CN107916135A

CN107916135A - The hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula is like secondary hydrogenation method

Info

Publication number: CN107916135A
Application number: CN201610920700.1A
Authority: CN
Inventors: 何巨堂
Original assignee: 何巨堂
Current assignee: Luoyang Rui Hua new energy technology development Co., Ltd.
Priority date: 2016-10-11
Filing date: 2016-10-11
Publication date: 2018-04-17

Abstract

The hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula is like secondary hydrogenation method, in the back-mixing stream expanded bed reactor BRXE of secondary hydrogenation reaction process BR, one-stage hydrogenation reaction product ARP is mixed with BRXE intermediate product BRXE 8P to be gone upward to the de- liquid zone domain in top and separates phegma BRXEP LR and gassiness material product BRXEP M, it is BRXE 8P that the BR upstreams hydroconversion reaction zone of BRXEP LR return BRXE DBP, which starts the cycle over hydro-conversion, in the gas phase H₂Volumetric concentration is high, high selectivity is carried out under conditions of low, the high boiling hydrocarbon concentration height low with low boiling hydrocarbon concentration in liquid phase of impurity volumetric concentration, highly effective hydrogenation reaction, significantly inhibits high boiling hydrocarbon thermal condensation and low boiling hydrocarbon secondary cracking；Low boiling hydrocarbon enters gas phase discharge BRXE in gas air lift ARP liquid phases in BRXE 8；BRP, which enters three sections of hydrogenation process CR, can build like three sections of hydrogenation processes.

Description

The hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula is like secondary hydrogenation method

Technical field

The back segment upper feeding back-mixing hydrocarbon material of stream expanded bed reactor formula is like secondary hydrogenation method, in secondary hydrogenation reaction process In the back-mixing stream expanded bed reactor BRXE of BR, one-stage hydrogenation reaction product ARP mixes uplink with BRXE intermediate products BRXE-8P Liquid zone domain, which is taken off, to top separates phegma BRXEP-LR's and gassiness material product BRXEP-M, BRXEP-LR return BRXE-DBP It is BRXE-8P that BR upstreams hydroconversion reaction zone, which starts the cycle over hydro-conversion, in the gas phase H₂Volumetric concentration is high, impurity volumetric concentration is low High selectivity, significantly highly effective hydrogenation reaction, suppression are carried out under conditions of, high boiling hydrocarbon concentration height low with low boiling hydrocarbon concentration in liquid phase High boiling hydrocarbon thermal condensation processed and low boiling hydrocarbon secondary cracking；Low boiling hydrocarbon enters gas phase in gas air lift ARP liquid phases in BRXE-8 Discharge BRXE；BRP, which enters three sections of hydrogenation process CR, can build like three sections of hydrogenation processes.

Background technology

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

Expanded bed reactor of the present invention, is vertical up-flow reactor, and using catalyst when belongs to expanded bed reaction Device；The vertical central axis upright for referring to working status reactor after installing is in ground；Up flow type refers to reaction process thing Material main body flow direction travels through reaction compartment or catalyst bed or the catalyst co-flow with uplink from bottom to top；Expanded bed Refer to that working status catalyst bed is in swelling state, catalyst bed expansion ratio, which is defined as catalyst bed, reaction original The ratio of the maximum height CWH of working status when material passes through and the height CUH of the empty bed static condition of the catalyst bed KBED, in general, referred to as slight expanded-bed when KBED is less than 1.10, KBED between 1.25~1.55 when referred to as ebullated bed, and suspension bed It is considered as the expanded bed of most extreme form.

Back-mixing stream expanded bed reaction zone of the present invention, refers to the mode of operation of the reaction zone using expanded bed reactor There are liquid stream back-mixing, there are circulation fluid in other words；Back-mixing stream or circulation fluid, refer to the intermediate product XK or final at flow points K At least a portion liquid phase XK-L in product X K is as circulating fluid XK-LR return logistics XK upstream reaction zones, circulating fluid XK- The reaction product of LR flows through K points and is present among XK.The mode for forming back-mixing stream can be any appropriate mode, such as set Built-in inner ring flow cartridge, built-in outer shroud flow cartridge, built-in liquid collecting cup+diversion pipe+circulating pump, external circulation pipe etc..

Hot high score device of the present invention, refers to the gas-liquid separation for separating hydrogenation reaction intermediate product or final product Equipment.

Two sections of the present invention or multi-stek hydrogenation method, refer to the hydrogenation side comprising two conversion zones or multiple conversion zones Method.

A hydrogenation reaction section of the present invention, refers to it adding entering a hydrogenation process since hydrocarbon feed Hydrogen product gas-liquid separation obtains the flow section untill at least one liquid product being made of at least a portion generation oil, comprising this The gas-liquid separation process of the hydrogenation process of hydrogenation reaction section and the hydrogenation reaction product of this section.Therefore, one-stage hydrogenation method, Refer to that the process of initial hydrocarbon feedstock only includes the stream of a hydrogenation reaction section and a hydrogenation products gas-liquid separation process Journey mode, described hydrogenation reaction section, can use the hydrogenation reaction of 1 or 2 or more serial operation as needed Device, therefore number of reactors and form are not the foundations for determining conversion zone, the reaction that one or some tandem reactors form walks Suddenly a hydrogenation reaction section completed in meaning could be formed with its product separator common combination.

Secondary hydrogenation method of the present invention, refers to that the process of initial hydrocarbon feedstock includes liquid material work flow For the flow model formed " by two different hydrogenation processes and hydrogenation products gas-liquid separation process " of serial operation, its The logistics of middle at least a portion one-stage hydrogenation generation oil composition enters secondary hydrogenation reaction process.

Three sections of method of hydrotreating of the present invention, refer to that the process of initial hydrocarbon feedstock includes liquid material work flow For the flow model formed " by three different hydrogenation processes and hydrogenation products gas-liquid separation process " of serial operation, its The logistics of middle at least a portion one-stage hydrogenation generation oil composition enters secondary hydrogenation reaction process, the life of at least a portion secondary hydrogenation Logistics into oil composition enters three sections of hydrogenation processes.The flowage structure of the method for hydrotreating of more multistage, according to mentioned above principle class Push away.Multi-stek hydrogenation method, refer to initial hydrocarbon feedstock process include liquid material work flow for serial operation " by The flow model of three or more different hydrogenation processes and hydrogenation products gas-liquid separation process " composition.

Three sections of method of hydrotreating, refer to that the process of initial hydrocarbon feedstock comprising liquid material work flow is serial operation The flow model formed " by three different hydrogenation processes and hydrogenation products gas-liquid separation process ", according to this definition, It is obvious that the gas-liquid separation process of the difference section hydrogenation products, can independently carry out, can also partly or entirely combine into OK.

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

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, for the generation hydrofinishing of its feedstock oil of hydrocarbon oil hydrogenation process and/or add The product of hydrogen heat cracking reaction generation at least a portion more low molecular weight, for coal liquifaction hydrogenation process, thermosol occurs for its feed coal It is swollen, once the reaction such as pyrolysis, the secondary thermal cracking of intermediate product, free radical stabilized hydrogenation, thermal condensation generation at least a portion is conventional Boiling point is less than 450 DEG C of hydrocarbon products.

Hydrocarbon material hydrogenation process of the present invention, exemplary are that high temperature coal-tar floating bed hydrogenation deep refining is anti- Process, middle coalite tar floating bed hydrogenation heat cracking reaction process, direct hydrogenation liquefaction of coal reaction process, oily coal is answered to refine add altogether Hydrogen reaction process, petroleum based heavy fuel oils suspension bed or boiling bed hydrogenation cracking reaction process.

Hydrocarbon material hydrogenation reaction of the present invention, its reaction product BASE-ARP, is at least gas-liquid two-phase logistics, most feelings Condition belongs to gas, liquid, solid three-phase logistics.Hydrogenation reaction effluent ARP-X of the present invention is used to discharge hydrogenation reaction product BASE- ARP, occurs in the form of 1 tunnel or 2 tunnels or multichannel material, is gas phase or liquid phase or gas-liquid mixed phase or gas-liquid-solid three-phase logistics.

Retouched below in conjunction with hydrogenation process, the coal liquifaction hydrogenation process of middle coalite tar raw material hydrocarbon AR1F State.

Hydrocarbon material hydrogenation process TR of the present invention, includes either shallow hydrogenation process AR and deep hydrogenation process BR, the present invention The secondary hydrogenation method, emphasis are related to the deep hydrogenation process BR of hydrocarbon material, more particularly to higher boiling liquid phase during BR The deep hydrogenation mode of the hydrocarbon component deep hydrogenation mode and/or not deeply-liquefied coal tissue, key are related to deep hydrogenation and reacted The optimization of journey thermodynamic condition, is related to and improves hydrogen partial pressure, improves hydrogenation selectivity and improve high boiling hydrocarbon concentration in liquid phase, carry Catalyst concn, raising reactive hydrogen supply rate, raising goal response speed shorten thermal response time etc. in high liquid phase, and then It is related to the change of overall hydrogenation process.

The raw material hydrocarbon AR1F 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 TR using up flow type expanded bed；Hydrogenation process TR can be to be hydrogenated with Process based on refining reaction is that the hydrocracking reaction of substantial amounts of hydrofining reaction and relatively small amount occurs；Hydrogenation reaction mistake Journey TR can also be that substantial amounts of hydrofining reaction, substantial amounts of hydrocracking reaction occur for hydrocracking process.

Coal liquifaction hydrogenation process, because comprising coal dust and the circulation dregs of fat, its suitable method of hydrotreating is to use up flow type The hydrogenation process TR of expanded bed；Hydrogenation process TR is typically anti-with swelling reaction, pyrolytic reaction, hydrogenation thermal cracking Answer, the reaction process based on the reaction of free radical stabilized hydrogenation, but the thermal condensation reaction that pyrolysis intermediate product heavy hydrocarbon also occurs is given birth to Into asphaltene, preasphaltene, the secondary heat scission reaction that hydrocarbon products among pyrolysis occur generates small molecule hydrocarbon and gas.

The heat from hydrogenation for the raw material hydrocarbon AR1F that heavy distillat of the normal boiling point of either middle coalite tar higher than 350 DEG C forms Cracking process, or coal liquifaction hydrogenation process, the operation scheme of optimization is usually using at least 2 up flow type expanded bed reactions Device, substantially anterior hydrogenation reactor carries out either shallow hydrogenation process AR at this time, rear portion hydrogenation reactor carries out deep hydrogenation process BR； Either shallow hydrogenation process AR, operation temperature is usually higher, typically up to 350~430 DEG C, generally up to 380~415 DEG C, but should Reaction temperature value generally compared with deep hydrogenation process BR reaction temperature value it is lower, such as usually it is low go out 15~50 DEG C；Depth adds Hydrogen process BR, operation temperature is usually higher, typically up to 410~470 DEG C, generally up to 425~455 DEG C, the reaction temperature one As higher compared with the reaction temperature of either shallow hydrogenation process AR be such as usually higher by 15~50 DEG C or higher.

The normal boiling point of middle coalite tar is higher than 350 DEG C of heavy distillat raw material hydrocarbon AR1F, low boiling hydrocarbon cut therein I.e. the hydrocarbon component of the normal boiling point less than 330 DEG C evaporates i.e. the hydrocarbon component split-phase ratio of the normal boiling point higher than 330 DEG C with high boiling hydrocarbon, usually Impurity content is relatively low, residual carbon content is relatively low, in the hydrofining reaction process TR using up flow type expanded bed such as suspension bed In, compared with high boiling hydrocarbon-fraction, usual impurity element therein is easier hydrogenation hydrogenolysis and deviates from, wherein low boiling hydrocarbon cut Colloid be easier to be hydrogenated with de- carbon residue, therefore as hydrogenation degree is deepened, the hydrogenation removing impurities matter of low boiling hydrocarbon cut, hydrogenation are de- residual Carbon task is completed first, but the de- carbon residue task of the hydrogenation removing impurities matter of high boiling hydrocarbon cut, hydrogenation is not yet completed at this time, if after Continuous combined depth hydrogenation, is bound to cause the excessive hydrogenation of low boiler cut, excessive thermal cracking, and the depth of high boiling hydrocarbon-fraction Hydrogenation process certainly will need more subsequent reactions spaces, and the middle hydrogenation products of low boiler cut are reduced as diluent The concentration of high boiling hydrocarbon cut thus reduce reaction speed, and middle the hydrogenation products participation catalyst surface of low boiler cut is competing Absorption and the contention to reactive hydrogen are striven, at this time, in order to improve the selectivity of high boiling hydrocarbon hydrogenation process, is wished in technique by low boiling Point intermediate product such as foreign gas, normally gaseous hydrocarbon, naphtha component etc. discharge reaction process in time, and will be produced among higher boiling Thing continues deep hydrofinishing reaction or recycled hydrofining；Recycled hydrofining, can utilize low boiling point raw material components The advantage that the viscosity of overall liquid phase is greatly lowered under existence condition, the diffusion velocity of high boiling component is accelerated accelerates hydrogenation anti- Should, and the quality of the hydrogenation final products of high boiling hydrocarbon component can be realized by flexibly adjusting recycle ratio, reaction temperature etc. Control, in other words, certainly exists the hydrofinishing recycle oil being made of heavy distillat unconverted oil at this time..

