CN107916138A

CN107916138A - A kind of hydrocarbon material secondary hydrogenation method with expanded bed reactor and single hot high score device

Info

Publication number: CN107916138A
Application number: CN201610899944.6A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
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

A kind of hydrocarbon material secondary hydrogenation method with expanded bed reactor and single hot high score device, hydrocarbon material one-stage hydrogenation reaction product ARP enters the liquid S1L that one section of thermal high separation process S1 is separated into gas S1V and may be containing solid, at least a portion S1L is blended in BR progress secondary hydrogenation reactions BRR as secondary hydrogenation process BR liquid charging stocks and high-purity hydrogen and is converted into product BRP, high selectivity, quick progress target hydrogenation reaction, can significantly inhibit thermal condensation reaction and secondary cracking reaction among the liquid phase of hydrogen rich gas, the gas phase of poor impurity and rich high boiling hydrocarbon；The gas of BRP can carry out air lift to the liquid phase of ARP in S1；The liquid of BR reactors discharge can return to S1 combined recoveries in the product CRP of three sections of hydrogenation process CR；Backend hydrogenation product can return to upstream difference hydrogenation process and form a variety of circulation process；Backend hydrogenation process preferably uses higher boiling hydrogen supply hydrocarbon.

Description

A kind of hydrocarbon material secondary hydrogenation method with expanded bed reactor and single hot high score device

Technical field

A kind of hydrocarbon material secondary hydrogenation method with expanded bed reactor and single hot high score device, hydrocarbon material one-stage hydrogenation reaction The liquid S1L that product ARP is separated into gas S1V and may be containing solid into one section of thermal high separation process S1, at least one Divide S1L to be blended in BR progress secondary hydrogenation reactions BRR as secondary hydrogenation process BR liquid charging stocks and high-purity hydrogen to be converted into Product BRP, high selectivity, quick progress target hydrogenation among the liquid phase of hydrogen rich gas, the gas phase of poor impurity and rich high boiling hydrocarbon Reaction, can significantly inhibit thermal condensation reaction and secondary cracking reaction；The gas of BRP can carry out air lift to the liquid phase of ARP in S1；BR The liquid of reactor discharge can return to S1 combined recoveries in the product CRP of three sections of hydrogenation process CR；On backend hydrogenation product returns A variety of circulation process are formed when swimming different hydrogenation processes；Backend hydrogenation process preferably uses higher boiling hydrogen supply hydrocarbon.

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.

The hydrogenation liquefaction reaction of solid material AR1FS of the present invention, refers to adding for carbon containing, protium solid such as coal Hydrogen produces the reaction of conventional liquid hydrocarbon.

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 circular response liquid in other words；Back-mixing stream or circulation fluid, refer to the intermediate product XK at flow points K Or at least a portion liquid phase XK-L in final product XK is as circulating fluid XK-RL return logistics XK upstream reaction zones, circulation The reaction product of liquid stream XK-RL flows through K points and is present among XK.

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.

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.

Hydrogenation process, coal liquifaction hydrogenation process below in conjunction with middle coalite tar raw material hydrocarbon AR1FL carry out Description.

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 AR1FL that heavy distillat of the normal boiling point of middle coalite tar higher than 350 DEG C forms, because being dripped comprising coal Green grass or young crops, its suitable method of hydrotreating are the hydrogenation process TR using up flow type expanded bed；Hydrogenation process TR can be with Process based on hydrofining reaction is that the hydrocracking reaction of substantial amounts of hydrofining reaction and relatively small amount occurs；Hydrogenation is anti- The process TR of answering 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 hydrogenation for the raw material hydrocarbon AR1FL that heavy distillat of the normal boiling point of either middle coalite tar higher than 350 DEG C forms Thermal cracking process, or coal liquifaction hydrogenation process, the operation scheme of optimization are anti-usually using at least 2 up flow type expanded beds Device is answered, 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, still The 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 Hydrogenation process BR, operation temperature is usually higher, typically up to 410~470 DEG C, generally up to 425~455 DEG C, the reaction temperature It is generally higher compared with the reaction temperature of either shallow hydrogenation process AR to 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 AR1FL, 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 AR1FL 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 AR1FL, Either shallow hydrogenation process AR, can produce substantial amounts of low molecular weight low-boiling point gas component, source is：

1. part organic impurities O, S, N in raw material A R1FL are converted into low-boiling foreign gas component H₂O、H₂S、 NH₃It 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 R1FL is converted into low-boiling gas component CO, CO₂, it is present in gas Xiang Zhong；

3. the side chain of portion of paraffins, cycloalkane in raw material A R1FL or intermediate product, the side chain of aromatic hydrocarbons, cracking fracture Generate 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 A R1FL or intermediate product, the side chain of aromatic hydrocarbons, cracking fracture The more low-boiling naphtha component C of generation₅~NBP200, is present in gas phase in reactor operating condition lower part；NBP200 Represent 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 routine The inclined tetramethyl that hendecane that boiling point is 196 DEG C, the pentamethyl benzofuran that normal boiling point is 196 DEG C, normal boiling point 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 and final product high pressure hot separator between reactor, i.e., will be hot between reactor The hot high score oil of high-pressure separator is introduced into second stage reactor, so that the shortcomings that avoiding foregoing schemes, but increase a set of reaction High pressure hot separator between device, 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：Before using a high pressure hot separator Put, for there is the high boiling point product in the intermediate product of preferable operability or deep hydrogenation product to carry out deep hydrogenation, be Deep hydrogenation reaction process is quick, high selectivity carries out target hydrogenation reaction, it is necessary to effectively optimize thermodynamic condition, i.e., must One or several operating parameter in hydrogen partial pressure, raising catalyst concn, raising liquid phase in high boiling hydrocarbon concentration must be improved Numerical value.

The present invention it is basic contemplate be：A kind of hydrocarbon material secondary hydrogenation side with expanded bed reactor and single hot high score device Method, hydrocarbon material one-stage hydrogenation reaction product ARP are separated into gas S1V into one section of thermal high separation process S1 and may contain solid The liquid S1L of body, at least a portion S1L are blended in BR as secondary hydrogenation process BR liquid charging stocks and high-purity hydrogen and carry out two Section hydrogenation reaction BRR is converted into product BRP, the high selection among the liquid phase of hydrogen rich gas, the gas phase of poor impurity and rich high boiling hydrocarbon Property, it is quick carry out target hydrogenation reaction, thermal condensation reaction and secondary cracking reaction can be significantly inhibited；The gas of BRP can be right in S1 The liquid phase of ARP carries out air lift；The liquid of BR reactors discharge can return to S1 in the product CRP of three sections of hydrogenation process CR and combine back Receive；Backend hydrogenation product forms a variety of circulation process when returning to upstream difference hydrogenation process；Backend hydrogenation process preferably uses Higher boiling hydrogen supply hydrocarbon.

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

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.

When BRP returns to S1 combined recoveries, the gas component such as hydrogen can carry out air lift to the liquid phase of ARP and realize two in BRP Secondary use, high pressure hot separator at this time is a kind of equipment of combination function, and major function has：

It is the gas-liquid separator of reaction product ARP 1. for one-stage hydrogenation reaction process；

It is the air stripper of liquid in reaction product ARP 2. for one-stage hydrogenation reaction process；

It is the feed surge tank of reaction raw materials 3. for secondary hydrogenation reaction process；

It is the gas-liquid separator of reaction product BRP 4. for secondary hydrogenation reaction process；

It is the air stripper of liquid in reaction product BRP 5. for secondary hydrogenation reaction process；

It is the concentrate device of catalyst in reaction process liquid phase feed 6. for secondary hydrogenation reaction process；

It is circulation heat cracking reaction process recycle oil surge tank, its liquid level can 7. for secondary hydrogenation reaction process Expression for the thermal cracking conversion ratio of BR；The change of its liquid level can indicate the adjusting of the operation temperature of BR；

8. for overall hydrogenation process, high pressure hot separator and secondary hydrogenation reaction process BR constitute one section Two sections of selectivity circulation hydrogenation of heavy products are hydrogenated with, that is, constitute the unconverted oil short-circuit cycle flow of reaction process, outside In the range of row's hydrogenation liquid phase product solid thing concentration, the height of pyrocondensation compound concentration limit limits value, it can pursue and realize that the limit adds Hydrogen cracking converts, to reduce the total amount and solids total amount that outer row is hydrogenated with liquid product to greatest extent；It is therefore desirable to hot gas separated by high pressure separator S1 has the function of preferably to take off low boiling component, i.e., with certain separation or fractional distillation functions；With regard to overall hydrogenation process Speech, is a kind of reaction with " reaction-distillation-reaction ", distillation coupling body.

In order to realize the clear separation of low boiling hydrocarbon in ARP, high boiling hydrocarbon, reduce normal boiling point in BR1FL and be less than setting Dedicated air lift hydrogen can be applied in combination to prevent the excessive thermal cracking of low boiling hydrocarbon in the content for the hydrocarbon component that such as 330 DEG C of value Hot logistics, that is, set hydrogen stripping section, then realize further integrating for flow at this time.

One-stage hydrogenation reactor assembly of the present invention, hot high score device, second-stage hydrogenation reactor system, its general effect can be real Existing hydrogenation reaction, the separation of the high pressure of product ARP and BRP, hot high score oil gas carries, the liquid-phase hydrogenatin of unconverted oil selectivity efficient is reacted Etc. multiple functions, its technological effect or aim at：

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

2. realizing the short-circuit cycle of unconverted oil, the number of oil and solid in the product arranged outside hot high score can be greatly lowered Amount, can simplify hot high score oil separation process, and the scale of its separation and/or fractionating section can be greatly lowered, can be significantly Reduce investment and energy consumption；

Because reducing non-targeted heat cracking reaction, therefore unconverted oil systemic circulation can be used to improve liquid than operation scheme Body yield；

3. realizing the short-circuit cycle of unconverted oil, the technique purpose for the net product arranged outside hot high score, which is converted into, discharges useless urge Agent, thermal condensation product, the use for the few efficient hydrogenation catalyst of dosage create condition, can only discharge very small amount at this time Hot high score oil to discharge minimal amount of dead catalyst, thermal condensation product；

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 short-circuit cycle of unconverted oil, " shorten unconverted oil to greatest extent and enter circulation hydrogenation reaction mistake The flowing time there are thermal condensation tendency of the no hydrogen adjoint process of journey ", can effectively reduce pyrocondensation compound production；

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

5. realizing the short-circuit cycle of unconverted oil, the unconverted oil concentration in hot high score oil, Ke Yiyou can be effectively improved Effect improves 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 reaction of one-stage hydrogenation reaction liquid product -- the cascade reaction of overhydrocracking reaction, or carry out coal The cascade reaction of the overhydrocracking reaction of the one-stage hydrogenation reaction liquid product of liquefaction hydrogenation process；

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.

In order to significantly reduce investment outlay, it is necessary to realize the short-circuit cycle of reactive moieties unconverted oil, of the invention expires This requirement of foot, and produce " the secondary use of secondary hydrogenation reaction process hydrogen gas stream " with " can doing things by following nature ", into One step improves the effect for the hydrogen for adding BR reaction process.

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 reactive moieties short-circuit cycle flow of oil is converted, can be to greatest extent " before shortening unconverted oil be recycled into hydrogenation process The time of the flow process there are thermal condensation tendency of no hydrogen adjoint process ", therefore, appearance of the invention is inevitable.

Can be with the other technologies of combination application, such as the step of increase liquid scrubbing gas separated by high pressure separator, the hot high score oil of increase hydrogen air lift De- light component the step of, inject into the net product of hot high score oil the step of flux oil reduces solid concentration, be net to hot high score oil The step of cooling oil reduces its temperature etc. is injected in product.

