hydrogenation reactor system according to claim 1, it is characterised in that：

(1) hydrogen supply hydrocarbon material is included in the first hydrogenation process R10, raw material R10F.