The raw material hydrocarbon AR1F 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 single hop one way of expanded bed such as suspension bed hydrogenation heat cracking reaction process TR, it is often impossible to realize 100% full conversion, because Excessive hydrogenation thermal cracking conversion per pass can cause the more aerogenesis of low boiling hydrocarbon overcracking in raw material and middle hydrogenation products The more green coke charcoals of the excessive thermal condensation of body, high boiling hydrocarbon, the distribution of severe exacerbation product, shorten the continuous cycle of operation, in other words, in order to Improved to greatest extent using feedstock oil, raising liquid yield, extend the reaction process continuous cycle of operation, usually certainly exist double distilled Divide the overhydrocracking process of unconverted oil.

In coal liquifaction hydrogenation process, liquid yield is improved in order to improve lique faction of coal rate, it is often desirable that living in coal Property component (vitrinite, chitin group) be bordering on whole liquefaction and inert component (inertinite) moderately liquefies, but because activity in coal Component (vitrinite, chitin group) is easy to liquefaction and inert component (inertinite) is difficult to liquefy, so, inert component (inertinite) The liquefied rear portion conversion zone of appropriateness, be exactly active component liquefaction products secondary pyrolytic reaction, necessarily cause raw material hydrogen supply agent Overcracking fecund gas, the more green coke charcoals of the excessive thermal condensation of high boiling hydrocarbon with intermediate product hydrocarbon, the distribution of severe exacerbation product, contracting The short continuous cycle of operation, in other words, coal liquefaction hydrogenation process usually certainly exist a nonideal overhydrocracking Journey.

On the premise of there are deep hydrogenation process, concentration of component in deep hydrogenation process raw material (hydrogen, foreign gas, Low boiling hydrocarbon, high boiling hydrocarbon), high boiling hydrocarbon concentration in catalyst concn, liquid phase is greatly affected in hydrogen partial pressure, liquid phase, And then directly strong influence hydrogenation reaction selectivity, reactive hydrogen supply rate, goal response time etc., and then directly influence strongly Thermal condensation reaction quantity, secondary pyrolysis stoichiometric number amount, decide the good and bad success or failure of technical process.

In the hydrogenation process TR or coal liquifaction hydrogenation process TR of middle coalite tar raw material hydrocarbon AR1F, shallow Hydrogenation process AR is spent, substantial amounts of low molecular weight low-boiling point gas component can be produced, source is：

1. part organic impurities O, S, N in raw material A R1F are converted into low-boiling foreign gas component H₂O、H₂S、NH₃ It is present in gas phase, since organic impurities O, S, N content are very high in raw material, therefore foreign gas yield is very big；

2. the oxygen-containing functional group in part in raw material A R1F is converted into low-boiling gas component CO, CO₂, it is present in gas phase In；

3. the side chain of portion of paraffins, cycloalkane in raw material A R1F or intermediate product, the side chain of aromatic hydrocarbons, cracking fracture life Into low-boiling conventional gas component C₁~C₄, it is present in gas phase；

4. the side chain of portion of paraffins, cycloalkane in raw material R1FL or intermediate product, the side chain of aromatic hydrocarbons, cracking fracture life Into more low-boiling naphtha component C₅~NBP200, is present in gas phase in reactor operating condition lower part；NBP200 tables Show the fraction section that normal boiling point is 200 DEG C, its pure component can be normal boiling point between 195~205 DEG C of component, such as conventional boiling The inclined tetramethyl that the hendecane, the pentamethyl benzofuran that normal boiling point is 196 DEG C, normal boiling point that point is 196 DEG C are 198.4 DEG C Toluidines that benzene, normal boiling point are 200 DEG C, two or six xylenols that normal boiling point is 201 DEG C, 4 methyl that normal boiling point is 203 DEG C Hydrogenate indenes etc..

In hydrogenation process TR, heavy hydrocarbon, either shallow conversion product in anterior hydrogenation process product enter follow-up add In hydrogen processing procedure such as deep hydrofinishing process or hydrocracking process, following shadow will be produced if above-mentioned gaseous component exists Ring：

1. foreign gas component H₂O、H₂S、NH₃、CO、CO₂With very high phase concentrations such as 7~13%, can significantly it drop Low hydrogen gas concentration, that is, significantly reduce hydrogen gaseous phase partial pressure value；

H₂O、H₂S、NH₃Hetero atom (non-hydrogen atom) have lone electron to being electron donor, can adsorb in gas phase On the activated centre on middle hydrogenation catalyst surface, catalyst activity is reduced；

Oxygen and carbon in CO have lone electron to being electron donor, can adsorb hydrogenation catalyst surface in the gas phase Activated centre on, reduce catalyst activity；

CO₂In oxygen there is lone electron to being electron donor, hydrogenation catalyst surface in the gas phase can be adsorbed On activated centre, catalyst activity is reduced；

CO、CO₂Active hydrogen atom can also be consumed and be converted into H₂O、CH₄；

2. conventional gas component C₁~C₄, with 2.0~5.0% phase concentrations, can reduce density of hydrogen reduces hydrogen Gaseous phase partial pressure value；

3. naphtha component C₅~NBP200 components, NBP200~NBP330 components, the unsaturated bond of its unsaturated component Active hydrogen atom can be consumed and be converted into saturated bond, heat cracking reaction consumption active hydrogen atom generation more low-carbon occurs for constituent part Several the hydrocarbon components, usually this is a kind of process for reducing the hydrocarbon component value.

Therefore, the low boiling component for avoiding or eliminating the either shallow hydrogenation process AR generations of hydrogenation process TR enters subsequently Deep hydrogenation process BR, will produce influences directly below and indirectly：

1. significantly improving density of hydrogen, that is, significantly improve hydrogen gaseous phase partial pressure value；

2. reducing impurity composition gaseous phase partial pressure, catalyst activity is improved, or reduce catalyst amount；

3. the low boiling hydrocarbon quantity reduced in follow-up hydrogenation processing procedure raw material hydrocarbon avoids the secondary of these low boiling hydrocarbons Hydrogenation；And the hydrogen feed newly added then has air lift effect, make the part low boiling point in follow-up hydrogenation processing procedure raw material hydrocarbon Hydrocarbon is transferred to gas phase by liquid phase, so that its one way avoids processing in reaction zone multi-reflow by subsequent reaction zone, subsequent reactions Area can perform high boiling component desired temperature, expected cycle-index, the deep hydrogenation of expeced time, it is evident that be remarkably improved Catalyst reaction selectivity, shorten the goal response time, suppresses side reaction, increases target product yield；

4. suppress negative reaction, mainly suppress thermal condensation reaction, extend catalyst life or increase row access cycle or Reduce decaying catalyst emission index, reduce catalyst consumption, improve reaction under high pressure system operability (reduce liquid viscosity, Reduce organic condensation thing deposition velocity, reduce solids content i.e. reduction solid erosion rate) extend the continuous cycle of operation；

5. improving selectivity of the active hydrogen atom to goal response, hydrogen consumption is reduced；

6. improve the yield of higher carbon number hydrocarbon component；

7. being influenced as indirect, because improving hydrogen dividing potential drop, the hot tearing rate of heavy constituent such as gum asphalt can be improved, can be reduced The thermal condensation rate of high heavy constituent such as gum asphalt；

8. being influenced as indirect, because improving hydrogen dividing potential drop, reaction temperature can be reduced or improve air speed, that is, reduce operating severity Or improve processing capacity；

9. because realizing the concentration of catalyst solid, that is, catalyst concn is improved, new addition catalyst can be reduced Quantity；

10. reduce the quantity of new addition catalyst, you can reduce decaying catalyst discharge capacity, it is possible to reduce be catalyzed with inactivation The quantity of the not retortable heavy oil of agent discharge, you can to increase liquid yield；

(11) because improving hydrogen partial pressure and/or improving catalyst concn, active hydrogen atom in liquid phase can be improved Concentration, so under the premise of operability is ensured, can allow successive depths hydrogenation process BR to be grasped under the conditions of more stringent Make such as to improve hydrofinishing depth and/or improve one way hot tearing rate, can so reduce circulation hydrogenation material such as unconverted oil The quantity of the circulation slurry oil of composition reduces recycle ratio, reduces high pressure hot separator, high pressure hot separator bottom dropping valve, follow-up The liquid processing capacity and solid flow of fractionating system；

(12) because the liquid phase of follow-up hydrogenation processing procedure be mainly made of high boiling hydrocarbon, operation temperature it is high, therefore thermal cracking The number of free radical higher of process, fresh hydrogen supply dissolvent is added in successive depths hydrogenation process BR, can be significantly improved liquid phase hydrogen and be turned Speed is moved, gives full play to the hydrogen supply effect of fresh hydrogen supply dissolvent, the stabilized hydrogenation reaction speed of free radical can be dramatically speeded up, significantly Suppress macromolecular thermal condensation reaction, significantly inhibit the reaction of intermediate product secondary cracking, improve thermal cracking product property, improve cracking Liquid oil yield.

In general, the gaseous component that the either shallow hydrogenation process AR of hydrogenation process TR is produced is prevented to be hydrogenated with into successive depths The mode of process BR, is the independent thermal high air lift separation for setting independent high pressure hot separator or being set using hydrogen stripping step Device, hot high score oil return to hydrogenation process TR (the first reaction zone or subsequent reaction zone) cyclic process, and this flow belongs to single A kind of hydrogenation method for coal tar suspension bed of heterogeneous catalysis of section circulation process such as ZL201010217358.1, Recycle oil logistics processing method described in a kind of coal direct liquefaction methods of ZL200610090484.9, the program make recycle oil and original Material be hydrogenated with the lump, flow simply invest it is low, be avoided that the low boiling component flashed off circulation hydrogenation, but this single hop circulate There are following major defect for flow：

1. since the component composition and initial feed hydrocarbon of recycle oil (or circulation fluid is expected admittedly) are there are bigger difference, it is suitable There are larger for reaction condition such as operation temperature, hydrogen partial pressure, reaction time, side reaction and reaction mechanism of negative reaction etc. Difference, it is impossible to simple unified；And recycle oil is in successive depths hydrogenation process BR, a hydrogenation products liquid phase with initial feed hydrocarbon It is in together in " low hydrogen gas, high impurity gaseous environment " caused by " a hydrogenation products gas phase ", and usually recycle oil is for one The gaseous component of secondary hydrogenation products has the function of that certain " absorbing liquid " can dissolve low boiling hydrocarbon component, such recycle oil Hydrogenation process is difficult to the liquid phase state that expected " low boiling hydrocarbon liquid concentration is low, high boiling hydrocarbon liquid concentration is high " is presented, Circulation hydrogenation reaction poor selectivity, side reaction is more, negative reaction is more, and reaction efficiency is low, thermal condensation produce rate is high, it is difficult to realizes Gao Xuan Selecting property, the reaction of efficient deep hydrofinishing and/or hydrogenation heat cracking reaction effect, and can be only formed circulation hydrogenation reaction inferior；

2. high pressure hot separator uses a large amount of air lift hydrogen, it is big to increase the volume of independent high pressure hot separator, investment Greatly, hydrogen utilization ratio is low；

3. independent high pressure hot separator is set or carries out hydrogen air lift operation, and its operation temperature is typically reaction system Peak, easily induce pyrocondensation compound deposition；

4. and the operation steady in a long-term of instrument system particularly level gauging and control system, accurate measurement difficulty are big；

5. setting independent high pressure hot separator, the hazardous material (fluids) quantity increase of reaction system storage, danger are big, and operation is multiple Miscellaneous, investment is greatly.

Since there are above-mentioned shortcomings, the first choice not usually in engineering.

The gaseous component that the either shallow hydrogenation process AR of hydrogenation process TR is produced is prevented to enter successive depths hydrogenation process The another way of BR is to set high pressure hot separator between reactor, i.e., draws the hot high score oil of high pressure hot separator between reactor Enter in second stage reactor, so that the shortcomings that avoiding foregoing schemes, but there are following major defect for this single hop circulation process：

1. due to the hydrocarbon ils in either shallow hydrogenation process AR products, hydrogenation depth is too low therefore containing a large amount of viscosity are big, surface The inferior heavy oil that power is big, easily foams, and contain the materials such as a large amount of solid catalysts, fine coal either shallow conversion product, its solid contents Height, poor fluidity, translucency are low, physical property fluctuation is big, and high pressure hot separator is difficult to complete preferable gas-liquid separation between reactor；

2. high pressure hot separator between reactor, its solid contents is high, material heat endurance is poor, in the poor of liquid phase buffer area Low flow velocity flows under hydrogen atmosphere, easily induces solid deposition, produces easily deposition heavy hydrocarbon thermal condensation thing；

3. high pressure hot separator between reactor, the behaviour steady in a long-term of instrument system particularly level gauging and control system Make, accurately measurement difficulty is big；Independent high pressure hot separator, the hazardous material (fluids) quantity increase of reaction system storage, danger are set Greatly, complicated, investment is greatly；

4. since the operation temperature of successive depths hydrogenation process BR is usually compared with the operation temperature higher of either shallow hydrogenation process AR, So high pressure hot separator is inconvenient to use cooling operation to suppress thermal condensation between reactor；

5. for coal liquefaction hydrogenation process, entrained solid in the gas that high pressure hot separator is discharged between reactor, belongs to Coal either shallow conversion product, if directly recycled, will cause more liquefied residue discharge capacitys and entrained oil loss amount；Such as introduce independence Hydrogenation process, then cause flow to complicate；

In order to overcome above-mentioned existing process defect, main task of the invention is：Without using high pressure hot separator premise Under, deep hydrogenation is carried out for the high boiling point product in intermediate product or deep hydrogenation product, in order to be reacted in deep hydrogenation Journey is quick, high selectivity carries out target hydrogenation reaction, it is necessary to effectively optimizes thermodynamic condition, i.e., must improve hydrogen partial pressure, carry The numerical value of one or several operating parameter in high catalyst concentration, raising liquid phase in high boiling hydrocarbon concentration.