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 a kind of expanded bed reactor and two sections of the hydrocarbon material of single hot high score device Method of hydrotreating, hydrocarbon material can be oil and/or coal.

Second purpose of the invention is to propose a kind of coal tar secondary hydrogenation side with expanded bed reactor and single hot high score device Method.

3rd purpose of the invention is to propose a kind of coal liquefaction secondary hydrogenation side with expanded bed reactor and single hot high score device Method.

4th purpose of the invention is to propose a kind of hydrocarbon material secondary hydrogenation side with expanded bed reactor and single hot high score device Method, each reaction process use hydrogen supply hydrocarbon.

5th purpose of the invention is to propose a kind of hydrocarbon material secondary hydrogenation side with expanded bed reactor and single hot high score device Method, back segment reaction product return to upstream difference hydrogenation process and form a variety of circulation process.

6th purpose of the invention is to propose a kind of hydrocarbon material secondary hydrogenation side with expanded bed reactor and single hot high score device Method, proposes the organization plan of its supporting high pressure hot separator.

The content of the invention

A kind of hydrocarbon material secondary hydrogenation method with expanded bed reactor and single hot high score device of the present invention, 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 liquefaction 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 one-stage hydrogenation reaction process AR, the hydrogenation reactor used is up flow type expanded bed hydrogenation reactor, is used At least 1 hydrogenation reactor；

(2) in one section of thermal high separate section S1, at least a portion one-stage hydrogenation reaction product ARP and at least one are separated Point flow B RP-KS from step (4), obtains one section of hot gas separated by high pressure separator S1V gas and may the liquid material containing solid particle S1L；

S1 at least discharges 2 road liquid material XL, the 1st road liquid containing the liquid hydrocarbon from one-stage hydrogenation reaction product ARP Body material XL1 is used as the net product X L-P of liquid as secondary hydrogenation raw material BR1F, the 2nd road liquid material XL；

Gas ARP-V and liquid A RP-L are separated into S1, the net product ARP of one-stage hydrogenation reaction process；

Gas stream BRP-KS-V and liquid stream BRP-KS-L are separated into S1, flow B RP-KS；

Liquid of at least a portion from the net product ARP of one-stage hydrogenation reaction process, makes as secondary hydrogenation raw material BR1F With；

There may be liquid of the part from flow B RP-KS, is recycled as secondary hydrogenation raw material BR1F；

(3) 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, one section of hot high score oil S1L of at least a portion enters two as secondary hydrogenation raw material BR1F and hydrogen-rich stream BR1FH Section hydrogenation process BR carries out secondary hydrogenation reaction BRR and obtains secondary hydrogenation reaction product BASE-BRP, discharges secondary hydrogenation Reaction effluent BRP-X, discharge secondary hydrogenation react net product BRP；

In secondary hydrogenation reaction process BR, the hydrogenation reactor used is up flow type expanded bed hydrogenation reactor, is used At least 1 hydrogenation reactor；

In secondary hydrogenation reaction process BR, the volumetric concentration of hydrogen is higher than in net product ARP balance gas phases ARP-V in gas phase Hydrogen volumetric concentration, the volumetric concentration of impurity composition is less than the impurity group in net product ARP balance gas phases ARP-V in gas phase The volumetric concentration divided；

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

When solid particle is carried in secondary hydrogenation reaction process BR, in liquid phase, the weight of the solid particulate matter carried in liquid phase Ratio is measured, higher than the weight ratio of the net product ARP balance liquid phases ARP-L solid particulate matters carried.

(4) the recovery section Z100 of net product BRP is reacted in secondary hydrogenation, two sections at least partially based on step (3) The flow B RP-KS of the net product BRP of hydrogenation reaction enters one section of thermal high separate section S1.

The present invention, usual secondary hydrogenation react net product BRP and return to one section of thermal high separate section S1 combined recovery：

(2) in one section of thermal high separate section S1, one-stage hydrogenation reaction product ARP and the logistics from step (4) are separated BRP-KS, obtain one section of hot gas separated by high pressure separator S1V gas and may be containing solid particle one section of hot high score oil S1L liquid；

One section of hot high score oil S1L is at least divided into 2 tunnels, and the 1st tunnel is used as secondary hydrogenation raw material BR1F, and the 2nd tunnel is used as hot high score Oily net product S1LP, S1LP are used as the net product X L-P of liquid；

(4) the recovery section Z100 of net product BRP is reacted in secondary hydrogenation, the secondary hydrogenation reaction from step (3) is net Product BRP, one section of thermal high separate section S1 is returned as flow B RP-KS.

The present invention, secondary hydrogenation, which reacts one section of thermal high separate section S1 of net product BRP returns, independently to be recycled：

(2) in one section of thermal high separate section S1, one-stage hydrogenation reaction product ARP and the logistics from step (4) are separated BRP-KS；

The net product ARP of one-stage hydrogenation reaction process is separated into gas ARP-V and liquid A RP-L in space DA；

Second-stage reaction product BRP is separated into gas BRP-V and liquid B RP-L in independent gas-liquid separation space DB；Liquid BRP-L points are 2 tunnels, discharge S1 from the liquid phase region of space DB as product BRP-LP all the way, all the way as recycle oil BRP-LR certainly The liquid phase region of space DB, which is discharged into after space DA is mixed with liquid A RP-L, is used as heat of mixing high score oil S1L, and at least a portion is mixed The feedstock hydrocarbon BR1F that hot high score oil S1L is closed as secondary hydrogenation reaction process BR is used；

The present invention, secondary hydrogenation, which reacts net product BRP, can enter the hydrogenation reaction space of one-stage hydrogenation reaction process AR Middle composition circulation process：

(1) in one-stage hydrogenation reaction process AR, the secondary hydrogenation from step (4) reacts net product BRP at least partially, Mixed with the first raw material A R1F or one section hydrogenation reaction intermediate product and carry out hydrogenation reaction；

(2) in one section of thermal high separate section S1, it is high that at least a portion one-stage hydrogenation reaction product ARP is separated into one section of heat Point gas S1V gases and may the hot high score oil liquid material S1L containing solid particle；

At least there are 2 road liquid material S1L, the 1st tunnel is used as secondary hydrogenation raw material BR1F, and it is net that the 2nd tunnel is used as hot high score oil Product S1LP, S1LP are used as the net product X L-P of liquid；

(4) the recovery section Z100 of net product BRP is reacted in secondary hydrogenation, at least a portion secondary hydrogenation reacts net product BRP enters in the hydrogenation reaction space of one-stage hydrogenation reaction process AR.

The present invention, the collection liquid BRX-TL of secondary hydrogenation reaction process can be used as recycle oil BRX-RL to return to secondary hydrogenation Circulation process is formed in the upstream hydrogenation reaction space of the product BRX-UP of reaction process BR：

(3) in secondary hydrogenation reaction process BR, the hydrogenation reactor used is up flow type expanded bed hydrogenation reactor, is made With at least 1 hydrogenation reactor, received wherein the top of a hydrogenation reactor BRX takes off liquid space BRX-TZ using built-in liquid Collection cup LD carries out product and takes off liquid and liquid collection water conservancy diversion acquisition collection liquid BRX-TL and gassiness product BRX-MP；

In the bottom of hydrogenation reactor BRX, reaction feed enters the lower part of expanded bed hydrogenation reactor BRX by feed inlet Reaction zone flows up and passes through central reaction zone and top reaction zone becomes product BRX-UP, and liquid space BRX- is taken off at top TZ, product BRX-UP carry out de- liquid separation, and at least a portion liquid enters in liquid collection cups LD and flowed into along catheter LK For collection liquid BRX-TL, remaining gassiness product BRX-MP is through product diversion pipe discharge reactor B RX；

After the pressurized step PL pressurizations of at least a portion collection liquid BRX-TL secondary hydrogenation is returned to as recycle oil BRX-RL In the upstream hydrogenation reaction space of the product BRX-UP of reaction process BR.

The present invention, may be constructed three sections of hydrogenation flows：

In the bottom of hydrogenation reactor BRX, reaction feed enters the lower part of expanded bed hydrogenation reactor BRX by feed inlet Reaction zone flows up and passes through central reaction zone and top reaction zone becomes product BRX-UP, and liquid space BRX-TZ is taken off at top Region, product BRX-UP carry out de- liquid separation, and at least a portion liquid enters in liquid collection cups LD and flowed along catheter LK As collection liquid BRX-TL, remaining gassiness product BRX-MP is through product diversion pipe discharge reactor B RX；

(4) recovery section of net product BRP is reacted in secondary hydrogenation, at least a portion collection liquid BRX-TL adds as three sections The raw material CR1F and hydrogen-rich stream CR1FH of hydrogen reaction process CR enters three sections of hydrogenation reaction CRR of CR progress and obtains three sections of hydrogenation Reaction product BASE-CRP, discharges three sections of hydrogenation reaction effluent CRP-X, the net product CRP of three sections of hydrogenation reactions of discharge；

The net product CRP of three sections of hydrogenation reactions goes recovery section.

Three sections of hydrogenation flows of the present invention, the net product CRP of three sections of hydrogenation reactions can go three sections of thermal high separate sections CS1：

(4) recovery section of net product BRP is reacted in secondary hydrogenation, using three sections of thermal high separate section CS1, at least one Three sections of the part net product CRP of hydrogenation reaction is separated into three sections of hot gas separated by high pressure separator CS1V gases into three sections of thermal high separate section CS1 With three sections of hot high score oil CS1L liquid that may be containing solid particle.

Three sections of hydrogenation flows of the present invention, the net product CRP of three sections of hydrogenation reactions can enter secondary hydrogenation reaction process BR Any hydrogenation reaction space in：

(2) in one section of thermal high separate section S1, separation one-stage hydrogenation reaction product ARP, two sections from step (4) plus Hydrogen reacts net product BRP, obtain one section of hot gas separated by high pressure separator S1V gas and may be containing solid particle one section of hot high score oil S1L liquid Body；

One section of hot high score oil S1L is at least divided into 2 tunnels, and the 1st tunnel is used as secondary hydrogenation raw material BR1F, and the 2nd tunnel is as hot high score Oily net product S1LP is used；

(4) recovery section of net product BRP is reacted in secondary hydrogenation, secondary hydrogenation reacts net product BRP and goes one section of heat high Press separate section S1；

The net product CRP of three sections of hydrogenation reactions, into any hydrogenation reaction space of secondary hydrogenation reaction process BR.

Three sections of hydrogenation flows of the present invention, the net product CRP of three sections of hydrogenation reactions can remove one section of thermal high separate section S1：

(2) in one section of thermal high separate section S1, separation one-stage hydrogenation reaction product ARP, two sections from step (4) plus Hydrogen reacts net product BRP, the net product CRP of three sections of hydrogenation reactions from step (4), obtain one section of hot gas separated by high pressure separator S1V gas and One section of hot high score oil S1L liquid that may be containing solid particle；

(4) recovery section of net product BRP is reacted in secondary hydrogenation, secondary hydrogenation reacts net product BRP and goes one section of heat high Separate section S1, the net product CRP of three sections of hydrogenation reactions is pressed to remove one section of thermal high separate section S1.

Three sections of hydrogenation flows of the present invention, the flow C RP-KS based on the net product CRP of three sections of hydrogenation reactions remove one-stage hydrogenation In any hydrogenation reaction space of reaction process AR：

(1) in one-stage hydrogenation reaction process AR, the flow C RP-KS at least partially from step (4), with the first raw material AR1F or one section hydrogenation reaction intermediate product mix and carry out hydrogenation reaction；

(2) in one section of thermal high separate section S1, separation one-stage hydrogenation reaction product ARP, the logistics from step (4) BRP-KS, obtain one section of hot gas separated by high pressure separator S1V gas and may be containing solid particle one section of hot high score oil S1L liquid；

(4) recovery section of net product BRP, the secondary hydrogenation at least partially based on step (3) are reacted in secondary hydrogenation The flow B RP-KS for reacting net product BRP enters one section of thermal high separate section S1, at least partially based on three sections of hydrogenation reactions The flow C RP-KS of net product CRP is gone in any hydrogenation reaction space of one-stage hydrogenation reaction process AR.

