CN109749778A

CN109749778A - A kind of hydrogenation modification reaction method of the material of the high aromatic hydrocarbons containing higher boiling

Info

Publication number: CN109749778A
Application number: CN201811500298.7A
Authority: CN
Inventors: 何巨堂
Original assignee: Luoyang Rui Hua New Energy Technology Development Co Ltd
Current assignee: Luoyang Rui Hua New Energy Technology Development Co Ltd
Priority date: 2018-11-29
Filing date: 2018-11-29
Publication date: 2019-05-14

Abstract

A kind of hydrogenation modification reaction method of the material of the high aromatic hydrocarbons containing higher boiling, high aromatic hydrocarbons material BRF is hydrocarbon-bearing material of the possibility containing solid particle for the high aromatic carbon hydrocarbon for being 350~650 DEG C comprising normal boiling point, the light asphalt extracted suitable for coal tar pitch is converted into the hydrogenation modification reaction process BRA of the raw material of high-quality carbon fiber or needle coke or other function carbon materials, BRA preferably uses up flow type expanded bed hydrogenator, the hydrogenation reaction based on hydrofining reaction occurs, wish that reaction product carbon atom number is constant, ring-type knot is constant, reduce part aromatic carbon rate or and removing part organic impurities such as sulphur, nitrogen, oxygen, metal, usually major part hydrogen is consumed in hydrofining reaction；The hydrogenation catalyst that BRA often uses hydrofining reaction function strong such as high dispersive catalyst with base of molybdenum can inhibit thermal cracking, thermal condensation reaction with dilution hydrocarbon or with hydrogen supply hydrocarbon to reduce reaction temperature, and rear portion can connect refining reaction process BRK after low temperature.

Description

A kind of hydrogenation modification reaction method of the material of the high aromatic hydrocarbons containing higher boiling

Technical field

The present invention relates to a kind of hydrogenation modification reaction method of the material of high aromatic hydrocarbons containing higher boiling, high aromatic hydrocarbons material BRF is packet Hydrocarbon-bearing material of the possibility containing solid particle containing the high aromatic carbon hydrocarbon that normal boiling point is 350~650 DEG C, is suitable for coal tar pitch In the light asphalt that the extracts raw material that is converted into high-quality carbon fiber or needle coke or other function carbon materials hydrogenation modification it is anti- It answers process BRA, BRA preferably to use up flow type expanded bed hydrogenator, the hydrogenation reaction based on hydrofining reaction occurs, Wish reaction product carbon atom number it is constant, it is cyclic annular knot it is constant, reduce part aromatic carbon rate or and removing part organic impurities such as sulphur, Nitrogen, oxygen, metal, usually major part hydrogen are consumed in hydrofining reaction；BRA often with hydrofining reaction function it is strong plus hydrogen urge Agent such as high dispersive catalyst with base of molybdenum can inhibit thermal cracking, thermal condensation with dilution hydrocarbon or with hydrogen supply hydrocarbon to reduce reaction temperature Reaction；The rear portion reaction process BRA can be with the lower reaction process BRK of tandem reaction temperature, and can carry out accurate depth adds hydrogen Refining reaction, the olefins hydrogenation reaction including eliminating heat reactivity；High aromatic hydrocarbons material BRF can carry out branch charging plus hydrogen is anti- It answers.

Background technique

High aromatic hydrocarbons material BRF of the present invention is to include and usually main be 350~650 DEG C comprising normal boiling point and be rich in Double ring arene or with the high aromatic carbon rate hydro carbons of polycyclic aromatic hydrocarbon and lightweight wax can be can be containing the hydrocarbon-bearing material of solid particle Oily (being mainly made of the hydrocarbon that normal boiling point is 350~470 DEG C), heavy wax oil (are mainly 450~570 DEG C by normal boiling point Hydrocarbon composition), the miscella of one or more of decompression residuum (being mainly made of normal boiling point higher than 530 DEG C of hydrocarbon), such as stone Wax slop, the Rfcc Products wax oil (heavy-cycle oil, clarified oil), coking heavy oil device wax slop, carbon of oil base viscous crude The distilled oil or extraction of the high wax slop of the double ring arene and polycyclic aromatic hydrocarbon content that hydrogen material heat from hydrogenation cracking generates, coal tar heavy oil Take oil.

High aromatic hydrocarbons light wax oil BRF-LAVGO of the present invention is mainly to be made of the hydrocarbon that normal boiling point is 350~470 DEG C Rich in double ring arene or with polycyclic aromatic hydrocarbon and can be containing the wax oil of solid particle, such as Rfcc Products light wax oil The distilled oil or extraction oil of (heavy-cycle oil, clarified oil), coking heavy oil device light wax oil, coal tar heavy oil.