The present invention it is basic contemplate be：The hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula is like secondary hydrogenation side Method, in the back-mixing stream expanded bed reactor BRXE of secondary hydrogenation reaction process BR, in one-stage hydrogenation reaction product ARP and BRXE Between product BRXE-8 mixing go upward to the de- liquid zone domain in top and separate phegma BRXEP-LR and gassiness material product BRXEP-M, It is BRXE-8 that the BR upstreams hydroconversion reaction zone BRA of BRXEP-LR returns BRXE-DBP, which starts the cycle over hydro-conversion, in the gas phase H₂ Volumetric concentration is high, it is high to be carried out under conditions of low, the high boiling hydrocarbon concentration height low with low boiling hydrocarbon concentration in liquid phase of impurity volumetric concentration Selectivity, highly effective hydrogenation reaction, significantly inhibit high boiling hydrocarbon thermal condensation and low boiling hydrocarbon secondary cracking；Gas air lift in BRXE-8 Low boiling hydrocarbon enters gas phase discharge BRXE in ARP liquid phases；BRP, which enters three sections of hydrogenation process CR, can build like three sections of hydrogenation processes.

The present invention, in liquid connects multisection type reaction process, is formed the high-purity hydrogen of substep addition with cross-flow, had Act on below：

1. adding chemistry consumption hydrogen step by step, prevent single hop from excessive hydrogen to oil volume ratio occur, beneficial to raising reaction compartment liquid phase ratio Rate；

2. exhaust carries each section of low-boiling products and leaves reaction compartment in time step by step, low-boiling products are avoided in reaction system Detrimental accumulation；Multi-stek hydrogenation process, each section of new hydrogen is also stripping gas；

3. each section is respectively formed high hydrogen/feedstock ratio, the high hydrogen partial pressure environment of whole process is formed；

4. add quenching hydrogen step by step, its operation temperature flexible adjustment, air lift and/or cooling feedstock oil (and higher level's liquid phase production Thing), in low boiling hydrocarbon can form notable temperature drop, and the reaction heat that each section of gassiness product then carries the hydrocarbon ils steam of upper state Discharge reaction process is without entering back segment reaction process in time；

5. air lift forms " being hydrogenated with during classification control " feature step by step, air lift makes high boiling hydrocarbon in liquid phase be enriched with step by step step by step, more Section hydrogenation process, has " low boiling hydrocarbon hydrogenation reaction step lack the time is short, high boiling hydrocarbon hydrogenation reaction step more times are grown " Feature.

In fact, since raw material A R1F contains substantial amounts of organic oxygen, organic nitrogen, short-side chain aromatic yl group, its hydrogenation products Containing a large amount of water, ammonia, CO, conventional gas hydrocarbon, and thermal cracking also produces substantial amounts of normal boiling point between 50~330 DEG C of hydrocarbon group Divide, water partial pressure, the ammonia of gas phase in the deep hydrogenation step of hydro-upgrading product quality are particularly determined to reduce reaction process Partial pressure, CO partial pressures, low boiling hydrocarbon liquid concentration, improve hydrogen partial pressure, improve liquid-phase catalysis agent concentration, improve liquid phase unconverted oil It is dense, avoid secondary thermal cracking of low-boiling products etc., usually using substantial amounts of recycle hydrogen as gaseous phase diluent or liquid phase stripping agent. The present invention searches out a kind of high effective way for playing its effect for a large amount of circulating hydrogens at the same time.

The one-stage hydrogenation reaction process AR or secondary hydrogenation process BR or three sections of hydrogenation process CR of the present invention, as needed, 1 can be used or be used in series 2 or be used in series more hydrogenation reactors, the working method of reactor A RZ can be appointed A kind of suitable up flow type expanded bed reactor form.

In order to improve the hydrogen partial pressure of two sections or three sections hydrogenation processes, realize best hydrogenation effect, preferably ensure Into the hydrogen volume purity of the hydrogen gas stream of backend hydrogenation process, usually above 95%, 98% is generally greater than, preferably higher than 99.9%, that is to say, that first by fresh hydrogen.

The back segment upper feeding back-mixing hydrocarbon material of stream expanded bed reactor formula of the present invention utilizes back segment back-mixing like secondary hydrogenation method The gas-liquid separating function and liquid distribution function at the top of expanded bed reactor BRXE are flowed, makes the leading portion product entered from BRXE tops Abjection foreign gas, conventional gas hydrocarbon, the hydrocarbon liquid XL of low boiling point conventional liq hydrocarbon are obtained, part hydrocarbon liquid XL is as back segment hydrocarbon feed Mixed with high-purity hydrogen and carry out deep hydrogenation, its technological effect or aimed at：

1. secondary hydrogenation reaction process BR, can perform the deep hydrofinishing reaction and/or overhydrocracking of high selectivity Reaction, i.e., totality hydrogenation process yield of light oil can significantly improve, hydrogenated products quality can significantly improve, pyrocondensation compound Yield can reduce；

2. realize the one way deep conversion of one section of unconverted oil, can be greatly lowered high pressure hot separator arrange to separation, The hot high score oil of fractionating system and its quantity of the solid carried, can simplify hot high score oil separation process, can significantly drop Its low separation and/or the scale of fractionating section, can be greatly lowered investment and energy consumption；

Because reducing non-targeted heat cracking reaction, therefore high conversion secondary hydrogenation operation scheme can be used, improved total Body one way liquid yield；

3. realizing the one way deep conversion of unconverted oil, the technique purpose for the net product arranged outside hot high score is converted mainly into Dead catalyst, thermal condensation product are discharged, the use for the few efficient hydrogenation catalyst of dosage creates condition, can only arrange at this time Go out minimal amount of hot high score oil to discharge minimal amount of dead catalyst, thermal condensation product；

Certainly, since the deep conversion of unconverted oil is conversion per pass, it is impossible to full conversion, therefore recycle oil quantity simply drops Low rather than cancellation；

It is obvious that it can significantly slow down the impingment corrosion of hot high score oil pressure reducing valve；Because it is total to considerably reduce material Measure, reduce solids quantity, reducing low boiling point and easily vaporize composition quantities,

4. realizing the one way deep conversion of unconverted oil, " shorten unconverted oil to greatest extent and enter circulation hydrogenation instead Answer the flowing time there are thermal condensation tendency of the no hydrogen adjoint process of process ", it can effectively reduce pyrocondensation compound production；

The heavy hydrocarbon quantity entrained by pyrocondensation thing discharge fractionating system can be reduced；

5. realizing the one way deep conversion of unconverted oil, the unconverted oil concentration in hot high score oil can be effectively improved, can To effectively improve reaction, the operability of fractionating system and the continuous cycle of operation.

Said from combination application angle, by taking coal tar hydrogenating reaction process, coal liquifaction hydrogenation process as an example, the present invention is extremely Rare following several application modes：

1. using the present invention structure two sections or multi-stek hydrogenation process, the gas such as foreign gas, light hydrocarbon component can be discharged immediately Body product, in the main body reaction compartment of subsequent reactions section, forms hydrogen volume concentration higher, that is, hydrogen partial pressure higher, impurity volume The lower gaseous environment of concentration and low boiling component liquid concentration is lower, high boiling component liquid concentration higher, catalyst liquid phase are dense The liquid phase environment of higher is spent, can effectively suppress thermal condensation reaction and secondary thermal cracking, improve reaction selectivity and reaction speed；

For example the operation gross pressure for 20MPa, vapor phase hydrogen concentration can bring up to 85~93% by 70% and improve 15~23%, hydrogen partial pressure can improve 3.0~4.6MPa, this is surprising effect, can increase substantially reaction speed and anti- It selectively should significantly suppress thermal condensation reaction, secondary thermal cracking；In other words, ensureing that hydrogen partial pressure numerical value is 14.0MPa Under the premise of, operation stagnation pressure can be reduced to 15~16.5MPa, this is surprising effect, and plant investment, energy consumption can significantly drop It is low.Equipment safety can increase substantially, and be more conducive to the secondary pyrolysis for avoiding low boiling hydrocarbon, because operation stagnation pressure Decline beneficial to low boiling hydrocarbon vaporization；

The present invention, secondary hydrogenation reaction process BR can carry out deep hydrofinishing reaction, for example carry out high temperature coal-tar The deep hydrofinishing reaction of asphalt component, under conditions of not causing overcracking to react, carries out depth removing impurities matter and selection Property aromatic moiety saturated reaction, produces the aromatic fraction of extremely low impurity content, and some of which aromatic fraction can pass through appropriateness Dehydrogenation hot-working is converted into low impurity, the aromatic fraction of high aromatic carbon rate, the original as production coal-based needle coke or coal measures carbon fiber Material；

The present invention, secondary hydrogenation reaction process BR can carry out overhydrocracking reaction, for example carry out medium temperature coal tar The overhydrocracking reaction of the one-stage hydrogenation reaction liquid product of asphalt component, or carry out medium temperature coal tar asphalt component The deep hydrofinishing of one-stage hydrogenation reaction liquid product reacts the cascade reaction of overhydrocracking reaction, or carries out coal The cascade reaction of the overhydrocracking reaction of the one-stage hydrogenation reaction liquid product of liquefaction hydrogenation process；

In short, reaction process can significantly improve feed stock conversion；Improve operability；

2. for recycle oil systemic circulation flow existing for " reactive moieties-fractionating section ", because can be formed initial The high conversion per pass of raw material reaction process, so that the unconverted oil recycle oil quantity for reducing reaction-fractionation systemic circulation drops Low systemic circulation ratio, reduces the process scale of the circulation oil system of reaction-fractionation systemic circulation, reduces investment, reduces energy consumption；

3. catalyst amount ratio can be reduced and reduce decaying catalyst discharge capacity, therefore, it is possible to reduce be catalyzed with inactivation The quantity of the not retortable heavy oil of agent discharge, you can to increase liquid yield；

4. due to the condition with high hydrogen partial pressure and/or high liquid catalyst agent concentration, this can be used with tandem sequence repeats Invention, can obtain diverse location, different hydrogenation depths, the hydrogenated liquid product of different quality, as different purposes；Can be from respectively The high pressure hot separator of level product discharges product liquids at different levels；

5. because can suppress thermal condensation, therefore the operability that can improve reaction under high pressure system (reduces organic condensation produce Amount, reduction organic condensation thing deposition velocity, reduction liquid phase viscosity, reduction solids content reduce solid erosion rate) i.e. extension The continuous cycle of operation, improves reactor, high pressure hot separator, high pressure hot separator bottom high-pressure difference tapping valve, hot low point of oil Evaporate the operating environment of system；

6. in order to strengthen a certain operation target, multiple combinations technique can be formed with flexible configuration flow；

7. it is suitable for new device or existing apparatus transformation.

From the point of view of the thermal condensation time for suppressing unconverted oil circulating path, the high boiling hydrocarbon component that the present invention is formed is not The one way deep conversion flow of oil is converted, to greatest extent " unconverted oil can be shortened and be recycled into the hydrogen-free before hydrogenation process The time of the flow process there are thermal condensation tendency of gas adjoint process ", therefore, appearance of the invention is inevitable.

The step of with the other technologies of combination application, can such as increasing the liquid scrubbing of gas separated by high pressure separator BS1V, increase hydrogen BH air lifts The step of de- light component of hot high score oil, inject into the net product of hot high score oil the step of flux oil reduces solid concentration, to heat The step of injection cooling oil reduces its temperature in the net product of high score oil etc..

The present invention, can be by changing the Process flow of each section of hydrogenation process, can be other suitable by combining processing In the hydrocarbon material of joint processing, a variety of groups can be formed by combining the downstream processing methods of hydrocarbon ils in a variety of hot gas separated by high pressure separators Close technique.

The method of the invention has no report.

Therefore, the first object of the present invention is to propose the hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula like two sections Method of hydrotreating, hydrocarbon material can be oil and/or coal.

Second purpose of the invention is to propose back segment upper feeding back-mixing stream expanded bed reactor formula coal tar like secondary hydrogenation side Method.

3rd purpose of the invention is to propose that a kind of back segment upper feeding back-mixing stream expanded bed reactor formula coal liquifaction adds like two sections Hydrogen methods.

4th purpose of the invention is to propose the hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula like secondary hydrogenation side Method, each reaction process use hydrogen supply hydrocarbon.

5th purpose of the invention is to propose the hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula like secondary hydrogenation side Method, back segment reaction product return to upstream difference hydrogenation process and form a variety of circulation process.