Structurally and operationally mode is the 1st kind of the high pressure hot separator S1E of the present invention：

(2) in one section of thermal high separate section S1, high pressure hot separator S1E, separation one-stage hydrogenation reaction product ARP are used Net product BRP is reacted with the secondary hydrogenation from step (4), one section of hot gas separated by high pressure separator S1V gas is obtained and solid may be contained One section of hot high score oil S1L liquid of grain；Period, the gas phase air lift one-stage hydrogenation that net product BRP is reacted with secondary hydrogenation reacted Low boiling component in Cheng Jing product ARP liquid phases；

Gas-liquid separation is carried out in the upper space DU of high pressure hot separator S1E, the net product ARP of one-stage hydrogenation reaction process, It is separated into the gas ARP-V flowed up and the liquid phase liquid A RP-L to flow downward；Liquid A RP-L is downward through gas-liquid contact Area Z1, becomes ARP-LD i.e. Z1L processes after carrying out the vaporization flash distillation of liquid phase with the gas BRP-V counter current contactings flowed up herein Central space DM falls into lower space DA, leaves the upward flowing air of bubbling area Z1 and gas ARP-V is mixed into one section of heat Gas separated by high pressure separator S1V gases；

Gas-liquid separation is carried out in the central space DM of high pressure hot separator S1E, second-stage reaction product BRP, is separated into upwards Liquid phase the liquid B RP-L, liquid A RP-L for flowing through the gas BRP-V of bubbling area Z1 and flowing downward fall into lower part sky Between be mixed into one section of hot high score oil S1L liquid with ARP-LD in DA.

Structurally and operationally mode is the 2nd kind of the high pressure hot separator S1E of the present invention：

(2) in one section of thermal high separate section S1, using high pressure hot separator S1E, stripping section Z1 and lower air lift in setting Section Z2, separates one-stage hydrogenation reaction product ARP and the secondary hydrogenation from step (4) reacts net product BRP, and uses air lift hydrogen Gas BH, obtain one section of hot gas separated by high pressure separator S1V gas and may be containing solid particle one section of hot high score oil S1L liquid；In upper air lift Section Z1, the low boiling point in the net product ARP liquid phases of gas phase air lift one-stage hydrogenation reaction process of net product BRP is reacted with secondary hydrogenation Component；In lower stripping section Z2, with secondary hydrogenation of the air lift hydrogen BH air lifts from step (4) react net product BRP liquid phase and Low boiling component in liquid phase from the net product ARP of one-stage hydrogenation reaction process；

Gas-liquid separation is carried out in the upper space DU of high pressure hot separator S1E, the net product ARP of one-stage hydrogenation reaction process, It is separated into the gas ARP-V flowed up and the liquid phase liquid A RP-L to flow downward；Liquid A RP-L is downward through gas-liquid contact Area Z1, becomes upper stripping section discharge liquor after carrying out the vaporization flash distillation of liquid phase with the gas BRP-V counter current contactings flowed up herein Liquid phase liquid A RP-LD, that is, Z1L, leaves the upward flowing air of Z1 and gas ARP-V is mixed into one section of hot gas separated by high pressure separator S1V gas；

Gas-liquid separation is carried out in the central space DM of high pressure hot separator S1E, second-stage reaction product BRP, is separated into upwards Flow through the gas BRP-V and liquid phase the liquid B RP-L, liquid phase liquid B RP-L to flow downward of stripping section Z1 and from upper The liquid Z1L of stripping section is mixed and is downward through lower stripping section Z2, herein with the air lift hydrogen BH counter current contactings that flow up into Become lower stripping section discharge liquor Z2L after the vaporization flash distillation of row low boiling component, Z2L, which is fallen into lower space DA, becomes one section of heat height Divide oil S1L liquid.

Structurally and operationally mode is the 3rd kind of the high pressure hot separator S1E of the present invention：

Gas-liquid separation is carried out in the upper space DU of high pressure hot separator S1E, the net product ARP of one-stage hydrogenation reaction process, It is separated into the gas ARP-V flowed up and the liquid phase liquid A RP-L to flow downward；Liquid A RP-L is downward through gas-liquid contact Area Z1, becomes upper stripping section discharge liquor after carrying out the vaporization flash distillation of liquid phase with the gas BRP-V counter current contactings flowed up herein ARP-LD, that is, Z1L falls falls into lower space DA by central space DM, and the upward flowing air and gas ARP-V for leaving Z1 are mixed into For one section of hot gas separated by high pressure separator S1V gas；

Separated in the central space DM of high pressure hot separator S1E, second-stage reaction product BRP in independent gas-liquid separation space DB For gas BRP-V and liquid B RP-L；Liquid B RP-L points are 2 tunnels, and the first via is as product BRP-LP from the liquid phase region of space DB S1 is discharged, the second tunnel is discharged into after space DA is mixed with liquid Z1L as recycle oil BRP-LR from the liquid phase region of space DB to be made For heat of mixing high score oil S1L.

Structurally and operationally mode is the 4th kind of the high pressure hot separator S1E of the present invention：

(2) in one section of thermal high separate section S1, using high pressure hot separator S1E, stripping section Z1 and lower air lift in setting Section Z2, separates one-stage hydrogenation reaction product ARP and the secondary hydrogenation from step (4) reacts net product BRP, and uses air lift hydrogen Gas BH, obtains one section of hot gas separated by high pressure separator S1V gas, one section of hot high score oil S1L liquid and product BRP- that may be containing solid particle LP；In upper stripping section Z1, the net product ARP liquid of gas phase air lift one-stage hydrogenation reaction process of net product BRP is reacted with secondary hydrogenation Low boiling component in phase；In lower stripping section Z2, net product is reacted with secondary hydrogenation of the air lift hydrogen BH air lifts from step (4) Low boiling component in the liquid phase of BRP and liquid phase from the net product ARP of one-stage hydrogenation reaction process；

Gas-liquid separation is carried out in the upper space DU of high pressure hot separator S1E, the net product ARP of one-stage hydrogenation reaction process, It is separated into the gas ARP-V flowed up and the liquid phase liquid A RP-L to flow downward；Liquid A RP-L is downward through gas-liquid contact Area Z1, becomes upper stripping section discharge liquor after carrying out the vaporization flash distillation of liquid phase with the gas BRP-V counter current contactings flowed up herein ARP-LD, that is, Z1L, leaves the upward flowing air of Z1 and gas ARP-V is mixed into one section of hot gas separated by high pressure separator S1V gas；

Separated in the central space DM of high pressure hot separator S1E, second-stage reaction product BRP in independent gas-liquid separation space DB For gas BRP-V and liquid B RP-L；Liquid B RP-L points are 2 tunnels, and the first via is as product BRP-LP from the liquid phase region of space DB S1 is discharged, the second tunnel is discharged from the liquid phase region of space DB as recycle oil BRP-LR and mixed with the liquid Z1L from upper stripping section And lower stripping section Z2 is downward through, the vaporization for carrying out low boiling component with the air lift hydrogen BH counter current contactings flowed up herein is dodged Become lower stripping section discharge liquor Z2L after steaming, Z2L, which is fallen into lower space DA, is used as heat of mixing high score oil S1L.

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, one-stage hydrogenation reaction process AR, a kind or several that existing solid particle can be in following：

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：

(3) 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：

(3) 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：

(3) 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, in one section of thermal high separate section S1, using high pressure hot separator S1E, can set air lift hydrogen BH Stripping section, air lift hydrogen BH liquid phases of the net product ARP of air lift one-stage hydrogenation reaction process and/or from step (4) in stripping section The net product of hydrogenation reaction liquid phase；

20 DEG C of bodies of the standard state volume flow BH-V of air lift hydrogen BH and the conventional liquid phase hydrocarbon in the first raw material A R1F The ratio of product amount is K900, and K900 is usually 30~3000, generally 300~1000.

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) one sections of thermal high separate section S1, operating condition are：Temperature is 320~450 DEG C, pressure is 6~30MPa；

(3) 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) one sections of thermal high separate section S1, operating condition are：Temperature is 360~440 DEG C, pressure is 12~25MPa；

(3) 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；

(3) 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；

(3) 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%；

(3) 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%；

(3) 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) one sections of thermal high separate section S1, operating condition are：Temperature is 320~450 DEG C, pressure be 6.0~ 30.0MPa；

(3) 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) one sections of thermal high separate section S1, operating condition are：Temperature is 360~440 DEG C, pressure be 12.0~ 25.0MPa；

(3) 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, in one section of thermal high separate section S1, is divided using air lift hydrogen BH air lift one-stage hydrogenation reaction products ARP During the liquid A RP-L separated out, the air lift hydrogen BH used is preferably from circulating 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；

(3) 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；

(3) 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 can be：

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

(3) 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 can be：

(3) 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 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；

(3) 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 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；

(3) 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 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；

(3) it is anti-in secondary hydrogenation reaction process BR, the overhydrocracking for carrying out the oily high boiling component of one-stage hydrogenation generation 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 that the present invention is a kind of with expanded bed reactor and the 1st kind of the hydrocarbon material secondary hydrogenation method of single hot high score device The principle process schematic diagram of technical solution.

As shown in Figure 1, the reaction combined feed AR1TF comprising conventional liquid hydrocarbon, hydrogen enters one-stage hydrogenation reaction process AR, One-stage hydrogenation reaction process AR up flow type expanded bed hydrogenation reactor AR1, AR2 using 2 serial operations is shown in the figure Situation, one section of first hydrogenation reactor AR1, one section of second hydrogenation reactor AR2 can be empty cartridge type suspension bed or set liquid The hydrogenation reactor of phase product recycle system, one-stage hydrogenation reaction product AR2P, that is, ARP enter one section of thermal high point through pipeline 109 One section of hot high score oil that the one section of hot gas separated by high pressure separator S1V gas discharged along pipeline 201 is separated into from part S1 and is discharged along pipeline 202 S1L (containing solid particle) liquid.

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 process AR enters one section of first hydrogenation reactor through road 105 AR1 carries out one section of first hydrogenation reaction and obtains one section of first hydrogenation reaction product AR1P；AR1P enters one section second through road 106 and adds Hydrogen reactor AR2 carries out one section of second hydrogenation reaction and obtains one section of second hydrogenation reaction product AR2P and be used as one section of end reaction Product ARP.

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 The either shallow coal liquefaction hydrogenation reaction such as coal swelling, pyrolysis of coal, hydrogenation, one section of first hydrogenation reactor AR1 can be to set liquid product The floating bed hydrogenation reactor of the circulatory system；One section of second hydrogenation reactor AR2 carries out depth coal liquefaction hydrogenation reaction, one section the Two hydrogenation reactor AR2 are the floating bed hydrogenation reactor for setting the liquid product circulatory system, are contained in reaction product AR2P light 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 thermal high separate section operability, the hydrocarbon group for the recycle oil AR2-RL that one section of second hydrogenation reactor AR2 is produced Divide the high boiling hydrocarbon of matter oil in preferably abjection light oil and at least a portion, to avoid unhelpful the having of light oil, middle matter oil 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 and/or either shallow hydrogenation of coal tar Cracking reaction, one section of first hydrogenation reactor AR1 can be empty cartridge type suspension bed or set the hydrogenation of the liquid product circulatory system anti- Answer device；One section of second hydrogenation reactor AR2 carries out coal tar overhydrocracking reaction, and one section of second hydrogenation reactor AR2 is The floating bed hydrogenation reactor of the liquid product circulatory system is set, contains light oil, middle matter oil and heavy in reaction product AR2P Oil and can not distillation such as catalyst, ash content, semicoke, asphalitine etc., under the premise of thermal high separate section operability is ensured, The hydrocarbon component for the recycle oil AR2-RL that one section of second hydrogenation reactor AR2 is produced preferably deviates from matter in light oil and major part The high boiling hydrocarbon of oil, to avoid unhelpful harmful circulation thermal cracking of light oil, middle matter oil.