The content of the invention

The hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula of the present invention is like secondary hydrogenation method, it is characterised in that bag Containing following steps：

(1) in one-stage hydrogenation reaction process AR, there are hydrogen, hydrocarbon liquid phase, there may be the mixed phase thing of solid particle at the same time Under the conditions of material, the first raw material A R1F at least containing carbon and protium enters one section of one-stage hydrogenation reaction process AR progress and adds Hydrogen reaction ARR obtains one-stage hydrogenation reaction product BASE-ARP, discharges one-stage hydrogenation reaction effluent ARP-X, and one section of discharge adds The net product ARP of hydrogen reaction process；

First raw material A R1F, includes liquid material AR1FL and solid particulate materials AR1FS that may be present；

In one-stage hydrogenation reaction process AR, there are hydrogen, hydrocarbon liquid phase, there may be solid particle at the same time；

One-stage hydrogenation reacts ARR, includes the hydrofining reaction of at least a portion liquid material AR1FL, may include extremely The hydrocracking reaction of few a part of liquid material AR1FL, may include at least a portion solid material AR1FS that may be present Hydrogenation heat cracking reaction；

One-stage hydrogenation reaction process AR, may use catalyst ARC；

One-stage hydrogenation reaction product BASE-ARP, at the same time may the mixed phase containing solid particle containing hydrogen, hydrocarbon liquid phase Material；

Material based on one-stage hydrogenation reaction product BASE-ARP is used as one-stage hydrogenation reaction effluent ARP-X, and one section adds Hydrogen reaction effluent ARP-X, occurs, one-stage hydrogenation reaction effluent ARP-X is gas in the form of 1 tunnel or 2 tunnels or multichannel material Phase or liquid phase or gas-liquid mixed phase or gas-liquid-solid three-phase logistics；

In the first hydrogenation process AR, using expanded bed hydrogenation reactor, at least 1 hydrogenation reactor is used；

The net product ARP of at least a portion is used as secondary hydrogenation top charging BR1FM；

(2) in secondary hydrogenation reaction process BR, there are hydrogen, hydrocarbon liquid phase, there may be the mixed phase thing of solid particle at the same time Under the conditions of material, secondary hydrogenation raw material BR1FM and hydrogen-rich stream BR1FH enter secondary hydrogenation reaction process BR and carry out secondary hydrogenation Reaction BRR obtains secondary hydrogenation reaction product BASE-BRP, discharges secondary hydrogenation reaction effluent BRP-X, discharges secondary hydrogenation React net product BRP；

In the back-mixing stream expanded bed reactor BRXE of secondary hydrogenation reaction process BR, one-stage hydrogenation reaction product ARP with BRXE intermediate products BRXE-8P is blended in the de- liquid zone domain in top and separates phegma BRXEP-LR and gassiness material product BRXEP-M, It is BRXE-8P that the BR upstreams hydroconversion reaction zone of BRXEP-LR returns BRXE-8P, which starts the cycle over hydro-conversion,；

In the main body reaction compartment of secondary hydrogenation reaction process BR, vapor phase hydrogen volumetric concentration is higher than one section of product ARP's Balance the hydrogen volume concentration of gas phase ARP-V, balance gas phase ARP- of the gaseous impurities volume components concentration less than one section of product ARP The impurity composition volumetric concentration of V；

In secondary hydrogenation reaction process BR, balance liquid phase of the high boiling hydrocarbon weight concentration higher than one section of product ARP of liquid phase The high boiling hydrocarbon weight concentration of ARP-L, balance liquid phase ARP-L of the low boiling hydrocarbon weight concentration less than one section of product ARP of liquid phase Low boiling hydrocarbon weight concentration；

When solid particle is carried in secondary hydrogenation reaction process BR, in liquid phase, the weight for the solid particulate matter that liquid phase carries Than the weight ratio for the solid particulate matter that the balance liquid phase ARP-L higher than one section of product ARP is carried；

In the second hydrogenation process BR, using expanded bed hydrogenation reactor, at least 1 hydrogenation reactor is used；

(3) recovery section of net product BRP is reacted in secondary hydrogenation, recycling secondary hydrogenation reacts net product BRP.

The present invention, in secondary hydrogenation reaction process BR, the working method of back-mixing stream expanded bed reactor BRXE can be selected from 1 kind or several of combination of following manner：

1. using built-in guide shell, circulation flow field in guide shell is formed；

2. using built-in guide shell, the guide shell outside circulation flow field in reactor is formed；

3. liquid collecting cup BR1LD, liquid phase delivery line BR1LK, liquid pressing pump BR1-9C are set, in liquid collecting cup lower disposed one The logistics distributor BR1MG of the net product ARP of section hydrogenation process；

4. setting liquid collecting cup BR1LD, liquid phase delivery line BR1LK, liquid pressing pump BR1-9C, one is arranged on liquid collecting cup top The logistics distributor BR1MG of the net product ARP of section hydrogenation process；

5. using the external circulation pipe of reactor B RXE, form reactor B RXE tops reaction zone liquid phase and flow down to return and react The device outside circulation of device BRXE lower reaction zones；

6. other effective means.

The present invention, reacts the recovery section of net product BRP in secondary hydrogenation, can set three sections of hydrogenation process CR；

The net product BRP of at least a portion secondary hydrogenation reaction process BR are used as three sections of hydrogenation top charging CR1FM；

In three sections of hydrogenation process CR, there are hydrogen, hydrocarbon liquid phase, there may be the mixed phase material of solid particle at the same time Under the conditions of, three sections of hydrogenating materials CR1FM and hydrogen-rich stream CR1FH enter three sections of hydrogenation process CR and carry out three sections of hydrogenation instead Answer CRR to obtain three sections of hydrogenation reaction product BASE-CRP, discharge three sections of hydrogenation reaction effluent CRP-X, it is anti-to discharge three sections of hydrogenation Answer net product CRP；

In the back-mixing stream expanded bed reactor CRXE of three sections of hydrogenation process CR, secondary hydrogenation reaction product BRP with CRXE intermediate products CRXE-8P is blended in the de- liquid zone domain in top and separates phegma CRXEP-LR and gassiness material product CRXEP-M, It is CRXE-8P that the CR upstreams hydroconversion reaction zone of CRXEP-LR returns CRXE-8P, which starts the cycle over hydro-conversion,；

In the main body reaction compartment of three sections of hydrogenation process CR, vapor phase hydrogen volumetric concentration is higher than two sections of product BRP's Balance the hydrogen volume concentration of gas phase BRP-V, balance gas phase BRP- of the gaseous impurities volume components concentration less than two sections of product BRP The impurity composition volumetric concentration of V；

In three sections of hydrogenation process CR, balance liquid phase of the high boiling hydrocarbon weight concentration higher than two sections of product BRP of liquid phase The high boiling hydrocarbon weight concentration of BRP-L, balance liquid phase BRP-L of the low boiling hydrocarbon weight concentration less than two sections of product BRP of liquid phase Low boiling hydrocarbon weight concentration；

When solid particle is carried in three sections of hydrogenation process CR, in liquid phase, the weight for the solid particulate matter that liquid phase carries Than the weight ratio for the solid particulate matter that the balance liquid phase BRP-L higher than two sections of product BRP is carried；

In the 3rd hydrogenation process CR, using expanded bed hydrogenation reactor, at least 1 hydrogenation reactor is used.

The present invention, in three sections of hydrogenation process CR, the working method of back-mixing stream expanded bed reactor CRXE can be selected from 1 kind or several of combination of following manner：

3. liquid collecting cup CR1LD, liquid phase delivery line CR1LK, liquid pressing pump CR1-9C are set, in liquid collecting cup lower disposed two The logistics distributor CR1MG of the net product BRP of section hydrogenation process；

4. setting liquid collecting cup CR1LD, liquid phase delivery line CR1LK, liquid pressing pump CR1-9C, two are arranged on liquid collecting cup top The logistics distributor CR1MG of the net product BRP of section hydrogenation process；

5. using the external circulation pipe of reactor CRXE, form reactor CRXE tops reaction zone liquid phase and flow down to return and react The device outside circulation of device CRXE lower reaction zones；

6. other effective means.

The present invention, in secondary hydrogenation reaction process BR, the hydrocarbonaceous liquid of at least a portion secondary hydrogenation reaction process BR discharges Body logistics, may return in the hydrogenation reaction space of one-stage hydrogenation reaction process AR, with the first raw material A R1F or in-between productions Thing is mixed.

The present invention, in three sections of hydrogenation process CR, the hydrocarbonaceous liquid of three sections of hydrogenation process CR discharges of at least a portion Body logistics, may return in the hydrogenation reaction space of secondary hydrogenation reaction process BR, or reacted back to one-stage hydrogenation It is mixed in the hydrogenation reaction space of journey AR with the first raw material A R1F or in-between products.

The present invention, one-stage hydrogenation reaction process AR, can be selected from a kind or 2 kinds or several of following hydrogenation process 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 for including the use of hydrogen supply dissolvent oil adds Hydrogen direct liquefaction liquefaction process, coal refines process to oil 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 weight 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 one-stage hydrogenation reaction process AR, existing solid particle can be in following a kind or several：

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

2. catalyst granules；

3. iron rust particle；

4. particles of inorganic material；

5. coking of coal process produce into the solid particle 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 one-stage hydrogenation reaction product BASE-ARP.

The present invention, the expanded bed reactor, mode of operation can be selected from a kind or several of combinations in following：

1. suspension bed, that is, slurry bed system；

2. ebullated bed；

3. slight expanded-bed.

The present invention, secondary hydrogenation reaction process BR operating conditions are usually：

(2) normal boiling point is higher than 330 DEG C in total the hydrocarbon component in secondary hydrogenation reaction process BR, the liquid phase of reaction compartment The weight concentration of the hydrocarbon component is more than 60%, and hydrogen volume concentration is more than 80% in the gas phase of reaction compartment.

The present invention, secondary hydrogenation reaction process BR operating conditions are generally：

(2) normal boiling point is higher than 330 DEG C in total the hydrocarbon component in secondary hydrogenation reaction process BR, the liquid phase of reaction compartment The weight concentration of the hydrocarbon component is more than 70%, and hydrogen volume concentration is more than 85% in the gas phase of reaction compartment.

The present invention, secondary hydrogenation reaction process BR operating condition preferablies are：

(2) normal boiling point is higher than 330 DEG C in total the hydrocarbon component in secondary hydrogenation reaction process BR, the liquid phase of reaction compartment The weight concentration of the hydrocarbon component is more than 80%, and hydrogen volume concentration is more than 90% in the gas phase of reaction compartment.

The present invention, during using floating bed hydrogenation reactor, operating condition is usually：

(1) one-stage hydrogenation reaction process AR, using floating bed hydrogenation reactor, operating condition is：Reaction temperature for 320~ 450 DEG C, 6~30MPa of reaction pressure, 0.2~5.0h of volume space velocity of reaction compartment^-1, hydrogen to oil volume ratio 100~3000；

(2) secondary hydrogenation reaction process BR, using floating bed hydrogenation reactor, operating condition is：Reaction temperature for 400~ 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 100~3000.

The present invention, during using floating bed hydrogenation reactor, operating condition is generally：

(1) one-stage hydrogenation reaction process AR, using floating bed hydrogenation reactor, operating condition is：Reaction temperature for 360~ 440 DEG C, 12~25MPa of reaction pressure, 0.2~5.0h of volume space velocity of reaction compartment^-1, hydrogen to oil volume ratio 200~1500；

(2) secondary hydrogenation reaction process BR, using floating bed hydrogenation reactor, operating condition is：Reaction temperature for 420~ 460 DEG C, 12~25MPa of reaction pressure, 0.2~5.0h of volume space velocity of reaction compartment^-1, hydrogen to oil volume ratio 200~1500.

The present invention, during using boiling bed hydrogenation reactor, operating condition is usually：

(1) one-stage hydrogenation reaction process AR, using boiling bed hydrogenation reactor, operating condition is：Reaction temperature for 320~ 450 DEG C, 6~30MPa of reaction pressure, 0.2~5.0h of volume space velocity of reaction compartment^-1, hydrogen to oil volume ratio 100~3000；

(2) secondary hydrogenation reaction process BR, using boiling bed hydrogenation reactor, operating condition is：Reaction temperature for 400~ 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 100~3000.

The present invention, during using boiling bed hydrogenation reactor, operating condition is generally：

(1) one-stage hydrogenation reaction process AR, using boiling bed hydrogenation reactor, operating condition is：Reaction temperature for 360~ 440 DEG C, 12~25MPa of reaction pressure, 0.2~5.0h of volume space velocity of reaction compartment^-1, hydrogen to oil volume ratio 200~1500；

(2) secondary hydrogenation reaction process BR, using boiling bed hydrogenation reactor, operating condition is：Reaction temperature for 420~ 460 DEG C, 12~25MPa of reaction pressure, 0.2~5.0h of volume space velocity of reaction compartment^-1, hydrogen to oil volume ratio 200~1500.

The present invention, during for oily hydrogenation process, each section of hydrogen consumption is generally：

(1) in oily hydrogenation process, in one-stage hydrogenation reaction process AR, the first raw material A R1F is from coal tar and mainly by normal Advise higher than 400 DEG C the hydrocarbon component HD of boiling point to form, the Unit Weight hydrogen consumption of the first raw material A R1F is 0.05~7.0%；

(2) secondary hydrogenation reaction process BR, chemical hydrogen consumption amount are 0.05 to the Unit Weight hydrogen consumption of the first raw material A R1F ~3.0%.

The present invention, during for Coal Liquefaction process, each section of hydrogen consumption is generally：

(1) in Coal Liquefaction process, in one-stage hydrogenation reaction process AR, the first raw material A R1F is coal dust AR1FS and confession The Unit Weight hydrogen consumption of hydrogen solvent orange 2 A R1FL, coal dust AR1FS are 2.5~10.0%；

(2) secondary hydrogenation reaction process BR, chemical hydrogen consumption amount to the Unit Weight hydrogen consumption of coal dust AR1FS for 0.05~ 3.0%.

The present invention, during for coal tar hydrogenating, the catalyst of use can be：

(1) coal tar is come from one-stage hydrogenation reaction process AR, the first raw material A R1F；The hydrogenation catalyst ARC used, is A kind of compound coal tar hydrogenation catalyst, includes high-activity component and low activity component；The high-activity component metal with it is low The weight ratio of activity component metal is 1: 10 to 10: 1；The high-activity component is the water soluble salt compound of molybdenum or its mixing Thing；The low activity component is ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, catalyst ARC water contents are less than 2wt%；ARC particle diameters are 1~100 μm of powdered granule.

(1) coal tar is come from one-stage hydrogenation reaction process AR, the first raw material A R1F；The hydrogenation catalyst ARC used, extremely Mo elements are included less, and Mo is M in the body of work form of one-stage hydrogenation reaction process AR₀S₂In, hydrogenation catalyst ARC for 1~ 100 μm of powdered granule.

The present invention, during for coal tar hydrogenating, detailed operating condition is usually：

(1) first raw material A R1F comes from coal tar, and the operating condition of one-stage hydrogenation reaction process AR is：Temperature for 320~ 450 DEG C, pressure be 6.0~30.0MPa, hydrogen to oil volume ratio is 100~3000, hydrogenation catalyst ARC add weight be raw material AR1F weight 0.001~8.0%, reaction compartment volume space velocity be 0.1~10.0hr^-1；The weight chemistry of first raw material A R1F Hydrogen consumption is 0.05~7.0%；

(2) secondary hydrogenation reaction process BR, operating condition are：Reaction temperature for 400~480 DEG C, reaction pressure 6.0~ 0.2~5.0h of volume space velocity of 30.0MPa, reaction compartment^-1, hydrogen to oil volume ratio 100~3000, chemical hydrogen consumption amount is to the first raw material The Unit Weight hydrogen consumption of AR1F is 0.05~3.0%.

The present invention, during for coal tar hydrogenating, detailed operating condition is generally：

(1) first raw material A R1F comes from coal tar, and the operating condition of one-stage hydrogenation reaction process AR is：Temperature for 360~ 440 DEG C, pressure be 12.0~25.0MPa, hydrogen to oil volume ratio is 300~1500, hydrogenation catalyst ARC add weight be raw material AR1F weight 0.5~5.0%, reaction compartment volume space velocity be 0.2~5.0hr^-1；The weight chemical hydrogen consumption of first raw material A R1F Measure as 0.5~5.5%；

(2) secondary hydrogenation reaction process BR, operating condition are：Reaction temperature is 420~460 DEG C, reaction pressure 12.0 0.2~5.0h of volume space velocity of~25.0MPa, reaction compartment^-1, hydrogen to oil volume ratio 300~1500, chemical hydrogen consumption amount is to the first original The Unit Weight hydrogen consumption for expecting AR1F is 0.3~2.0%.

The present invention, the hydrogenation process of the first raw material A R1F, can use hydrogen supply hydrocarbon material；First raw material A R1F can be with Include hydrogen supply hydrocarbon material；In secondary hydrogenation reaction process BR, mainly it can will be higher than what 300 DEG C of the hydrocarbon components formed by normal boiling point Hydrogen-containing hydrocarbon stream introduces the reaction compartment of secondary hydrogenation reaction process BR, with secondary hydrogenation raw material BR1F or its hydrogenation intermediate product Contact mixing；, can be by mainly by normal boiling point higher than the hydrogen supply hydrocarbon that 350 DEG C of the hydrocarbon components form in three sections of hydrogenation process CR Logistics introduces the reaction compartment of three sections of hydrogenation process CR, is contacted with three sections of hydrogenating materials CR1FL or its hydrogenation intermediate product Mixing.

The present invention, in secondary hydrogenation reaction process BR, in general, at least a portion hydrogen-rich stream BR1FH comes from new hydrogen.

The present invention, each conversion zone reactor number of units, is typically：

(1) in one-stage hydrogenation reaction process AR, 1~4 hydrogenation reactor is used；

(2) in secondary hydrogenation reaction process BR, 1~2 hydrogenation reactor is used.

The present invention, in oily hydrogenation process, each conversion zone reactor number of units is typically：

(1) coal tar is come from oily hydrogenation process, the first raw material A R1F, in one-stage hydrogenation reaction process AR, uses 1~3 Platform hydrogenation reactor；

(2) in secondary hydrogenation reaction process BR, 1 hydrogenation reactor is used.

The present invention, in Coal Liquefaction process, each conversion zone reactor number of units is typically：

(1) fine coal and hydrocarbon ils are included in Coal Liquefaction process, the first raw material A R1F, in one-stage hydrogenation reaction process AR, Use 2~3 hydrogenation reactors；

The present invention, each conversion zone mode of operation 1 can be：

(1) in oily hydrogenation process, in one-stage hydrogenation reaction process AR, it is substantially carried out hydrofining reaction；

(2) it is smart in secondary hydrogenation reaction process BR, the deep hydrogenation for being substantially carried out the oily high boiling component of one-stage hydrogenation generation System reaction.

The present invention, each conversion zone mode of operation 2 can be：

(2) in secondary hydrogenation reaction process BR, it is anti-to be substantially carried out being hydrocracked for the oily high boiling component of one-stage hydrogenation generation Should.

The present invention, each conversion zone mode of operation 3 can be：

(1) in oily hydrogenation process, in one-stage hydrogenation reaction process AR, it is substantially carried out hydrofining reaction and either shallow hydrogenation is split Change reaction；

(2) split in secondary hydrogenation reaction process BR, the deep hydrogenation for being substantially carried out the oily high boiling component of one-stage hydrogenation generation Change reaction.

The present invention, each conversion zone mode of operation 4 can be：

(1) in oily hydrogenation process, in one-stage hydrogenation reaction process AR, it is substantially carried out hydrofining reaction and is hydrocracked anti- Should；

(2) it is anti-in secondary hydrogenation reaction process BR, the hydrofinishing for being substantially carried out the oily high boiling component of one-stage hydrogenation generation It should be reacted with overhydrocracking.

The present invention, each conversion zone mode of operation 5 can be：

(1) in Coal Liquefaction process, in one-stage hydrogenation reaction process AR, carry out the pyrolytic reaction of coal, be hydrocracked instead Answer, the reaction of free radical stabilized hydrogenation；

(2) it is anti-in secondary hydrogenation reaction process BR, the overhydrocracking for carrying out one-stage hydrogenation product high boiling component Answer, the reaction of free radical stabilized hydrogenation.

The present invention, in secondary hydrogenation reaction process BR, the hydrogen volume concentration of hydrogen-rich stream BR1FH：Typically larger than 90%th, it is generally higher than 95%, more preferably greater than 99%.

The present invention, in three sections of hydrogenation process CR, the hydrogen volume concentration of hydrogen-rich stream CR1FH：Typically larger than 90%th, it is generally higher than 95%, more preferably greater than 99%.

Brief description of the drawings

Fig. 1 is the back segment upper feeding back-mixing hydrocarbon material of stream expanded bed reactor formula of the present invention like the 1st kind of secondary hydrogenation method The principle process schematic diagram of technical solution, includes one section of reaction process AR, secondary hydrogenation process BR.

As shown in Figure 1, the reaction combined feed AR1TF comprising conventional liquid hydrocarbon, hydrogen enters one-stage hydrogenation reaction process AR One section of first hydrogenation reactor AR1, one-stage hydrogenation reaction process AR uses, which are shown in the figure, the expansion of at least 1 up flow type The situation of bed hydroprocessing reactor A R1.One section of first hydrogenation reactor AR1 can be empty cartridge type suspension bed or set liquid product to follow The hydrogenation reactor of loop system.

As shown in Figure 1, the feedstock hydrocarbon AR1F conveyed through pipeline 101, the hydrogen material flow A R1FH conveyed with pipeline 102 After mixing, the combined feed AR1TF as one section of first hydrogenation reactor AR1 enters one section of first hydrogenation reactor AR1 through road 105 Carry out one section of first hydrogenation reaction to obtain one section of first hydrogenation reaction product AR1P and be used as one section of final reacting product ARP, pass through Top of the pipeline 106 as secondary hydrogenation process BR is fed, into the top of two section of first hydrogenation reactor BR1.

As shown in Figure 1, the liquid material that the high-purity hydrogen BR1FH and device internal upper part that are conveyed through pipeline 202 are returned mixes The bottom raw material BR1TF as two section of first hydrogenation reactor BR1 enters the uplink flowing of two section of first hydrogenation reactor BR1 afterwards And reaction process, carry out secondary hydrogenation reaction BRR and be converted into product BR1P-88, mixed with top charging AR1P.

As shown in Figure 1, in the back-mixing stream expanded bed reactor BR1E of secondary hydrogenation reaction process BR, one-stage hydrogenation reaction Product ARP is mixed with BR1E intermediate products BR1E-8P to be gone upward to the de- liquid zone domain in top and separates phegma BR1EP-LR and product The bottom hydroconversion reaction zone of BR1P, BR1EP-LR return BR1 start upstream hydrogenation reaction and are converted into BR1E-8P, in the gas phase H2 volumetric concentrations are high, are carried out under conditions of low, the high boiling hydrocarbon concentration height low with low boiling hydrocarbon concentration in liquid phase of impurity volumetric concentration High selectivity, highly effective hydrogenation reaction, significantly inhibit high boiling hydrocarbon thermal condensation and low boiling hydrocarbon secondary cracking；Gas in BR1E-8P Low boiling hydrocarbon enters gas phase in air lift ARP liquid phases, and BR1 is discharged with product BR1P.

Product BRP, the mode of recycling can be directly entered the i.e. BS1 of thermal high separate section BRP-S1 to be separated into hot high score Gas BRP-S1V bodies and hot high score oil BRP-S1L (may contain solid particle) liquid, can enter hydrogenation process BRP- BR1800 is converted into product BRP-BR1800-P and then recycles it.

As shown in Figure 1, usual two sections of product BR1P are containing some liquid from one-stage hydrogenation reaction product AR1P AR1P-M-L, therefore technical solution shown in Fig. 1 is not the secondary hydrogenation process of complete meaning, one-stage hydrogenation reaction product AR1P's Liquid is used as the ratio of secondary hydrogenation raw material, increases with the increase of back-mixing flow liquid phase ratio.

As shown in Figure 1, when one-stage hydrogenation reaction process AR perform coal liquifaction hydrogenation reaction when, feedstock hydrocarbon AR1F be comprising The coal of the raw materials such as coal dust, hydrogen supply dissolvent, circulation slurry oil, catalyst, vulcanizing agent, one section of first hydrogenation reactor AR1 are carried out Coal is swollen, is pyrolyzed, being hydrocracked The floating bed hydrogenation reactor of the liquid product circulatory system is set, to prevent particulate matter from precipitating；Containing light in reaction product AR1P Matter is oily, middle matter oil and mink cell focus and can not distillation such as catalyst, ash content, liquefaction semicoke, asphaltene, preasphaltene etc., protecting Under the premise of demonstrate,proving follow-up thermal high separate section operability, the recycle oil AR1P-LR of one section of first hydrogenation reactor AR1 generation The hydrocarbon component be preferably to deviate from the high boiling hydrocarbon of matter oil in light oil and at least a portion, it is oily to avoid light oil, middle matter Unhelpful harmful circulation thermal cracking.

As shown in Figure 1, when one-stage hydrogenation reaction process AR perform coal tar hydrogenating reaction when, feedstock hydrocarbon AR1F be comprising Coal tar, catalyst, the coal of vulcanizing agent, feedstock hydrocarbon AR1F are also possible that circulation slurry oil, hydrogen supply dissolvent, pyrolysis or dry Semicoke dust of process etc. is evaporated, one section of first hydrogenation reactor AR1 carries out the hydrofining reaction of coal tar and/or be hydrocracked Reaction, one section of first hydrogenation reactor AR1 can be empty cartridge type suspension bed or the hydrogenation reactor for setting the liquid product circulatory system； Contain light oil, middle matter oil and mink cell focus and can not distillation such as catalyst, ash content, semicoke, asphalitine in reaction product AR1P Deng, under the premise of follow-up thermal high separate section operability is ensured, the recycle oil of one section of first hydrogenation reactor AR1 generation The hydrocarbon component of AR1P-LR is preferably to deviate from the high boiling hydrocarbon of matter oil in light oil and major part, to avoid light oil, middle matter oil Unhelpful harmful circulation thermal cracking.

As shown in Figure 1, when one-stage hydrogenation reaction process AR performs the reaction of high temperature coal-tar deep hydrofinishing, hydrocarbon original Expect AR1F be comprising high temperature coal-tar, catalyst, vulcanizing agent slurry oil, feedstock hydrocarbon AR1F be also possible that circulation slurry oil, supply Semicoke dust of hydrogen solvent, pyrolysis or retort process etc., the hydrofinishing that one section of first hydrogenation reactor AR1 carries out coal tar are anti- Answer and/or either shallow coal hydrogenation cracking reaction, one section of first hydrogenation reactor AR1 can be empty cartridge type suspension bed or set liquid product The hydrogenation reactor of the circulatory system；In reaction product AR1P 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 the follow-up high pressure separate section operability of heat is ensured, one section of first hydrogenation is anti- The hydrocarbon component for answering the recycle oil AR1P-LR of device AR1 generations is preferably to deviate from the high boiling hydrocarbon of matter oil in light oil and major part, It is hydrogenated with to avoid the inefficient cycle of light oil, middle matter oil.