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；One section of second hydrogenation reactor AR2 carries out the reaction of coal tar deep refining and/or either shallow hydrogenation Cracking reaction, one section of second hydrogenation reactor AR2 are the floating bed hydrogenation reactor for setting the liquid product circulatory system, and reaction is produced In thing AR2P containing light oil, middle matter oil and mink cell focus and can not distillation such as catalyst, ash content, semicoke, asphalitine etc., protecting Under the premise of demonstrate,proving thermal high separate section operability, the hydrocarbon group for the recycle oil AR2-RL that one section of second hydrogenation reactor AR2 is produced Divide the high boiling hydrocarbon of matter oil in preferably abjection light oil and major part, the inefficient cycle to avoid light oil, middle matter oil adds Hydrogen.

As shown in Figure 1, in secondary hydrogenation reaction process BR, comprising conventional liquid hydrocarbon, hydrogen reaction combined feed BR1TF into Enter secondary hydrogenation reaction process BR, it is anti-using 1 up flow type expansion bed hydroprocessing that secondary hydrogenation reaction process BR is shown in the figure The situation of device BR1 is answered, two section of first hydrogenation reactor BR1 can be empty cartridge type suspension bed or set the liquid product circulatory system Hydrogenation reactor.

As shown in Figure 1, a part of S1L is used through pipeline 2022 as liquid S1LR, at least a portion S1LR is as two sections The feedstock hydrocarbon BR1F of hydrogenation process, after the hydrogen flow B R1FH conveyed with pipeline 302 is mixed, as two section first The combined feed BR1TF of hydrogenation process BR1 enters two section of first hydrogenation reactor BR1 through road 305 and carries out two section of first hydrogenation Reaction obtains two section of first hydrogenation reaction product BR1P.

As shown in Figure 1, a part of S1L is discharged through pipeline 2021 as product S1LP.

As shown in Figure 1, second-stage reaction product BR1P, that is, BRP, enters one section of S1 points of thermal high separate section through pipeline 309 From can so save a high pressure hot separator.

As shown in Figure 1, second-stage reaction product BR1P, that is, BRP, can also enter other processing roads through pipeline 309, pipeline 310 Footpath.

As shown in Figure 1, second-stage reaction product BR1P, that is, BRP and one-stage hydrogenation reaction product AR2P, that is, ARP is in S1 joints point From the gas mixing from BRP and ARP is S1V, and the liquid from BRP and ARP is mixed into S1L；A part of S1L is through pipeline 2021 as product S1LP discharges, and S1LP is the mixture of the liquid from BRP and ARP；A part of S1L is through 2022 conduct of pipeline Liquid S1LR is used, the feedstock hydrocarbon BR1FL that at least a portion S1LR pressurizes as secondary hydrogenation reaction process through pumping PK, with pipe After the hydrogen flow B R1FH mixing that road 302 conveys, the combined feed BR1TF as two section of first hydrogenation process BR1 is through road 305, which enter two section of first hydrogenation reactor BR1 progress, two section of first hydrogenation reaction, obtains two section of first hydrogenation reaction product BR1P； BR1P returns to one section of thermal high separate section S1 through road 309, because material S1LP is the mixture of the liquid from BRP and ARP, Therefore the program is not the secondary hydrogenation process of complete meaning.

Fig. 2 is that the present invention is a kind of with expanded bed reactor and the 2nd kind of the hydrocarbon material secondary hydrogenation method of single hot high score device The principle process schematic diagram of technical solution, with Fig. 1 shows secondary hydrogenation method of the invention the 1st kind of technical solution difference Part is：One-stage hydrogenation reaction product ARP is separated into gas ARP-V and liquid A RP- in the space DA of high pressure hot separator S1 L；In high pressure hot separator S1, set second-stage reaction product BRP independent gas-liquid separation space DB be separated into gas BRP-V and Liquid B RP-L；RP-L points of liquid B is 2 tunnels, discharges S1 through pipeline 290 from the liquid phase region of space DB as product BRP-LP all the way, It is discharged into all the way as recycle oil BRP-LR from the liquid phase region of space DB after space DA is mixed with liquid A RP-L and is used as the heat of mixing High score oil S1L, conveys through pipeline 2022, through pumping PK pressurizations, being conveyed all as secondary hydrogenation reaction process BR's through pipeline 301 Feedstock hydrocarbon BR1FL returns to secondary hydrogenation reaction process BR.

As shown in Fig. 2, product material S1LP, liquid A RP-L that discharging liquid ARP-L can be not present to fully enter two sections Hydrogenation process BR, so as to form the secondary hydrogenation process of complete meaning.

Fig. 3 is that the present invention is a kind of with expanded bed reactor and the 3rd kind of the hydrocarbon material secondary hydrogenation method of single hot high score device The principle process schematic diagram of technical solution, with Fig. 1 shows secondary hydrogenation method of the invention the 1st kind of technical solution difference Part is：Two section of first hydrogenation reactor BR1 of secondary hydrogenation reaction process BR is to set hanging for the liquid product circulatory system Floating bed hydrogenation reactor, is provided with liquid collection cups LD, catheter LK, the liquid B R1-RL of liquid collection cups LD discharges is by leading Liquid pipe LK enters after circulating pump PL pressurizations as two section of first hydrogenation reactor BR1 repeats itselfs oil, through pipeline 3021 and through pipe Enter two section of first hydrogenation reactor BR1 circulation hydrogenation after the raw material BR1F mixing that road 301 conveys.

Fig. 4 is the 4th kind of skill of the secondary hydrogenation method of a kind of hydrocarbon material expanded bed reactor of the invention and hot high score device The principle process schematic diagram of art scheme, comprising one section of reaction process AR, secondary hydrogenation process BR, represents of the invention with Fig. 3 The difference of 3rd kind of technical solution of secondary hydrogenation method is：Secondary hydrogenation reaction product BRP is through pipeline 309, pipeline 3030th, pipeline 3033 enters in the charging of one section of second hydrogenation reactor AR2, forms the part inverted sequence circulation between one section two sections Formula secondary hydrogenation flow；Or enter the charging of one section of first hydrogenation reactor AR1 through pipeline 309, pipeline 3030, pipeline 3032 In, form the circulating secondary hydrogenation flow of the sequence that is all-trans between one section two sections.

Inverted sequence secondary hydrogenation flow shown in Fig. 4, particularly suitable for the transformation of existing apparatus, because secondary hydrogenation reaction production Hydrogen in thing BRP can be little by secondary use, the hydrogen usage amount change of existing apparatus.This scheme is equivalent in routine One-stage hydrogenation reaction process circulating pump discharge recycle oil circulation process in, increase a hydrogenation reaction step.

Fig. 5 is the 1st kind of skill of three sections of method of hydrotreating of a kind of hydrocarbon material expanded bed reactor of the invention and hot high score device The principle process schematic diagram of art scheme, from Fig. 1 shows secondary hydrogenation method of the invention the 1st kind of technical solution it is different it Be in：To set, liquid product takes off liquid to two section of first hydrogenation reactor BR1 of secondary hydrogenation reaction process BR and liquid is collected The floating bed hydrogenation reactor of guiding system, is provided with liquid collection cups LD, catheter LK, the liquid of liquid collection cups LD discharges Feedstock hydrocarbons of the BR1-LXP (part for usually only accounting for liquid phase in whole product BR1P) as three sections of hydrogenation process CR CR1F, after the hydrogen flow C R1FH conveyed with pipeline 402 is mixed, the combined feed CRTF as three sections of hydrogenation process CR Enter three sections of hydrogenation reactor CR progress, three sections of hydrogenation reactions through road 405 and obtain three sections of hydrogenation reaction product CRP；CRP is through road 409 Into three sections of thermal high separate section CS1 or return to one section of thermal high separate section S1 combined separation.

Fig. 6 is the 2nd kind of skill of three sections of method of hydrotreating of a kind of hydrocarbon material expanded bed reactor of the invention and hot high score device The principle process schematic diagram of art scheme, from Fig. 3 represent secondary hydrogenation method of the invention the 3rd kind of technical solution it is different it Be in：The liquid B R1- of the liquid collection cups LD discharges of two section of first hydrogenation reactor BR1 of secondary hydrogenation reaction process BR RL separates the second road liquid and adds through piping 3022, pipeline 401 as three sections after catheter LK enters circulating pump PL pressurizations The feedstock hydrocarbon CR1F of hydrogen reaction process CR, after the hydrogen flow C R1FH conveyed with pipeline 402 is mixed, as three sections of hydrogenation The combined feed CRTF of reaction process CR enters three sections of hydrogenation reactor CR progress, three sections of hydrogenation reactions through road 405 and obtains three sections of hydrogenation Reaction product CRP；CRP returns to one section of thermal high separate section S1 combined separation through road 409.

As shown in fig. 6, secondary hydrogenation reaction product BRP returns to one section of thermal high separate section S1 through road 309.

As shown in fig. 6, three sections of hydrogenation reaction product CRP, can return to second-stage hydrogenation reactor BR1 through road 409, pipeline 410 Interior top reaction compartment.

Being mainly made of high boiling component from secondary hydrogenation reaction process BR and/or three sections of hydrogenation process CR Liquid material, can enter one-stage hydrogenation process AR progress hydrofinishings and such as be hydrogenated with saturation increase hydrogen-carbon ratio, reduce remaining carbon, The circulating deep hydrofinishing of composition high boiling hydrocarbon component-be hydrocracked flow.

Fig. 7 is the 3rd kind of skill of three sections of method of hydrotreating of a kind of hydrocarbon material expanded bed reactor of the invention and hot high score device The principle process schematic diagram of art scheme, comprising one section of reaction process AR, secondary hydrogenation process BR, three sections of hydrogenation process BR, with Fig. 6 The difference of 2nd kind of technical solution of the of the invention three section method of hydrotreating of expression is：Three sections of hydrogenation reaction product CRP warps Cross to pipeline 409, pipeline 4050, pipeline 4051 and enter in the charging of two section of first hydrogenation reactor BR1, form three sections and two sections Between inverted sequence circulation hydrogenation flow；Three sections of hydrogenation reaction product CRP, can be with pipeline 409, pipeline 4050, pipeline 4052, pipeline 4053 enter in the charging of one section of second hydrogenation reactor AR2, form the inverted sequence circulation hydrogenation flow between three sections and one section；Or Person passes through 409, pipeline 4050, pipeline 4052, pipeline 4054 and enters in the charging of one section of first hydrogenation reactor AR1, forms Inverted sequence circulation hydrogenation flow between three sections and one section.

Inverted sequence secondary hydrogenation flow shown in Fig. 7, particularly suitable for the transformation of existing apparatus, because three sections of hydrogenation reaction productions Hydrogen in thing CRP can be little by secondary use, the hydrogen usage amount change of existing apparatus.This scheme is equivalent in routine Circulating pump discharge recycle oil circulation process in, increase a hydrogenation reaction step.