As shown in Figure 1, enter in secondary hydrogenation reaction process BR, the reaction total material BR1TF comprising conventional liquid hydrocarbon, hydrogen Secondary hydrogenation reaction process BR, is shown in the figure secondary hydrogenation reaction process BR and uses 1 up flow type expanded bed hydrogenation reaction The situation of device BR1, two section of first hydrogenation reactor BR1 can be empty cartridge type suspension bed or set adding for the liquid product circulatory system Hydrogen reactor.

Fig. 2 is the back segment upper feeding back-mixing hydrocarbon material of stream expanded bed reactor formula of the present invention like the 2nd kind of secondary hydrogenation method The principle process schematic diagram of technical solution, comprising one section of reaction process AR, secondary hydrogenation process BR, with Fig. 1 shows the present invention The difference of the 1st kind of technical solution be：Two section of first hydrogenation reactor BR1, using built-in guide shell, circulation in formation Flow field, Fig. 2 are illustrated that one-stage hydrogenation reaction product ARP mixes uplink situation with BR1E intermediate products BR1E-8P, and ARP passes through Be arranged in the logistics distributor BR1MG of shaft core position, into guide shell inside make uplink flowing.

Fig. 3 is the back segment upper feeding back-mixing hydrocarbon material of stream expanded bed reactor formula of the present invention like the 3rd kind of secondary hydrogenation method The principle process schematic diagram of technical solution, comprising one section of reaction process AR, secondary hydrogenation process BR, with Fig. 1 shows the present invention The difference of the 1st kind of technical solution be：Two section of first hydrogenation reactor BR1, using built-in guide shell, forms internal outer Circulation flow field, Fig. 3 are illustrated that one-stage hydrogenation reaction product ARP mixes uplink situation, ARP with BR1E intermediate products BR1E-8P By the annular tube type logistics distributor BR1MG being arranged between guide shell and wall of reactor, into upper runner inside make uplink Flowing.

Fig. 4 is the back segment upper feeding back-mixing hydrocarbon material of stream expanded bed reactor formula of the present invention like the 4th kind of secondary hydrogenation method The principle process schematic diagram of technical solution, comprising one section of reaction process AR, secondary hydrogenation process BR, with Fig. 1 shows the present invention The difference of the 1st kind of technical solution be：Two section of first hydrogenation reactor BR1, sets liquid collecting cup BR1LD, liquid phase export Pipe BR1LK, liquid pressing pump BR1-9C；In the headroom of BR1, one-stage hydrogenation reaction product ARP and BR1E intermediate products BR1E-8P, in the mixed zone of liquid collecting cup lower disposed, logistics distributor BR1MG is mixed, and is gone upward to the de- liquid zone domain in top and is separated Phegma BR1EP-LR and product BR1P, phegma BR1EP-LR are by liquid collecting cup BR1LD, catheter BR1LK, liquid pressing pump Conveyed after BR19C pressurizations through pipeline 209, BR1 reaction compartments are returned as BR1 recycle oils BR1-LR.

Fig. 5 is the back segment upper feeding back-mixing hydrocarbon material of stream expanded bed reactor formula of the present invention like the 5th kind of secondary hydrogenation method The principle process schematic diagram of technical solution, comprising one section of reaction process AR, secondary hydrogenation process BR, with Fig. 1 shows the present invention The difference of the 4th kind of technical solution be：In the logistics distributor BR1MG of liquid collecting cup top arrangement AR1P.

Fig. 6 is the hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula of the present invention like the 1st kind of three sections of method of hydrotreating The principle process schematic diagram of technical solution, comprising one section of reaction process AR, secondary hydrogenation process BR, three sections of hydrogenation process BR, with The difference of 1st kind of technical solution of the secondary hydrogenation method of the invention that Fig. 4 is represented is：It is general to reuse the present invention Read, increase by three sections of hydrogenation process BR.

As shown in fig. 6, the liquid material that the high-purity hydrogen CR1FH and device internal upper part that are conveyed through pipeline 302 are returned mixes The bottom raw material CR1TF as three section of first hydrogenation reactor CR1 enters the uplink flowing of three section of first hydrogenation reactor CR1 afterwards And reaction process, carry out secondary hydrogenation reaction CRR and be converted into product CR1E-8P, mixed with top charging BR1P.

As shown in fig. 6, in the back-mixing stream expanded bed reactor CR1E of three section of first hydrogenation reactor CR1, secondary hydrogenation Reaction product BRP is mixed with CR1E intermediate products CR1E-8P to be gone upward to the de- liquid zone domain in top and separates phegma CR1EP-LR and production The bottom hydroconversion reaction zone of thing CR1P, CR1EP-LR return CR1 starts upstream hydrogenation reaction and is converted into CR1E-8P, in gas phase Middle H2 volumetric concentrations are high, under conditions of low, the high boiling hydrocarbon concentration height low with low boiling hydrocarbon concentration in liquid phase of impurity volumetric concentration into Row high selectivity, highly effective hydrogenation reaction, significantly inhibit high boiling hydrocarbon thermal condensation and low boiling hydrocarbon secondary cracking；Gas in CR1E-8P Low boiling hydrocarbon enters gas phase in body air lift BRP liquid phases, and CR1 is discharged with product CR1P.

Fig. 7 is the hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula of the present invention like the 2nd kind of three sections of method of hydrotreating The principle process schematic diagram of technical solution, comprising one section of reaction process AR, secondary hydrogenation process BR, three sections of hydrogenation process BR, with The difference for the 1st kind of technical solution like three sections of method of hydrotreating of the invention that Fig. 6 is represented is：Two section of first hydrogenation reaction Device BR1, using built-in guide shell, circulation flow field in formation, Fig. 7 is illustrated that among one-stage hydrogenation reaction product ARP and BR1E Product BR1E-8P mixes uplink situation, and ARP is by being arranged in the logistics distributor BR1MG of shaft core position, into inside guide shell Make uplink flowing；Three section of first hydrogenation reactor CR1, using built-in guide shell, circulation flow field in formation, Fig. 7 is illustrated that two Section hydrogenation reaction product BRP mixes uplink situation with CR1E intermediate products CR1E-8P, and BRP is by being arranged in the thing of shaft core position Fluidic distributor CR1MG, into guide shell inside make uplink flowing

Fig. 8 is the hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula of the present invention like the 3rd kind of three sections of method of hydrotreating The principle process schematic diagram of technical solution, comprising one section of reaction process AR, secondary hydrogenation process BR, three sections of hydrogenation process BR, with The difference for the 1st kind of technical solution like three sections of method of hydrotreating of the invention that Fig. 6 is represented is：Two section of first hydrogenation reaction Device BR1, using built-in guide shell, forms internal outside circulation flow field, Fig. 8 is illustrated that one-stage hydrogenation reaction product ARP and BR1E Intermediate product BR1E-8P mixes uplink situation, and ARP passes through the annular tube type flow distribution that is arranged between guide shell and wall of reactor Device BR1MG, into upper runner inside make uplink flowing；Three section of first hydrogenation reactor CR1, using built-in guide shell, forms Internal outside circulation flow field, Fig. 8 are illustrated that secondary hydrogenation reaction product BRP mixes market with CR1E intermediate products CR1E-8P Condition, BRP is by the annular tube type logistics distributor CR1MG that is arranged between guide shell and wall of reactor, into inside upper runner Make uplink flowing.

Fig. 9 is the hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula of the present invention like the 3rd kind of three sections of method of hydrotreating The principle process schematic diagram of technical solution, comprising one section of reaction process AR, secondary hydrogenation process BR, three sections of hydrogenation process BR, with The difference for the 1st kind of technical solution like three sections of method of hydrotreating of the invention that Fig. 6 is represented is：Two section of first hydrogenation reaction Device BR1, sets liquid collecting cup BR1LD, liquid phase delivery line BR1LK, liquid pressing pump BR1-9C；In the headroom of BR1, one section adds Hydroformylation reaction product ARP and BR1E intermediate product BR1E-8P, in the mixed zone of liquid collecting cup lower disposed logistics distributor BR1MG Mixing, goes upward to the de- liquid zone domain in top and separates phegma BR1EP-LR and product BR1P, phegma BR1EP-LR passes through liquid collecting cup Convey through pipeline 209 after BR1LD, catheter BR1LK, liquid pressing pump BR19C pressurizations, returned as BR1 recycle oils BR1-LR BR1 reaction compartments；Three section of first hydrogenation reactor CR1, sets liquid collecting cup CR1LD, liquid phase delivery line CR1LK, liquid pressing pump CR1-9C；In the headroom of CR1, secondary hydrogenation reaction product BRP and CR1E intermediate product CR1E-8P, in liquid collecting cup lower part The mixed zone of arrangement is mixed with logistics distributor CR1MG, is gone upward to the de- liquid zone domain in top and is separated phegma CR1EP-LR and product CR1P, phegma CR1EP-LR are after liquid collecting cup CR1LD, catheter CR1LK, liquid pressing pump CR1-9C pressurizations through pipeline 309 conveyings, CR1 reaction compartments are returned as CR1 recycle oils CR1-LR.

Figure 10 is the hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula of the present invention like the 3rd kind of three sections of method of hydrotreating The principle process schematic diagram of technical solution, comprising one section of reaction process AR, secondary hydrogenation process BR, three sections of hydrogenation process BR, with The difference for the 1st kind of technical solution like three sections of method of hydrotreating of the invention that Fig. 9 is represented is：Arranged on liquid collecting cup top The logistics distributor CR1MG of BR1P.

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.

Routine 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, refers to being in gaseous hydro carbons under normal condition, including methane, ethane, third Alkane, butane.

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

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

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

Light hydrocarbon of the present invention, is naphtha component, refers to that normal boiling point is 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, refers to that normal boiling point is higher than 330 DEG C of hydro carbons.

Hydrogen to oil volume ratio of the present invention, refers 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 AR1ZE-TL is carried, refers to the solid that collection liquid AR1ZE-TL is carried The ratio of the weight of particulate matter and the weight of pure liquid phase material.

Hydrogenation reaction space, refers 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 mixer, 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 is described below.

Coal tar of the present invention, refers 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 Miscella, the distillate of coal tar of temperature tar, different 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, usually 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 usually 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.

Since raw coal property and coking or gas-making process condition change within the specific limits, the property of coal tar is also one Determine 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 is typically high for 120~450 DEG C of the hydrocarbon components and normal boiling point comprising conventional boiling range In the mixture of 450 DEG C of the 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 the typical medium temperature coal tar of table 1

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 It is typically oil soluble metal compound such as cycloalkanes in cut, and usually using hydrogenolysis-prone metal component of iron, calcium, magnesium as key component 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 Belong to 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, and above-mentioned temperature range is usually 170~350 DEG C, 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 catalyst bed 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 usually High, gum level height simultaneously contains the more component easily reacted under the conditions of mitigation, therefore, the pre-add of the 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 usually use fixed bed hydrogenation technology 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, in order to prevent gum asphalt reunite trigger it is unnecessary 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 that conventional boiling range is 370~450 DEG C or heavy distillat The conversion product of hydrogenation aromatic moiety saturation or the hydrogenation aromatic moiety of middle cut FD2 of FD3 and residue oil fraction FD4 is satisfied The conversion product of sum.The conversion product of the hydrogenation aromatic moiety saturation of middle cut FD2 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, 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, refers 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, refers to that at least a portion hydrocracking reaction occurs The process that molecular weight is less than cracked stock molecular weight is produced, which generally comprises parallel hydrodemetallization, hydrofinishing, adds Hydrogen heat cracking reaction.In usually 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 at the same time Card reaction stream has been developed that varied by the catalyst bed 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, that 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, use can be reasonably selected to prior art or is used cooperatively, has been 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 cut and takes 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, is one or more metals of periodic table of elements group 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 segment 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, refers 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 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 are compared with the dihydro body of double ring arene, and 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 opposite 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, refers to the side for making coal liquefaction by hydrogenation under solvent naphtha existence condition Method, according to the difference of solvent naphtha and catalyst, pyrolysis way and is hydrogenated with the difference of mode and the difference of 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 1 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.Residual oil occurs hydrocracking and is converted into light oil at the same time.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 impact 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, the outer oil extraction or liquefied coal coil (being usually coal liquefaction light oil) or coal liquid that it is produced Carburetion modified oil, as long as its composition possesses raw material compositing characteristic of the present invention, can be processed using the method for the present invention.

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, refers 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 reaction process of hydrogenation liquefaction.

Liquefied coal coil of the present invention, refers to the oil product that the Coal liquefaction process produces, 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 the distillate that conventional boiling range is higher than 165 DEG C), 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 function of the group of good hydrogen supply 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.In general, at least a portion coal liquefaction light oil that Coal liquefaction process produces 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, at this time there are the outer oil extraction of A and B two-way, 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 attached drawing, attached drawing is drawn to describe the present invention, but it cannot be limited The application range of the fixed present invention.