Fig. 8 is the present invention a kind of expanded bed reactor and the joint heat of the hydrocarbon material secondary hydrogenation method of single hot high score device 1st kind of device structure functional schematic of the setting stripping step of high-pressure separator S1, with BRP-V air lifts ARP-L.

As shown in figure 8, one-stage hydrogenation reaction product ARP carries out gas-liquid point in the upper space DU of high pressure hot separator S1 From being separated into the gas ARP-V and liquid A RP-L flowed up, the herringbone of middle epimere be downward through after liquid A RP-L distributions Column plate region Z1, becomes liquid A RP-LD whereabouts after being vaporized flash distillation with the gas BRP-V counter current contactings flowed up herein To lower space DA；First air lift mass transfer section Z1 ascending vapors and ARP-V mixing are used as hot gas separated by high pressure separator S1V.

As shown in figure 8, the middle and lower sections in the high pressure hot separator of thermal high separate section S1, second-stage reaction product BRP It is separated into gas BRP-V and liquid B RP-L；Liquid B RP-L falls to bottom space DA, as mixed after being mixed with liquid A RP-LD Close hot high score oil S1L.

Fig. 9 is the present invention a kind of expanded bed reactor and the joint heat of the hydrocarbon material secondary hydrogenation method of single hot high score device High-pressure separator S1 setting stripping step the 2nd kind of device structure functional schematic, with Fig. 8 shows high pressure hot separator S1 The difference of the 1st kind of device structure be：In addition to BRP-V air lifts ARP-L, added in lower space with BH air lifts The function of the miscella of liquid A RP-LD and BRP-L, has gas stripping twice.

As shown in figure 9, one-stage hydrogenation reaction product ARP carries out gas-liquid point in the upper space DU of high pressure hot separator S1 From being separated into the gas ARP-V and liquid A RP-L flowed up, the backward herringbone column plate region that flowed down of liquid A RP-L distributions Z1, carried out herein with gas (including BRPV and gas from the Z2) counter current contacting flowed up after the vaporization flash distillation of liquid phase into To fall on the second air lift mass transfer section Z2 for being disposed with herringbone column plate under ARP-LD；First air lift mass transfer section Z1 ascending vapors and ARP- V mixing is used as hot gas separated by high pressure separator S1V.

As shown in figure 9, the middle and lower sections in the high pressure hot separator of thermal high separate section S1, second-stage reaction product BRP It is separated into gas BRP-V and liquid B RP-L；The second air lift mass transfer section Z2 is fallen under liquid B RP-L, mixed with liquid A RP-L, with The air lift hydrogen gas stream BH counter current contactings flowed from bottom to top, the liquid for leaving the second stripping section Z2 fall to bottom space DA works For heat of mixing high score oil S1L.

Figure 10 is the present invention a kind of expanded bed reactor and the joint of the hydrocarbon material secondary hydrogenation method of single hot high score device 3rd kind of device structure functional schematic of the setting stripping step of high pressure hot separator S1, setting second-stage reaction product BRP's is only Vertical gas-liquid separation space DB, with BRP-V air lifts ARP-L.

As shown in Figure 10, one-stage hydrogenation reaction product ARP carries out gas-liquid point in the upper space DU of high pressure hot separator S1 From being separated into the gas ARP-V and liquid A RP-L flowed up, the backward herringbone column plate region that flowed down of liquid A RP-L distributions Z1, is vaporized after flash distillation with the gas BRP-V counter current contactings flowed up as lower part sky is fallen under liquid A RP-LD herein Between DA；First air lift mass transfer section Z1 ascending vapors and ARP-V mixing are used as hot gas separated by high pressure separator S1V.

As shown in Figure 10, in the high pressure hot separator of thermal high separate section S1, second-stage reaction product BRP is in independent gas Liquid separated space DB is separated into gas BRP-V and liquid B RP-L；RP-L points of liquid B is 2 tunnels, all the way as product BRP-LP certainly S1 is discharged in the liquid phase region of space DB through pipeline 290, is discharged into sky from the liquid phase region of space DB as recycle oil BRP-LR all the way Between DA mixed with liquid A RP-LD after be used as heat of mixing high score oil S1L.

Figure 11 is the present invention a kind of expanded bed reactor and the joint of the hydrocarbon material secondary hydrogenation method of single hot high score device 4th kind of device structure functional schematic of the setting stripping step of high pressure hot separator S1, the heat of the invention represented with Figure 10 The something in common of the 3rd kind of device structure of high-pressure separator S1 is：In addition to BRP-V air lifts ARP-L, in lower space increase With the function of the miscella of BH air lift liquid As RP-LD and BRP-L, there is gas stripping twice.

As shown in figure 11, one-stage hydrogenation reaction product ARP carries out gas-liquid point in the upper space DU of high pressure hot separator S1 From being separated into the gas ARP-V and liquid A RP-L flowed up, the backward herringbone column plate region that flowed down of liquid A RP-L distributions First air lift mass transfer section Z1, is vaporized with gas (including BRPV and gas from the Z2) counter current contacting flowed up herein Become after flash distillation under liquid A RP-LD and fall on the second air lift mass transfer section Z2 for being disposed with herringbone column plate；On first air lift mass transfer section Z1 Rise gas phase and ARP-V mixing is used as hot gas separated by high pressure separator S1V.

As shown in figure 11, in the high pressure hot separator of thermal high separate section S1, second-stage reaction product BRP is in independent gas Liquid separated space DB is separated into gas BRP-V and liquid B RP-L；RP-L points of liquid B is 2 tunnels, all the way as product BRP-LP certainly S1 is discharged in the liquid phase region of space DB through pipeline 290, is discharged into the from the liquid phase region of space DB as recycle oil BRP-LR all the way Two air lift mass transfer section Z2 are mixed with liquid A RP-LD.

As shown in figure 11, the second stripping section Z2 of the middle and lower sections in the high pressure hot separator of thermal high separate section S1, Recycle oil BRP-LR and liquid A RP-LD, with the air lift hydrogen gas stream BH counter current contactings flowed from bottom to top, leaves the second air lift The liquid of section Z2 falls to bottom space DA as heat of mixing high score oil S1L.

Figure 12 is the present invention a kind of expanded bed reactor and the joint of the hydrocarbon material secondary hydrogenation method of single hot high score device The 5th kind of device structure functional schematic of high pressure hot separator S1, with Fig. 8 shows high pressure hot separator S1 of the invention The something in common of a kind of device structure is：2, high pressure hot separator S1 spaces point area uses, and equivalent to 2 high pressure hot separators are simultaneously Connection operation.

As shown in figure 12, one-stage hydrogenation reaction product ARP carries out gas-liquid separation in the space S 1D1 of high pressure hot separator S1, The gas ARP-V and liquid A RP-L flowed up is separated into, liquid B RP-L enters second-stage hydrogenation reactor BR1 as S1LR In.

As shown in figure 12, secondary hydrogenation reaction product BRP carries out gas-liquid separation in the space S 1D2 of high pressure hot separator S1, The gas BRP-V and liquid B RP-L flowed up is separated into, liquid B RP-L is used as product BRP-LP.

As shown in figure 12, gas ARP-V and gas BRP-V mixing is used as hot gas separated by high pressure separator S1V.

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 ARZE-TL is carried, refers to the solid that collection liquid ARZE-TL is carried The ratio of the weight and the weight of pure liquid phase material of grain thing.

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；

Inventor：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.

Inventor：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；

Inventor：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；

Inventor：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；

Inventor：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；

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 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.

Reference examples

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

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

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

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

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

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

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

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

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

Mixed material slurry oil and hydrogen mix, after heating furnace preheats, and enter first after the mixing of surplus stock hydrogen Floating bed hydrogenation reactor A R1 is converted into the first floating bed hydrogenation reaction product AR1P, the first floating bed hydrogenation reactor A R1 Empty barrel reactor, liquid-phase hydrogenatin reaction include hydrogen supply dissolvent molecule and provide reactive hydrogen to coal tar heavy duty oil molecule or building stone The hydrogen aromatic carbon rate that liquid phase hydrogen transfer reactions, i.e. hydrogen supply dissolvent molecule loses activity improves, coal tar heavy duty oil molecule or building stone knot Closing reactive hydrogen aromatic carbon rate reduces the de- carbon residue reaction of i.e. formation hydrogenation.

First floating bed hydrogenation reactor A R1, operation temperature is relatively low, to suppress thermal condensation reaction, with hydrofining reaction Reacted for main target.

Second floating bed hydrogenation reactor A R2, to set the floating bed hydrogenation of the carrying liqs product circulation of liquid collection cups Reactor, the first floating bed hydrogenation reaction product AR1P are converted into the second floating bed hydrogenation reaction product AR2P in AR2, and circulation adds Work product liquid.Second floating bed hydrogenation reactor A R2, using systemic circulation than backmixing of liquid phase recycle cracking operation mode, circulation Weight of oil is 4~6 to the weight ratio AR2-RLK of fresh feed, and the operating point AR2-RLK values in this example are 5；Second suspension bed The recycle oil of hydrogenation reactor AR2 discharges returns to the first floating bed hydrogenation reactor A R1 entrances.

Second floating bed hydrogenation reactor A R2, operation temperature is higher, anti-as main target using either shallow hydrocracking reaction Should.

3rd floating bed hydrogenation reactor A R3, to set the floating bed hydrogenation of the carrying liqs product circulation of liquid collection cups Reactor, the second floating bed hydrogenation reaction product AR2P are converted into the 3rd floating bed hydrogenation reaction product AR3P in AR3, and circulation adds Work product liquid.3rd floating bed hydrogenation reactor A R3, using systemic circulation than backmixing of liquid phase recycle cracking operation mode, circulation Weight of oil is 4~6 to the weight ratio AR3-RLK of fresh feed, and the operating point AR3-RLK values in this example are 5；3rd suspension bed The recycle oil of hydrogenation reactor AR3 discharges returns to the 3rd floating bed hydrogenation reactor A R1 entrances.

3rd floating bed hydrogenation reactor A R3, operation temperature highest are anti-as main target using overhydrocracking reaction Should.

Suspension bed hydrogenation catalyst used is a kind of compound suspension bed hydrogenation catalyst of molybdenum-iron, and used catalyst includes height Active metal component molybdenum and low activity metal component iron, wherein high-activity component metal molybdenum and the weight of low activity component metals iron Than for 1: 500, catalyst water content is less than 0.5wt%, and particle diameter is 1~100 μm of powdered granule.The catalyst is to contain iron Measure and be ground into powdered granule less than 100 μm for 58wt% bloodstone (main ingredient Fe2O3), then by 10% ammonium molybdate Aqueous solution is equably sprayed on particle, and spray flux is about molybdenum: iron weight ratio be equal to 1: 500, through at 100 DEG C dry 1 it is small when, Obtain the powdered granule catalyst that water content is less than 0.5wt%.

Table 5 is one-stage hydrogenation reaction process AR reaction conditions.

It is conventional in balance gas phase AR3P-V, balance liquid phase AR3P-L that table 6 is the 3rd floating bed hydrogenation reaction product AR3P The quantity and ASTM-D86 data of liquid hydrocarbon.

Balance gas phase AR3P- under material composition and operating condition that table 7 is the 3rd floating bed hydrogenation reaction product AR3P V, the composition of liquid phase AR3P-L is balanced.

Table 8 is reaction product AR3P gas phases composition analysis (the non-row solids of stream components flow rate).