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

1. reactor shell；

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

3. the up flow type hydrogenation main reaction space being arranged in reactor enclosure body, usually using catalyst during working status, It is used to be uniformly distributed charging usually using charging distributed component；

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

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

6. reactor intermediate feed distributor (or distributor), such as mixer 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, measures 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 is external insulation material, supporting item (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, usually draws off the decreased catalysis of activity from bed bottom in an intermittent fashion Agent, fills into fresh catalyst from bed top in an intermittent fashion and maintains bed catalyst reserve；

3. slight expanded-bed.

The characteristic of the present invention is described below.

One-stage hydrogenation reaction process AR, may use catalyst ARC；

6. other effective means.

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

2. catalyst granules；

3. iron rust particle；

4. particles of inorganic material；

5. coking of coal process produce into the solid particle in coal tar；

7. the solid particle from shale；

8. the solid particle from oil-sand；

1. suspension bed, that is, slurry bed system；

2. ebullated bed；

3. slight expanded-bed.

The present invention, each conversion zone mode of operation 1 can be：

The present invention, each conversion zone mode of operation 2 can be：

The present invention, each conversion zone mode of operation 3 can be：

The present invention, each conversion zone mode of operation 4 can be：

The present invention, each conversion zone mode of operation 5 can be：

Suspended-bed reactor of the present invention, its structure type can be any one suitable forms, can be empty cylinder Suspended-bed reactor can be so as to shape using internal circulation guide shell so as to form piston flow or the back-mixing stream there are interior circulation Circulation or internal outside circulation in into inside, can be collected using top product liquid with flow guide system so as to be pressurizeed by circulating System forms the back-mixing flow pattern for forcing inner recirculation flow.

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 reaction process 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.The 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 dimethyl disulfide 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, hydrogenation reaction effluent is separated into one in volume into high pressure hot separator at this time On the hot gas separated by high pressure separator gas that is mainly made of hydrogen and one be mainly made of conventional liq hydrocarbon and solid that may be present Hot high score 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, since a large amount of high boiling components enter in hot high score fluid body, realizes 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 be undergone to avoid hot gas separated by high pressure separator 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, usually 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 usually 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 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 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 the ammonia and hydrogen sulfide absorbed in hydrogenation reaction effluent, prevents that to form sulphur hydrogenation ammonia or more sulphur ammonia Crystallization Pluggings changes Hot device passage, increases system pressure drop.The injection rate of the washings, should determine 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, reduces catalyst activity, and the ammonia volumetric concentration of usual gas separated by high pressure separator is more low better, is generally no greater than 200PPm (v), preferably less In 50PPm (v).The cold high pressure separator operating pressure subtracts actual pressure drop, cold anticyclone for hydrogenation reaction partial pressure The difference of separate section operating pressure and hydrogenation reaction pressure, unsuitable too low or excessive, generally 0.35~3.2MPa, be usually 0.5~1.5MPa.The hydrogen volume concentration value of the 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 is returned 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, for this reason, according to Specific feedstock property, reaction condition, product distribution, can exclude a part of cold gas separated by high pressure separator to exclude the first that reaction produces 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 recycling 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, generally 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.

In general, in order to manufacture most rational hydrogen partial pressure, new hydrogen preferentially enters secondary hydrogenation reaction process BR and three Section hydrogenation process CR, remaining new hydrogen enter one-stage hydrogenation reaction process AR.

In general, the air lift hydrogen that one section of one section of thermal high separation process S1 is used, uses circulating hydrogen.

In general, in order to manufacture the active hydrogen condition of quick offer, will be mainly by normal boiling point higher than 300 DEG C or higher than 330 DEG C The hydrogen-containing hydrocarbon stream of the hydrocarbon component composition introduces secondary hydrogenation reaction process BR and/or three sections of hydrogenation process CR.

Embodiment

Embodiment one

Coal tar suspension bed hydrocracking process, one-stage hydrogenation process are common process, use the setting of 2 serial operations The floating bed hydrogenation reactor of liquid collecting cup and itself fluid circulation system, the operation of the second floating bed hydrogenation reactor product ARP Pressure is 20.0MPa, operation temperature is 455 DEG C, and the hydrogen volume concentration of the balance gas phase ARP-V of ARP is 70.0%, gas phase hydrogen Gas partial pressure value 14.0MPa.

Using secondary hydrogenation method of the present invention, a hydrogenation step, one section of second floating bed hydrogenation reactor A R2 row are added The product ARP gone out is used as second stage reactor top hydrogenating materials.

Two section of first hydrogenation reactor BR1, sets liquid collecting cup BR1LD, liquid phase delivery line BR1LK, liquid pressing pump BR1- 9C；In the headroom of BR1, one-stage hydrogenation reaction product ARP and BR1E intermediate product BR1E-8P, are arranged on liquid collecting cup top Mixed zone with logistics distributor BR1MG mix, liquid zone domain is taken off at top and separates phegma BR1EP-LR and product BR1P, flow back Liquid BR1EP-LR is conveyed after liquid collecting cup BR1LD, catheter BR1LK, liquid pressing pump BR19C pressurizations through pipeline 209, is used as BR1 recycle oils BR1-LR returns to BR1 reaction compartments；Recycle oil BR1-LR quantity is one-stage hydrogenation reaction product ARP balance liquid phases 6~7 times of amount, can make one-stage hydrogenation reaction product ARP balance amount of liquid phase enters collection liquid circulation hydrogenation more than 70% share.

Secondary hydrogenation raw material BR1FL, mixes with new hydrogen and carries out deep hydrogenation thermal cracking, hydrogen-oil ratio 700, its reactor enters Implication phase hydrogen volume concentration is about 90~91%, and vapor phase hydrogen partial pressure value is up to 18.1MPa, is higher by the gas phase hydrogen of product ARP Gas partial pressure value reaches 4.1MPa, this is surprising mutability effect.

Embodiment two

Based on embodiment one, recycle oil BR1-LR quantity is 8~9 times of one-stage hydrogenation reaction product ARP balance amount of liquid phase, Can make one-stage hydrogenation reaction product ARP balance amount of liquid phase enters collection liquid circulation hydrogenation more than 80% share.

Embodiment three

Based on embodiment two, in secondary hydrogenation reaction process BR, using being mainly higher than 330 DEG C of the hydrocarbon component groups by normal boiling point Into hydrogen-containing hydrocarbon stream, mixed with secondary hydrogenation raw material BR1F, the Mixing ratio by weight example of hydrogen-containing hydrocarbon stream and hydrogenating materials BR1F For 0.35: 1.

Example IV

Coal Liquefaction process, one section of coal liquefaction are conventional coal liquefaction craft, use the setting collection of 2 serial operations The floating bed hydrogenation reactor of liquid cup and itself fluid circulation system, the operation pressure of the second floating bed hydrogenation reactor product ARP Power is 20.0MPa, operation temperature is 455 DEG C, and the hydrogen volume concentration of the balance gas phase ARP-V of ARP is 70.0%, vapor phase hydrogen Partial pressure value 14.0MPa.

Using secondary hydrogenation method of the present invention, a hydrogenation step, one section of second floating bed hydrogenation reactor A R2 row are added The collection liquid AR2P-L gone out, after pump pressurizes, first via AR2P-L adds as AR2 recycle oils, the second road AR2P-L as two sections Hydrogen feedstock BR1FL is used, secondary hydrogenation raw material BR1FL quantity, the top of equivalent to one section second floating bed hydrogenation reactor A R2 The 70~85% of the balance amount of liquid phase of net product AR2-UP-PU, the present embodiment considers by 70%.

Secondary hydrogenation raw material BR1FL, mixes with new hydrogen and carries out deep hydrogenation thermal cracking, hydrogen-oil ratio 700, its reactor enters Implication phase hydrogen volume concentration is 90.5%, and vapor phase hydrogen partial pressure value is up to 18.1MPa, is higher by the vapor phase hydrogen point of product ARP Pressure value reaches 4.1MPa, this is surprising mutability effect.

Embodiment five

Based on example IV, in secondary hydrogenation reaction process BR, using being mainly higher than 330 DEG C of the hydrocarbon component groups by normal boiling point Into hydrogen-containing hydrocarbon stream, mixed with secondary hydrogenation raw material BR1F, the Mixing ratio by weight example of hydrogen-containing hydrocarbon stream and hydrogenating materials BR1F For 0.35: 1.

Claims

1. the hydrocarbon material of back segment upper feeding back-mixing stream expanded bed reactor formula is like secondary hydrogenation method, it is characterised in that includes following step Suddenly：

(1) in one-stage hydrogenation reaction process AR, there are hydrogen, hydrocarbon liquid phase, there may be the mixed phase material bar of solid particle at the same time Under part, it is anti-that the first raw material A R1F at least containing carbon and protium enters one-stage hydrogenation reaction process AR progress one-stage hydrogenations Answer ARR to obtain one-stage hydrogenation reaction product BASE-ARP, discharge one-stage hydrogenation reaction effluent ARP-X, discharge one-stage hydrogenation is anti- Answer the net product ARP of process；

One-stage hydrogenation reacts ARR, includes the hydrofining reaction of at least a portion liquid material AR1FL, may include at least one The hydrocracking reaction of operative liquid raw material A R1FL, may include adding at least a portion solid material AR1FS that may be present Hydrogen heat cracking reaction；

One-stage hydrogenation reaction process AR, may use catalyst ARC；

One-stage hydrogenation reaction product BASE-ARP, for mixed phase material that at the same time may be containing solid particle containing hydrogen, hydrocarbon liquid phase；

Material based on one-stage hydrogenation reaction product BASE-ARP is used as one-stage hydrogenation reaction effluent ARP-X, and one-stage hydrogenation is anti- Answer effluent ARP-X, occur in the form of 1 tunnel or 2 tunnels or multichannel material, one-stage hydrogenation reaction effluent ARP-X for gas phase or Liquid phase or gas-liquid mixed phase or gas-liquid-solid three-phase logistics；

(2) in secondary hydrogenation reaction process BR, there are hydrogen, hydrocarbon liquid phase, there may be the mixed phase material bar of solid particle at the same time Under part, secondary hydrogenation raw material BR1FM and hydrogen-rich stream BR1FH enter secondary hydrogenation reaction process BR and carry out secondary hydrogenation reaction BRR obtains secondary hydrogenation reaction product BASE-BRP, discharges secondary hydrogenation reaction effluent BRP-X, discharge secondary hydrogenation reaction Net product BRP；

In the back-mixing stream expanded bed reactor BRXE of secondary hydrogenation reaction process BR, one-stage hydrogenation reaction product ARP and BRXE Intermediate product BRXE-8P is blended in the de- liquid zone domain in top and separates phegma BRXEP-LR and gassiness material product BRXEP-M, It is BRXE-8P that the BR upstreams hydroconversion reaction zone of BRXEP-LR returns BRXE-8P, which starts the cycle over hydro-conversion,；

In the main body reaction compartment of secondary hydrogenation reaction process BR, balance of the vapor phase hydrogen volumetric concentration higher than one section of product ARP The hydrogen volume concentration of gas phase ARP-V, balance gas phase ARP-V of the gaseous impurities volume components concentration less than one section of product ARP Impurity composition volumetric concentration；

In secondary hydrogenation reaction process BR, balance liquid phase ARP-L of the high boiling hydrocarbon weight concentration higher than one section of product ARP of liquid phase High boiling hydrocarbon weight concentration, the low boiling of the low boiling hydrocarbon weight concentration of liquid phase less than the balance liquid phase ARP-L of one section of product ARP Point hydrocarbon weight concentration；

When solid particle is carried in secondary hydrogenation reaction process BR, in liquid phase, the weight ratio for the solid particulate matter that liquid phase carries is high In the weight ratio for the solid particulate matter that the balance liquid phase ARP-L of one section of product ARP is carried；

2. secondary hydrogenation method according to claim 1, it is characterised in that：

(2) in secondary hydrogenation reaction process BR, the working method of back-mixing stream expanded bed reactor BRXE is selected from a kind of following manner Or several combination：

3. setting liquid collecting cup BR1LD, liquid phase delivery line BR1LK, liquid pressing pump BR1-9C, add for one section in liquid collecting cup lower disposed The logistics distributor BR1MG of the net product ARP of hydrogen reaction process；

4. setting liquid collecting cup BR1LD, liquid phase delivery line BR1LK, liquid pressing pump BR1-9C, arrange that one section adds on liquid collecting cup top The logistics distributor BR1MG of the net product ARP of hydrogen reaction process；

5. using the external circulation pipe of reactor B RXE, form reactor B RXE tops reaction zone liquid phase and flow down Returning reactor The device outside circulation of BRXE lower reaction zones；

6. other effective means.