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

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

The cut C analysis data of 3 medium temperature coal tar of table

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

4 medium temperature coal tar distillation fraction yield table of table

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

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

Conventional liquid in balance gas phase AR3P-V, the balance liquid phase AR3P-L of the 3rd floating bed hydrogenation reaction product AR3P of table 6 The quantity and ASTM-D86 data of state hydrocarbon

The 3rd floating bed hydrogenation reaction product AR3P of table 7 material composition and operating condition under balance gas phase AR3P-V, Balance the composition of liquid phase AR3P-L

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

8 reaction product AR3P gas phases composition analysis of table (the non-row solids of stream components flow rate)

	Flow rate value, kg-mol/hr	Molar ratio	Partial pressure value, MPa
				Total flow rate	1015.908	100.00%	21.600
Ingredient names
				H₂O	55.701	5.48%	1.184
H₂S	2.613	0.26%	0.056
				NH₃	13.637	1.34%	0.290
H₂	710.781	69.97%	15.112
				METHANE	70.158	6.91%	1.492
ETHANE	18.987	1.87%	0.404
				PROPANE	7.542	0.74%	0.160
IBUTANE	13.306	1.31%	0.283

Embodiment

Embodiment one

Based on reference examples, in order to improve the selectivity of the deep hydrogenation heat cracking reaction of high boiling component, using the present invention A kind of hydrocarbon material secondary hydrogenation method with expanded bed reactor and single hot high score device, flow is as shown in Figure 1, joint thermal high point 2, device structure such as Figure 12, high pressure hot separator S1 spaces point area from device S1 uses, and equivalent to 2 high pressure hot separators are simultaneously Connection operation.Secondary hydrogenation reaction process BR uses 1 up flow type expanded bed hydrogenation reactor BR1.

One-stage hydrogenation reaction product ARP carries out gas-liquid separation in the space S 1D1 of high pressure hot separator S1, is separated into upwards The gas ARP-V and liquid A RP-L of flowing, liquid B RP-L enter in second-stage hydrogenation reactor BR1 as S1LR.

Secondary hydrogenation reaction product BRP carries out gas-liquid separation in the space S 1D2 of high pressure hot separator S1, is separated into upwards The gas BRP-V and liquid B RP-L of flowing, liquid B RP-L are used as product BRP-LP.Gas ARP-V and gas BRP-V mixing is used Make hot gas separated by high pressure separator S1V.

Second-stage hydrogenation reactor BR1, using new hydrogen as hydrogen-rich stream BR1FH, flow for 12328 standard cubic meters/ When, the ratio with 20 DEG C of 26.7 cubes ms/hour of volume amounts of " coal tar heavy oil, hydrogen supply agent " in fresh feed AR1F is 462。

Table 9 is Balance Air phase composition (the non-row solid of stream components flow rate of second-stage hydrogenation reactor BR1 combined feeds BR1TF Thing).

Table 10 is for second-stage hydrogenation reactor BR1 entrance Balance Air phase compositions and partial pressure and compared with reference examples.

Conventional liquid forms in the balance liquid phase that table 11 is second-stage hydrogenation reactor BR1 combined feeds BR1TF.Can from table 11 To find out, in liquid phase normal boiling point less than 330 DEG C of low boiling hydrocarbon quantity by 12.1 tons/when be reduced to 6.4 tons/when, reduce To about the 53% of reference examples.

Meanwhile balance liquid phase total amount by 28.7 tons/when be reduced to 23.4 tons/when, be reduced to about the 81.5% of reference examples, this The concentration of catalyst has brought up to about the 123% of reference examples in sample liquid phase.

As can be seen from Table 11, in liquid phase normal boiling point higher than 330 DEG C of high boiling hydrocarbon quantity by 16.6 tons/when carry Up to 17.0 tons/when, increase to about the 102% of reference examples；The weight of low boiling hydrocarbon of the normal boiling point higher than 330 DEG C in liquid phase Concentration brings up to 72.5% by 57.8%, and low boiling hydrocarbon is 0.38: 1 with high boiling hydrocarbon weight ratio；Ensureing unconverted oil processing Measure it is constant on the premise of, second-stage reaction charging quantity, which can be reduced to 79.7% i.e. processing capacity of reference examples, to be reduced 20.3%.

Table 12 is the phase state analysis (the non-row solids of stream components flow rate) of second-stage hydrogenation reactor BR1 combined feeds BR1TF

The effect of embodiment one is shown as：

1. secondary hydrogenation reaction entrance Balance Air phase composition significantly improves

As can be seen from Table 9, the density of hydrogen of gas phase is balanced, is increased to 90.62% by 69.97%, hydrogen partial pressure 19.57MPa is increased to by 15.11MPa, amplification 29.53%, that is, be sharply increased 4.46MPa；

Meanwhile steam partial pressure, 0.173MPa is reduced to by 1.184MPa, the range of decrease 85.41%, that is, be greatly reduced 1.011MPa；

Meanwhile ammonia partial pressure, 0.039MPa is reduced to by 0.290MPa, the range of decrease 86.59%, that is, be greatly reduced 0.251MPa；

Meanwhile more than 72%, that is, 1.825MPa is greatly reduced in normally gaseous hydrocarbon partial pressure, the range of decrease；

This three, the low partial pressure 3.087MPa of co-falling, the rising to hydrogen partial pressure, contribution rate 69.2%, this is surprising dashes forward Degenerative effects；

2. secondary hydrogenation cracking process, the excessive heat cracking reaction of low boiling hydrocarbon is greatly lowered, hydrogenation reaction selectivity Improve

Low boiling hydrocarbon quantity in apparent recycle oil is reduced to about the 53% of reference examples, the depth of round hot tearing of recycle oil Change reaction process, the excessive heat cracking reaction amount of the low boiling hydrocarbon of generation is greatly reduced, reduces to about the 53% of reference examples；

Therefore, under target heat cracking reaction quantity permanence condition, hydrogen consumption, reduction gas or small molecule production can be reduced Rate, improves the macromolecular hydrocarbon liquid yield in light hydrocarbon and middle matter hydrocarbon；

3. deep hydrogenation process raw material quantity is greatly lowered, reactor volume can be reduced or improve thermal cracking conversion ratio

With being greatly lowered for the light hydrocarbon in second-stage reaction raw material and middle matter hydrocarbon quantity, in unconverted oil internal circulating load not Under conditions of change, second-stage reaction raw material absolute quantity can reduce 20.3%, therefore, in target thermal cracking conversion reaction quantity not Reactor volume can be reduced under the conditions of change, or thermal cracking conversion ratio can be improved under reactor volume permanence condition；

4. because equilibrium liquid phase transformation weight, beneficial to increasing reactive moieties single hop recycle oil quantity, or the overall single of higher is realized Journey splits rate, if it is considered that this Beneficial Effect, then hot high score oil total amount can also be reduced further.

Hot high score oil total amount, by dead catalyst amount, thermal condensation object amount is discharged, is given up in hot high score oil and is urged there are a lower limit The restriction of agent amount, the concentration of thermal condensation object amount.In this example, catalyst weight addition is the 1% of total liquid hydrocarbon material, semicoke Grain and ash content are the 1% of total liquid hydrocarbon material, and consideration thermal condensation green coke weight is the 1.5% of total liquid hydrocarbon material, adds up to total liquid The 3.5% of hydrocarbon material, calculates, hot high score oil total amount lower limit is total liquid according to solid particle weight content in hot high score oil for 15% The 23.3% of hydrocarbon material, about 9.5 tons/when.

It is thus possible to increase single hop cracked cycle oil quantity, improves overall cracking per pass, hot high score oil is further reduced Total amount and solid flow, to reduce hot high score oil system of processing, (it is high that high-pressure separator S1, hot high score oil SIL are depressured valve system, heat Point oil SIL is separated or fractionating system) scale create condition, investment and energy consumption can be greatly lowered, and asphalitine can be reduced Condensation product yield, improves processing safety.

Embodiment two

Based on embodiment one, by secondary hydrogenation reaction product BRP, the 3rd suspension bed of introducing one-stage hydrogenation reaction process AR In the reaction compartment of hydrogenation reactor AR3.

One-stage hydrogenation reaction product ARP carries out gas-liquid separation in high pressure hot separator S1, is separated into the gas flowed up ARP-V and liquid A RP-L, a part of liquid A RP-L enter in second-stage hydrogenation reactor BR1 as S1LR, a part of liquid ARP-L is as product S1LP.

Embodiment three

Based on embodiment two, by secondary hydrogenation reaction product BRP, the second suspension bed of introducing one-stage hydrogenation reaction process AR In the reaction compartment of hydrogenation reactor AR2.

Example IV

Based on embodiment two, by secondary hydrogenation reaction product BRP, the first suspension bed of introducing one-stage hydrogenation reaction process AR In the reaction compartment of hydrogenation reactor AR1.

Embodiment five

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.

Embodiment six

Coal Liquefaction process, one section of coal liquefaction are conventional coal liquefaction craft, product ARP operating pressures 20.0MPa, 455 DEG C of operation temperature, 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 is added, all will introduce the present invention by one section of hot high score oil Secondary hydrogenation reaction process BR, mixed with new hydrogen carry out deep hydrogenation thermal cracking, hydrogen-oil ratio 700, its reactor inlet gas 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 partial pressure value of product ARP Up to 4.1MPa, this is surprising mutability effect.

Embodiment seven

Based on embodiment six, 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.

Balance Air phase composition (the non-row solid of stream components flow rate of 9 second-stage hydrogenation reactor BR1 combined feeds BR1TF of table Thing)

10 second-stage hydrogenation reactor BR1 entrance Balance Air phase compositions of table and partial pressure and compared with reference examples

Conventional liquid forms in the balance liquid phase of 11 second-stage hydrogenation reactor BR1 combined feeds BR1TF of table

ASTM-D86 is distillated a little	Oily ASTM D86 in liquid phase	Wherein≤325 DEG C cut	Wherein >=335 DEG C cut
				1%, DEG C	1.401	99.939	353.568
5%, DEG C	112.768	124.561	353.96
				10%, DEG C	251.659	140.299	355.294
30%, DEG C	328.727	229.9	391.141
				50%, DEG C	380.104	267.111	447.945
70%, DEG C	461.421	289.774	467.853
				90%, DEG C	518.425	303.47	521.923
95%, DEG C	526.191	308.616	527.863
				99%, DEG C	569.717	308.616	573.148
Flow, kg/h	23393.346	6437.324	16956.022
				Weight yield	100.00%	27.52%	72.48%

The phase state analysis (the non-row solids of stream components flow rate) of 12 second-stage hydrogenation reactor BR1 combined feeds BR1TF of table

Claims

A kind of 1. hydrocarbon material secondary hydrogenation method with expanded bed reactor and single hot high score device, it is characterised in that include 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；

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 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 Liquefaction of hydrogen reacts；

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；

In one-stage hydrogenation reaction process AR, the hydrogenation reactor used is up flow type expanded bed hydrogenation reactor, uses at least 1 Platform hydrogenation reactor；

(2) come in one section of thermal high separate section S1, separation at least a portion one-stage hydrogenation reaction product ARP and at least a portion From the flow B RP-KS of step (4), obtain one section of hot gas separated by high pressure separator S1V gas and may be containing solid particle liquid material S1L；

S1 at least discharges 2 road liquid material XL, the 1st tunnel liquids containing the liquid hydrocarbon from one-stage hydrogenation reaction product ARP Material XL1 is used as the net product X L-P of liquid as secondary hydrogenation raw material BR1F, the 2nd road liquid material XL；

Gas ARP-V and liquid A RP-L are separated into S1, the net product ARP of one-stage hydrogenation reaction process；

Gas stream BRP-KS-V and liquid stream BRP-KS-L are separated into S1, flow B RP-KS；

Liquid of at least a portion from the net product ARP of one-stage hydrogenation reaction process, uses as secondary hydrogenation raw material BR1F；

There may be liquid of the part from flow B RP-KS, is recycled as secondary hydrogenation raw material BR1F；

(3) 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, one section of hot high score oil S1L of at least a portion enters two sections as secondary hydrogenation raw material BR1F and hydrogen-rich stream BR1FH and adds Hydrogen reaction process BR carries out secondary hydrogenation reaction BRR and obtains secondary hydrogenation reaction product BASE-BRP, discharge secondary hydrogenation reaction Effluent BRP-X, discharge secondary hydrogenation react net product BRP；

In secondary hydrogenation reaction process BR, the hydrogenation reactor used is up flow type expanded bed hydrogenation reactor, uses at least 1 Platform hydrogenation reactor；

In secondary hydrogenation reaction process BR, the volumetric concentration of hydrogen is higher than the hydrogen in net product ARP balance gas phases ARP-V in gas phase The volumetric concentration of gas, the volumetric concentration of impurity composition is less than the impurity composition in net product ARP balance gas phases ARP-V in gas phase Volumetric concentration；

In secondary hydrogenation reaction process BR, the weight concentration of high boiling hydrocarbon is higher than net product ARP balance liquid phases ARP-L's in liquid phase The weight concentration of high boiling hydrocarbon, low boiling point of the weight concentration of low boiling hydrocarbon less than net product ARP balance liquid phases ARP-L in liquid phase The weight concentration of hydrocarbon；

When solid particle is carried in secondary hydrogenation reaction process BR, in liquid phase, the weight ratio of the solid particulate matter carried in liquid phase, Higher than the weight ratio of the net product ARP balance liquid phases ARP-L solid particulate matters carried；

(4) the recovery section Z100 of net product BRP, the secondary hydrogenation at least partially based on step (3) are reacted in secondary hydrogenation The flow B RP-KS for reacting net product BRP enters one section of thermal high separate section S1.
2. secondary hydrogenation method according to claim 1, it is characterised in that：

(2) in one section of thermal high separate section S1, the one-stage hydrogenation reaction product ARP and flow B RP- from step (4) is separated KS, obtain one section of hot gas separated by high pressure separator S1V gas and may be containing solid particle one section of hot high score oil S1L liquid；

One section of hot high score oil S1L is at least divided into 2 tunnels, and the 1st tunnel is used as secondary hydrogenation raw material BR1F, and it is net that the 2nd tunnel is used as hot high score oil Product S1LP, S1LP are used as the net product X L-P of liquid；

(4) the recovery section Z100 of net product BRP is reacted in secondary hydrogenation, the secondary hydrogenation from step (3) reacts net product BRP, one section of thermal high separate section S1 is returned as flow B RP-KS.
3. secondary hydrogenation method according to claim 2, it is characterised in that：

(2) in one section of thermal high separate section S1, the one-stage hydrogenation reaction product ARP and flow B RP- from step (4) is separated KS；

The net product ARP of one-stage hydrogenation reaction process is separated into gas ARP-V and liquid A RP-L in space DA；

Second-stage reaction product BRP is separated into gas BRP-V and liquid B RP-L in independent gas-liquid separation space DB；RP-L points of liquid B For 2 tunnels, S1 is discharged from the liquid phase region of space DB as product BRP-LP all the way, all the way as recycle oil BRP-LR from space DB's Liquid phase region, which is discharged into after space DA is mixed with liquid A RP-L, is used as heat of mixing high score oil S1L, at least a portion heat of mixing high score Oily S1L is used as the feedstock hydrocarbon BR1F of secondary hydrogenation reaction process BR；

(4) the recovery section Z100 of net product BRP is reacted in secondary hydrogenation, the secondary hydrogenation from step (3) reacts net product BRP, one section of thermal high separate section S1 is returned as flow B RP-KS.
4. secondary hydrogenation method according to claim 1, it is characterised in that：

(1) in one-stage hydrogenation reaction process AR, the secondary hydrogenation from step (4) reacts net product BRP at least partially, with the One raw material A R1F or one section hydrogenation reaction intermediate product mix and carry out hydrogenation reaction；

(2) it is separated into one section of hot gas separated by high pressure separator in one section of thermal high separate section S1, at least a portion one-stage hydrogenation reaction product ARP S1V gases and may the hot high score oil liquid material S1L containing solid particle；

At least there are 2 road liquid material S1L, the 1st tunnel is used as secondary hydrogenation raw material BR1F, and the 2nd tunnel is used as the net product of hot high score oil S1LP, S1LP are used as the net product X L-P of liquid；

(4) the recovery section Z100 of net product BRP is reacted in secondary hydrogenation, at least a portion secondary hydrogenation reacts net product BRP Into in the hydrogenation reaction space of one-stage hydrogenation reaction process AR.
5. secondary hydrogenation method according to claim 1, it is characterised in that：

(3) in secondary hydrogenation reaction process BR, the hydrogenation reactor used is up flow type expanded bed hydrogenation reactor, using extremely Few 1 hydrogenation reactor, wherein the top of a hydrogenation reactor BRX, which takes off liquid space BRX-TZ, uses built-in liquid collection cups LD carries out product and takes off liquid and liquid collection water conservancy diversion acquisition collection liquid BRX-TL and gassiness product BRX-MP；

In the bottom of hydrogenation reactor BRX, reaction feed is reacted by feed inlet into the lower part of expanded bed hydrogenation reactor BRX Area flows up and passes through central reaction zone and top reaction zone becomes product BRX-UP, and liquid space BRX-TZ is taken off at top, produces Thing BRX-UP carries out de- liquid separation, and at least a portion liquid, which enters in liquid collection cups LD and becomes along catheter LK flowings, to be collected Liquid BRX-TL, remaining gassiness product BRX-MP are through product diversion pipe discharge reactor B RX；

After the pressurized step PL pressurizations of at least a portion collection liquid BRX-TL secondary hydrogenation reaction is returned to as recycle oil BRX-RL In the upstream hydrogenation reaction space of the product BRX-UP of process BR.
6. secondary hydrogenation method according to claim 1, it is characterised in that：

(3) in secondary hydrogenation reaction process BR, the hydrogenation reactor used is up flow type expanded bed hydrogenation reactor, using extremely Few 1 hydrogenation reactor, wherein the top of a hydrogenation reactor BRX, which takes off liquid space BRX-TZ, uses built-in liquid collection cups LD carries out product and takes off liquid and liquid collection water conservancy diversion acquisition collection liquid BRX-TL and gassiness product BRX-MP；

In the bottom of hydrogenation reactor BRX, reaction feed is reacted by feed inlet into the lower part of expanded bed hydrogenation reactor BRX Area flows up and passes through central reaction zone and top reaction zone becomes product BRX-UP, and liquid space BRX-TZ areas are taken off at top Domain, product BRX-UP carry out de- liquid separation, and at least a portion liquid enters in liquid collection cups LD and flowed into along catheter LK For collection liquid BRX-TL, remaining gassiness product BRX-MP is through product diversion pipe discharge reactor B RX；

(4) recovery section of net product BRP is reacted in secondary hydrogenation, at least a portion collection liquid BRX-TL is anti-as three sections of hydrogenation Answer the raw material CR1F and hydrogen-rich stream CR1FH of process CR to enter three sections of hydrogenation reaction CRR of CR progress and obtain three sections of hydrogenation reactions Product BASE-CRP, discharges three sections of hydrogenation reaction effluent CRP-X, the net product CRP of three sections of hydrogenation reactions of discharge；

The net product CRP of three sections of hydrogenation reactions goes recovery section.
7. secondary hydrogenation method according to claim 6, it is characterised in that：

(4) recovery section of net product BRP is reacted in secondary hydrogenation, uses three sections of thermal high separate section CS1, at least a portion The net product CRP of three sections of hydrogenation reactions is separated into three sections of hot gas separated by high pressure separator CS1V gases into three sections of thermal high separate section CS1 and can Three sections of hot high score oil CS1L liquid that can be containing solid particle.
8. secondary hydrogenation method according to claim 6, it is characterised in that：

(2) it is anti-in one section of thermal high separate section S1, separation one-stage hydrogenation reaction product ARP, the secondary hydrogenation from step (4) Answer net product BRP, obtain one section of hot gas separated by high pressure separator S1V gas and may be containing solid particle one section of hot high score oil S1L liquid；

One section of hot high score oil S1L is at least divided into 2 tunnels, and the 1st tunnel is used as secondary hydrogenation raw material BR1F, and the 2nd tunnel is net as hot high score oil Product S1LP is used；

(4) recovery section of net product BRP is reacted in secondary hydrogenation, secondary hydrogenation reacts net product BRP and removes one section of thermal high point From part S1；

The net product CRP of three sections of hydrogenation reactions, into any hydrogenation reaction space of secondary hydrogenation reaction process BR.
9. secondary hydrogenation method according to claim 6, it is characterised in that：

(2) it is anti-in one section of thermal high separate section S1, separation one-stage hydrogenation reaction product ARP, the secondary hydrogenation from step (4) Net product BRP, the net product CRP of three sections of hydrogenation reactions from step (4) are answered, obtains one section of hot gas separated by high pressure separator S1V gas and possibility One section of hot high score oil S1L liquid containing solid particle；

One section of hot high score oil S1L is at least divided into 2 tunnels, and the 1st tunnel is used as secondary hydrogenation raw material BR1F, and the 2nd tunnel is net as hot high score oil Product S1LP is used；

(4) recovery section of net product BRP is reacted in secondary hydrogenation, secondary hydrogenation reacts net product BRP and removes one section of thermal high point From part S1, the net product CRP of three sections of hydrogenation reactions removes one section of thermal high separate section S1.
10. secondary hydrogenation method according to claim 6, it is characterised in that：

(1) in one-stage hydrogenation reaction process AR, the flow C RP-KS at least partially from step (4), with the first raw material A R1F Or one section hydrogenation reaction intermediate product mixes and carries out hydrogenation reaction；

(2) in one section of thermal high separate section S1, separation one-stage hydrogenation reaction product ARP, the flow B RP- from step (4) KS, obtain one section of hot gas separated by high pressure separator S1V gas and may be containing solid particle one section of hot high score oil S1L liquid；

One section of hot high score oil S1L is at least divided into 2 tunnels, and the 1st tunnel is used as secondary hydrogenation raw material BR1F, and the 2nd tunnel is net as hot high score oil Product S1LP is used；

(4) recovery section of net product BRP is reacted in secondary hydrogenation, at least partially the secondary hydrogenation reaction based on step (3) The flow B RP-KS of net product BRP enters one section of thermal high separate section S1, is produced only based on three sections of hydrogenation reactions at least partially The flow C RP-KS of thing CRP is gone in any hydrogenation reaction space of one-stage hydrogenation reaction process AR.
11. secondary hydrogenation method according to claim 1, it is characterised in that：

(2) in one section of thermal high separate section S1, using high pressure hot separator S1E, separate one-stage hydrogenation reaction product ARP and come Net product BRP is reacted from the secondary hydrogenation of step (4), obtains one section of hot gas separated by high pressure separator S1V gas and may be containing solid particle One section of hot high score oil S1L liquid；Period, the gas phase air lift one-stage hydrogenation reaction process that net product BRP is reacted with secondary hydrogenation are net Low boiling component in product ARP liquid phases；

Gas-liquid separation, separation are carried out in the upper space DU of high pressure hot separator S1E, the net product ARP of one-stage hydrogenation reaction process For the gas ARP-V flowed up and the liquid phase liquid A RP-L to flow downward；Liquid A RP-L is downward through bubbling area Z1, Become ARP-LD i.e. Z1L processes middle part after carrying out the vaporization flash distillation of liquid phase with the gas BRP-V counter current contactings flowed up herein Space DM falls into lower space DA, leaves the upward flowing air of bubbling area Z1 and gas ARP-V is mixed into one section of hot high score Gas S1V gases；