3. secondary hydrogenation method according to claim 1, it is characterised in that：

(3) recovery section of net product BRP is reacted in secondary hydrogenation, three sections of hydrogenation process CR are set；

In three sections of hydrogenation process CR, there are hydrogen, hydrocarbon liquid phase, there may be the mixed phase material condition of solid particle at the same time Under, three sections of hydrogenating materials CR1FM and hydrogen-rich stream CR1FH enter three sections of hydrogenation process CR and carry out three sections of hydrogenation reactions CRR obtains three sections of hydrogenation reaction product BASE-CRP, discharges three sections of hydrogenation reaction effluent CRP-X, discharges three sections of hydrogenation reactions Net product CRP；

In the back-mixing stream expanded bed reactor CRXE of three sections of hydrogenation process CR, secondary hydrogenation reaction product BRP and CRXE Intermediate product CRXE-8P is blended in the de- liquid zone domain in top and separates phegma CRXEP-LR and gassiness material product CRXEP-M, It is CRXE-8P that the CR upstreams hydroconversion reaction zone of CRXEP-LR returns CRXE-8P, which starts the cycle over hydro-conversion,；

In the main body reaction compartment of three sections of hydrogenation process CR, balance of the vapor phase hydrogen volumetric concentration higher than two sections of product BRP The hydrogen volume concentration of gas phase BRP-V, balance gas phase BRP-V of the gaseous impurities volume components concentration less than two sections of product BRP Impurity composition volumetric concentration；

In three sections of hydrogenation process CR, balance liquid phase BRP-L of the high boiling hydrocarbon weight concentration higher than two sections of product BRP of liquid phase High boiling hydrocarbon weight concentration, the low boiling of the low boiling hydrocarbon weight concentration of liquid phase less than the balance liquid phase BRP-L of two sections of product BRP Point hydrocarbon weight concentration；

When solid particle is carried in three sections of hydrogenation process CR, in liquid phase, the weight ratio for the solid particulate matter that liquid phase carries is high In the weight ratio for the solid particulate matter that the balance liquid phase BRP-L of two sections of product BRP is carried；

4. secondary hydrogenation method according to claim 3, it is characterised in that：

(2) in three sections of hydrogenation process CR, the working method of back-mixing stream expanded bed reactor CRXE is selected from a kind of following manner Or several combination：

3. setting liquid collecting cup CR1LD, liquid phase delivery line CR1LK, liquid pressing pump CR1-9C, add for two sections in liquid collecting cup lower disposed The logistics distributor CR1MG of the net product BRP of hydrogen reaction process；

4. setting liquid collecting cup CR1LD, liquid phase delivery line CR1LK, liquid pressing pump CR1-9C, arrange that two sections add on liquid collecting cup top The logistics distributor CR1MG of the net product BRP of hydrogen reaction process；

5. using the external circulation pipe of reactor CRXE, form reactor CRXE tops reaction zone liquid phase and flow down Returning reactor The device outside circulation of CRXE lower reaction zones；

6. other effective means.

5. secondary hydrogenation method according to claim 1, it is characterised in that：

(2) in secondary hydrogenation reaction process BR, the hydrocarbonaceous liquid stream of at least a portion secondary hydrogenation reaction process BR discharges, is returned Return in the hydrogenation reaction space of one-stage hydrogenation reaction process AR, be mixed with the first raw material A R1F or in-between products.

6. secondary hydrogenation method according to claim 1, it is characterised in that：

(2) in three sections of hydrogenation process CR, the hydrocarbonaceous liquid stream of three sections of hydrogenation process CR discharges of at least a portion, is returned Return in the hydrogenation reaction space of secondary hydrogenation reaction process BR.

7. secondary hydrogenation method according to claim 1, it is characterised in that：

(2) in three sections of hydrogenation process CR, the hydrocarbonaceous liquid stream of three sections of hydrogenation process CR discharges of at least a portion, is returned Return in the hydrogenation reaction space of one-stage hydrogenation reaction process AR, be mixed with the first raw material A R1F or in-between products.

8. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) one-stage hydrogenation reaction process AR, 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 for including the use of hydrogen supply dissolvent oil is straight Connect liquefaction liquefaction process, coal refines process to oil 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.

9. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) in one-stage hydrogenation reaction process AR, a kind or several in following of existing solid particle：

2. catalyst granules；

3. iron rust particle；

4. particles of inorganic material；

5. coking of coal process produce into the solid particle in coal tar；

7. the solid particle from shale；

8. the solid particle from oil-sand；

10. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

The expanded bed reactor, a kind or several of combination of the mode of operation in following：

1. suspension bed, that is, slurry bed system；

2. ebullated bed；

3. slight expanded-bed.

11. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(2) normal boiling point is higher than 330 DEG C of hydrocarbon group in total the hydrocarbon component in secondary hydrogenation reaction process BR, the liquid phase of reaction compartment The weight concentration divided is more than 60%, and hydrogen volume concentration is more than 80% in the gas phase of reaction compartment.

12. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(2) normal boiling point is higher than 330 DEG C of hydrocarbon group in total the hydrocarbon component in secondary hydrogenation reaction process BR, the liquid phase of reaction compartment The weight concentration divided is more than 70%, and hydrogen volume concentration is more than 85% in the gas phase of reaction compartment.

13. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(2) normal boiling point is higher than 330 DEG C of hydrocarbon group in total the hydrocarbon component in secondary hydrogenation reaction process BR, the liquid phase of reaction compartment The weight concentration divided is more than 80%, and hydrogen volume concentration is more than 90% in the gas phase of reaction compartment.

14. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) one-stage hydrogenation reaction process AR, using floating bed hydrogenation reactor, operating condition is：Reaction temperature is 320~450 DEG C, 0.2~5.0h of volume space velocity of 6~30MPa of reaction pressure, reaction compartment^-1, hydrogen to oil volume ratio 100~3000；

(2) secondary hydrogenation reaction process BR, using floating bed hydrogenation reactor, operating condition is：Reaction temperature is 400~480 DEG C, 0.2~5.0h of volume space velocity of 6~30MPa of reaction pressure, reaction compartment^-1, hydrogen to oil volume ratio 100~3000.

15. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) one-stage hydrogenation reaction process AR, using floating bed hydrogenation reactor, operating condition is：Reaction temperature is 360~440 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；

(2) secondary hydrogenation reaction process BR, using floating bed hydrogenation reactor, operating condition is：Reaction temperature is 420~460 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.

16. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) one-stage hydrogenation reaction process AR, using boiling bed hydrogenation reactor, operating condition is：Reaction temperature is 320~450 DEG C, 0.2~5.0h of volume space velocity of 6~30MPa of reaction pressure, reaction compartment^-1, hydrogen to oil volume ratio 100~3000；

(2) secondary hydrogenation reaction process BR, using boiling bed hydrogenation reactor, operating condition is：Reaction temperature is 400~480 DEG C, 0.2~5.0h of volume space velocity of 6~30MPa of reaction pressure, reaction compartment^-1, hydrogen to oil volume ratio 100~3000.

17. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) one-stage hydrogenation reaction process AR, using boiling bed hydrogenation reactor, operating condition is：Reaction temperature is 360~440 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；

(2) secondary hydrogenation reaction process BR, using boiling bed hydrogenation reactor, operating condition is：Reaction temperature is 420~460 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.

18. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) in oily hydrogenation process, in one-stage hydrogenation reaction process AR, the first raw material A R1F is from coal tar and mainly by routinely boiling Higher than 400 DEG C the hydrocarbon component HD of point are formed, and the Unit Weight hydrogen consumption of the first raw material A R1F is 0.05~7.0%；

(2) secondary hydrogenation reaction process BR, chemical hydrogen consumption amount to the Unit Weight hydrogen consumption of the first raw material A R1F for 0.05~ 3.0%.

19. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) in Coal Liquefaction process, in one-stage hydrogenation reaction process AR, the first raw material A R1F is that coal dust AR1FS and hydrogen supply are molten The Unit Weight hydrogen consumption of agent AR1FL, coal dust AR1FS are 2.5~10.0%；

(2) secondary hydrogenation reaction process BR, chemical hydrogen consumption amount are 0.05~3.0% to the Unit Weight hydrogen consumption of coal dust AR1FS.

20. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) coal tar is come from one-stage hydrogenation reaction process AR, the first raw material A R1F；The hydrogenation catalyst ARC used, is a kind of Compound coal tar hydrogenation catalyst, includes high-activity component and low activity component；The high-activity component metal and low activity The weight ratio of component metals is 1: 10 to 10: 1；The high-activity component is the water soluble salt compound or its mixture of molybdenum； The low activity component is ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, catalyst ARC Water content is less than 2wt%；ARC particle diameters are 1~100 μm of powdered granule.

21. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) coal tar is come from one-stage hydrogenation reaction process AR, the first raw material A R1F；The hydrogenation catalyst ARC used, is at least wrapped Element containing Mo, Mo are M in the body of work form of one-stage hydrogenation reaction process AR₀S₂In, hydrogenation catalyst ARC is 1~100 μm Powdered granule.

22. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) first raw material A R1F comes from coal tar, and the operating condition of one-stage hydrogenation reaction process AR is：Temperature is 320~450 DEG C, pressure be 6.0~30.0MPa, hydrogen to oil volume ratio is 100~3000, hydrogenation catalyst ARC add weight be raw material A R1F weight Amount 0.001~8.0%, reaction compartment volume space velocity be 0.1~10.0hr^-1；The weight chemistry hydrogen consumption of first raw material A R1F For 0.05~7.0%；

23. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) first raw material A R1F comes from coal tar, and the operating condition of one-stage hydrogenation reaction process AR is：Temperature is 360~440 DEG C, pressure be 12.0~25.0MPa, hydrogen to oil volume ratio is 300~1500, hydrogenation catalyst ARC add weight be raw material A R1F Weight 0.5~5.0%, reaction compartment volume space velocity be 0.2~5.0hr^-1；The weight chemistry hydrogen consumption of first raw material A R1F is 0.5~5.5%；

(2) secondary hydrogenation reaction process BR, operating condition are：Reaction temperature is 420~460 DEG C, reaction pressure be 12.0~ 0.2~5.0h of volume space velocity of 25.0MPa, reaction compartment^-1, hydrogen to oil volume ratio 300~1500, chemical hydrogen consumption amount is to the first raw material The Unit Weight hydrogen consumption of AR1F is 0.3~2.0%.

24. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

The hydrogenation process of first raw material A R1F, uses hydrogen supply hydrocarbon material.

25. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

First raw material A R1F includes hydrogen supply hydrocarbon material.

26. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(2) in secondary hydrogenation reaction process BR, will mainly be drawn by normal boiling point higher than the hydrogen-containing hydrocarbon stream that 300 DEG C of the hydrocarbon components form Enter the reaction compartment of secondary hydrogenation reaction process BR, mixing is contacted with secondary hydrogenation raw material BR1FL or its hydrogenation intermediate product.

27. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(3) in three sections of hydrogenation process CR, will mainly be drawn by normal boiling point higher than the hydrogen-containing hydrocarbon stream that 350 DEG C of the hydrocarbon components form Enter the reaction compartment of three sections of hydrogenation process CR, mixing is contacted with three sections of hydrogenating materials CR1FL or its hydrogenation intermediate product.

28. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(2) new hydrogen is come from secondary hydrogenation reaction process BR, at least a portion hydrogen-rich stream BR1FH.

29. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

30. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) coal tar is come from oily hydrogenation process, the first raw material A R1F, in one-stage hydrogenation reaction process AR, is added using 1~3 Hydrogen reactor；

31. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) fine coal and hydrocarbon ils are included, in one-stage hydrogenation reaction process AR, uses 2 in Coal Liquefaction process, the first raw material A R1F ~3 hydrogenation reactors；

32. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(2) it is anti-in secondary hydrogenation reaction process BR, the deep hydrofinishing for being substantially carried out the oily high boiling component of one-stage hydrogenation generation Should.

33. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(2) in secondary hydrogenation reaction process BR, it is substantially carried out the hydrocracking reaction that one-stage hydrogenation generates oily high boiling component.

34. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) in oily hydrogenation process, in one-stage hydrogenation reaction process AR, it is substantially carried out hydrofining reaction and either shallow is hydrocracked instead Should；

(2) it is anti-in secondary hydrogenation reaction process BR, the overhydrocracking for being substantially carried out the oily high boiling component of one-stage hydrogenation generation Should.

35. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) in oily hydrogenation process, in one-stage hydrogenation reaction process AR, hydrofining reaction and hydrocracking reaction are substantially carried out；

(2) in secondary hydrogenation reaction process BR, be substantially carried out the oily high boiling component of one-stage hydrogenation generation hydrofining reaction and Overhydrocracking is reacted.

36. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(1) in Coal Liquefaction process, in one-stage hydrogenation reaction process AR, carry out the pyrolytic reaction of coal, hydrocracking reaction, from Reacted by base stabilized hydrogenation；

(2) reacted, certainly in secondary hydrogenation reaction process BR, the overhydrocracking for carrying out one-stage hydrogenation product high boiling component Reacted by base stabilized hydrogenation.

37. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(2) it is more than 90% in secondary hydrogenation reaction process BR, the hydrogen volume concentration of hydrogen-rich stream BR1FH.

38. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(2) it is more than 95% in secondary hydrogenation reaction process BR, the hydrogen volume concentration of hydrogen-rich stream BR1FH.

39. according to the secondary hydrogenation method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7, it is characterised in that：

(2) it is more than 99% in secondary hydrogenation reaction process BR, the hydrogen volume concentration of hydrogen-rich stream BR1FH.

40. secondary hydrogenation method according to claim 3, it is characterised in that：

(3) it is more than 90% in three sections of hydrogenation process CR, the hydrogen volume concentration of hydrogen-rich stream CR1FH.

41. secondary hydrogenation method according to claim 3, it is characterised in that：

(3) it is more than 95% in three sections of hydrogenation process CR, the hydrogen volume concentration of hydrogen-rich stream CR1FH.

42. secondary hydrogenation method according to claim 3, it is characterised in that：

(3) it is more than 99% in three sections of hydrogenation process CR, the hydrogen volume concentration of hydrogen-rich stream CR1FH.