Gas-liquid separation is carried out, is separated into and flows up in the central space DM of high pressure hot separator S1E, second-stage reaction product BRP Gas BRP-V through bubbling area Z1 falls into lower space DA with liquid phase the liquid B RP-L, liquid A RP-L to flow downward In with ARP-LD be mixed into one section of hot high score oil S1L liquid.
12. secondary hydrogenation method according to claim 11, it is characterised in that：

(2) in one section of thermal high separate section S1, using high pressure hot separator S1E, stripping section Z1 and lower stripping section Z2 in setting, Separate one-stage hydrogenation reaction product ARP and the secondary hydrogenation from step (4) react net product BRP, and use air lift hydrogen BH, One section of hot high score oil S1L liquid for obtaining one section of hot gas separated by high pressure separator S1V gas and may be containing solid particle；In upper stripping section Z1, The low boiling component in the net product ARP liquid phases of gas phase air lift one-stage hydrogenation reaction process of net product BRP is reacted with secondary hydrogenation； In lower stripping section Z2, the liquid phase of net product BRP is reacted and from one with secondary hydrogenation of the air lift hydrogen BH air lifts from step (4) Low boiling component in the liquid phase of the net product ARP of section hydrogenation process；

Gas-liquid separation, separation are carried out in the upper space DU of high pressure hot separator S1E, the net product ARP of one-stage hydrogenation reaction process For the gas ARP-V flowed up and the liquid phase liquid A RP-L to flow downward；Liquid A RP-L is downward through bubbling area Z1, Become upper stripping section discharge liquor liquid phase liquid after carrying out the vaporization flash distillation of liquid phase with the gas BRP-V counter current contactings flowed up herein Body ARP-LD, that is, Z1L, leaves the upward flowing air of Z1 and gas ARP-V is mixed into one section of hot gas separated by high pressure separator S1V gas；

Gas-liquid separation is carried out, is separated into and flows up in the central space DM of high pressure hot separator S1E, second-stage reaction product BRP Through the gas BRP-V and liquid phase the liquid B RP-L, liquid phase liquid B RP-L to flow downward of upper stripping section Z1 and from upper air lift The liquid Z1L of section is mixed and is downward through lower stripping section Z2, is carried out herein with the air lift hydrogen BH counter current contactings flowed up low Become lower stripping section discharge liquor Z2L after the vaporization flash distillation of boiling point component, Z2L, which is fallen into lower space DA, becomes one section of hot high score oil S1L liquid.
13. secondary hydrogenation method according to claim 11, it is characterised in that：

(2) in one section of thermal high separate section S1, using high pressure hot separator S1E, separate one-stage hydrogenation reaction product ARP and come Net product BRP is reacted from the secondary hydrogenation of step (4), obtains one section of hot gas separated by high pressure separator S1V gas and may be containing solid particle One section of hot high score oil S1L liquid；Period, the gas phase air lift one-stage hydrogenation reaction process that net product BRP is reacted with secondary hydrogenation are net Low boiling component in product ARP liquid phases；

Gas-liquid separation, separation are carried out in the upper space DU of high pressure hot separator S1E, the net product ARP of one-stage hydrogenation reaction process For the gas ARP-V flowed up and the liquid phase liquid A RP-L to flow downward；Liquid A RP-L is downward through bubbling area Z1, Become upper stripping section discharge liquor ARP-LD after carrying out the vaporization flash distillation of liquid phase with the gas BRP-V counter current contactings flowed up herein That is Z1L falls falls into lower space DA by central space DM, and the upward flowing air and gas ARP-V for leaving Z1 are mixed into one section Hot gas separated by high pressure separator S1V gases；

In the central space DM of high pressure hot separator S1E, second-stage reaction product BRP gas is separated into independent gas-liquid separation space DB Body BRP-V and liquid B RP-L；RP-L points of liquid B is 2 tunnels, and the first via is discharged as product BRP-LP from the liquid phase region of space DB S1, the second tunnel are discharged into after space DA is mixed with liquid Z1L as mixed as recycle oil BRP-LR from the liquid phase region of space DB Close hot high score oil S1L.
14. secondary hydrogenation method according to claim 13, it is characterised in that：

(2) in one section of thermal high separate section S1, using high pressure hot separator S1E, stripping section Z1 and lower stripping section Z2 in setting, Separate one-stage hydrogenation reaction product ARP and the secondary hydrogenation from step (4) react net product BRP, and use air lift hydrogen BH, Obtain one section of hot gas separated by high pressure separator S1V gas, one section of hot high score oil S1L liquid and product BRP-LP that may be containing solid particle； Upper stripping section Z1, in the net product ARP liquid phases of gas phase air lift one-stage hydrogenation reaction process that net product BRP is reacted with secondary hydrogenation Low boiling component；In lower stripping section Z2, react net product BRP's with secondary hydrogenation of the air lift hydrogen BH air lifts from step (4) Low boiling component in liquid phase and liquid phase from the net product ARP of one-stage hydrogenation reaction process；

Gas-liquid separation, separation are carried out in the upper space DU of high pressure hot separator S1E, the net product ARP of one-stage hydrogenation reaction process For the gas ARP-V flowed up and the liquid phase liquid A RP-L to flow downward；Liquid A RP-L is downward through bubbling area Z1, Become upper stripping section discharge liquor ARP-LD after carrying out the vaporization flash distillation of liquid phase with the gas BRP-V counter current contactings flowed up herein That is Z1L, leaves the upward flowing air of Z1 and gas ARP-V is mixed into one section of hot gas separated by high pressure separator S1V gas；

In the central space DM of high pressure hot separator S1E, second-stage reaction product BRP gas is separated into independent gas-liquid separation space DB Body BRP-V and liquid B RP-L；RP-L points of liquid B is 2 tunnels, and the first via is discharged as product BRP-LP from the liquid phase region of space DB S1, the second tunnel mixed as recycle oil BRP-LR from the discharge of the liquid phase region of space DB with the liquid Z1L from upper stripping section and to Under flow through lower stripping section Z2, after the vaporization flash distillation for carrying out low boiling component with the air lift hydrogen BH counter current contactings that flow up herein As lower stripping section discharge liquor Z2L, Z2L, which is fallen into lower space DA, is used as heat of mixing high score oil S1L.
15. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, 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；

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 are higher than the adding using expanded bed of hydrocarbon ils of 40%, the organic nitrogen weight content higher than 0.10% Hydrogen process.
16. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, it is characterised in that：

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

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.
17. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, 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.
18. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, it is characterised in that：

(3) 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.
19. secondary hydrogenation method according to claim 18, it is characterised in that：

(3) 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.
20. secondary hydrogenation method according to claim 18, it is characterised in that：

(3) 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.
21. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, it is characterised in that：

(2) in one section of thermal high separate section S1, using high pressure hot separator S1E, air lift hydrogen BH stripping sections, air lift hydrogen are set The gas BH liquid phase of the net product ARP of air lift one-stage hydrogenation reaction process and/or hydrogenation reaction from step (4) in stripping section is net The liquid phase of product；

20 DEG C of volume numbers of the standard state volume flow BH-V of air lift hydrogen BH and the conventional liquid phase hydrocarbon in the first raw material A R1F The ratio of amount is K900, and K900 is 30~3000.
22. secondary hydrogenation method according to claim 21, it is characterised in that：

(2) in one section of thermal high separate section S1, the K900 of air lift hydrogen BH is 300~1000.
23. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, 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) one sections of thermal high separate section S1, operating condition are：Temperature is 320~450 DEG C, pressure is 6~30MPa；

(3) 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.
24. secondary hydrogenation method according to claim 23, 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) one sections of thermal high separate section S1, operating condition are：Temperature is 360~440 DEG C, pressure is 12~25MPa；

(3) 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.
25. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, 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) one sections of thermal high separate section S1, operating condition are：Temperature is 320~450 DEG C, pressure is 6~30MPa；

(3) 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.
26. secondary hydrogenation method according to claim 25, 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) one sections of thermal high separate section S1, operating condition are：Temperature is 360~440 DEG C, pressure is 12~25MPa；

(3) 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.
27. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, 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%；

(3) 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%.
28. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, 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%；

(3) secondary hydrogenation reaction process BR, chemical hydrogen consumption amount are 0.05~3.0% to the Unit Weight hydrogen consumption of coal dust AR1FS.
29. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, 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.
30. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, 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.
31. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, 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%；

(2) one sections of thermal high separate section S1, operating condition are：Temperature is 320~450 DEG C, pressure is 6.0~30.0MPa；

(3) 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%.
32. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, 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) one sections of thermal high separate section S1, operating condition are：Temperature is 360~440 DEG C, pressure is 12.0~25.0MPa；

(3) 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%.
33. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, it is characterised in that：The hydrogenation process of first raw material A R1F, uses hydrogen supply hydrocarbon material.
34. two sections according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 add Hydrogen methods, it is characterised in that：First raw material A R1F includes hydrogen supply hydrocarbon material.
35. secondary hydrogenation method according to claim 1, it is characterised in that：

(3) 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 BR1F or its hydrogenation intermediate product.
36. secondary hydrogenation method according to claim 6, it is characterised in that：

(4) 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.
37. secondary hydrogenation method according to claim 1, it is characterised in that：

(3) new hydrogen is come from secondary hydrogenation reaction process BR, at least a portion hydrogen-rich stream BR1FH.
38. secondary hydrogenation method according to claim 1, it is characterised in that：

(2) in one section of thermal high separate section S1, the liquid isolated using air lift hydrogen BH air lift one-stage hydrogenation reaction products ARP Body ARP-L, the air lift hydrogen BH used come from circulating hydrogen.
39. secondary hydrogenation method according to claim 1, it is characterised in that：

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

(3) in secondary hydrogenation reaction process BR, 1~2 hydrogenation reactor is used.
40. secondary hydrogenation method according to claim 1, 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；

(3) in secondary hydrogenation reaction process BR, 1 hydrogenation reactor is used.
41. secondary hydrogenation method according to claim 1, 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；

(3) in secondary hydrogenation reaction process BR, 1 hydrogenation reactor is used.
42. secondary hydrogenation method according to claim 1, it is characterised in that：

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

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

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

(3) in secondary hydrogenation reaction process BR, it is substantially carried out the hydrocracking reaction that one-stage hydrogenation generates oily high boiling component.
44. secondary hydrogenation method according to claim 1, 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；

(3) 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.
45. secondary hydrogenation method according to claim 1, 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；

(3) 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.
46. secondary hydrogenation method according to claim 1, 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；

(3) reacted, certainly in secondary hydrogenation reaction process BR, the overhydrocracking for carrying out the oily high boiling component of one-stage hydrogenation generation Reacted by base stabilized hydrogenation.
47. secondary hydrogenation method according to claim 1, it is characterised in that：

(3) it is more than 90% in secondary hydrogenation reaction process BR, the hydrogen volume concentration of hydrogen-rich stream BR1FH.
48. secondary hydrogenation method according to claim 1, it is characterised in that：

(3) it is more than 95% in secondary hydrogenation reaction process BR, the hydrogen volume concentration of hydrogen-rich stream BR1FH.
49. secondary hydrogenation method according to claim 1, it is characterised in that：

(3) it is more than 99% in secondary hydrogenation reaction process BR, the hydrogen volume concentration of hydrogen-rich stream BR1FH.
50. secondary hydrogenation method according to claim 7, it is characterised in that：

(4) it is more than 90% in three sections of hydrogenation process CR, the hydrogen volume concentration of hydrogen-rich stream CR1FH.
51. secondary hydrogenation method according to claim 7, it is characterised in that：

(4) it is more than 95% in three sections of hydrogenation process CR, the hydrogen volume concentration of hydrogen-rich stream CR1FH.
52. secondary hydrogenation method according to claim 7, it is characterised in that：

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