High aromatic hydrocarbons wax slop BRF-HAVGO of the present invention is mainly to be made of the hydrocarbon that normal boiling point is 470~570 DEG C Rich in double ring arene or with polycyclic aromatic hydrocarbon and can be containing the wax oil of solid particle, such as Rfcc Products wax slop (heavy-cycle oil, clarified oil), coking heavy oil device wax slop, hydrocarbon material heat from hydrogenation cracking generate rich in double ring arene and more The wax slop of cycloaromatics, the distilled oil of coal tar heavy oil or extraction oil.

High aromatic hydrocarbons wax slop BRF-HAVGO of the present invention, can be direct hydrogenation liquefaction of coal reaction process or oily coal is total Refine hydrogenation process or heavy-oil hydrogenation heat cracking reaction process (referring mainly to floating bed hydrogenation heat cracking reaction process), heavy oil Catalytic cracking production, coking heavy oil generate the hydrocarbon that the normal boiling point in oil is usually 450~590 DEG C, generally 470~570 DEG C The fractionation fraction of composition formed rich in double ring arene or with the hydrocarbon component of polycyclic aromatic hydrocarbon works as base as fractional distillation process effluent When this is free of solid particle and aromatic carbon rate higher (coking value is higher), although fixed bed hydrogenation modified-reaction process can be used Process still (the catalyst runs period is short) at high cost, can be processed using boiling bed hydrogenation modification reaction process But it is at high cost, it can also be processed using floating bed hydrogenation reactive mode.When containing solid particle, should not usually adopt It is processed, can be processed still using boiling bed hydrogenation modification reaction process with fixed bed hydrogenation modified-reaction process Investment is high, catalyst consumption is at high cost, and is processed then cost using up flow type expanded bed hydrogenation reaction mode of the invention It is very low.

The light residual oil BRF-LRVGO of high aromatic hydrocarbons of the present invention is mainly to be made of the hydrocarbon that normal boiling point is 530~650 DEG C Rich in double ring arene or with polycyclic aromatic hydrocarbon and the de- drip of solvent of decompression residuum containing the residual oil of solid particle, can be can be Green oil, solvent-deasphalted oils, the solvent-deasphalted oils of coal tar heavy oil such as petroleum decompression residuum；The high light residual oil BRF- of aromatic hydrocarbons LRVGO, when being substantially free of solid particle and aromatic carbon rate higher (coking value is higher), it is difficult to modified anti-using fixed bed hydrogenation Process is answered to be processed (for example catalyst runs period is very short or usage amount causes greatly equipment investment very high) but at high cost, Process using boiling bed hydrogenation modification reaction process but at high cost, floating bed hydrogenation reaction side can also be used Formula is processed.When containing solid particle, should not usually be processed using fixed bed hydrogenation modified-reaction process, it can be with It is at high cost process still investment height, catalyst consumption using boiling bed hydrogenation modification reaction process, and uses of the invention Up flow type floating bed hydrogenation reactive mode carries out technique processing, and then cost is very low.

High aromatic hydrocarbons heavy resid BRF-HRVGO of the present invention is mainly made of for the hydrocarbon higher than 530 DEG C normal boiling point, leads to Often include 530~650 DEG C of the hydrocarbon component and the hydrocarbon molecule or molecule group such as glue bigger containing the higher molecular weight in other words of boiling point Asphalitine, has that hydrogen content is low, is easy to the characteristic of thermal condensation green coke, de- after can be the solvent extraction de-oiling of decompression residuum Oil asphalt oil, de-oiled asphalt oil, the de-oiled asphalt of coal tar heavy oil such as petroleum decompression residuum are oily；High aromatic hydrocarbons heavy resid BRF- HRVGO, when being substantially free of solid particle and aromatic carbon rate higher (coking value is higher), it is also difficult to modified using fixed bed hydrogenation Reaction process is processed (for example catalyst runs period is very short or usage amount causes greatly equipment investment very high) but cost Height process using boiling bed hydrogenation modification reaction process but invest that high, catalyst consumption cost is high, It can be processed using floating bed hydrogenation reactive mode.When containing solid particle, should not usually be changed using fixed bed hydrogenation Property reaction process processed, process using boiling bed hydrogenation modification reaction process but invest high, catalyst Consuming cost is high, and it is very low to use up flow type floating bed hydrogenation reactive mode progress technique of the invention to process then cost.

Therefore, high aromatic hydrocarbons material BRF of the present invention can be aromatic hydrocarbons light wax oil BRF-LAVGO, high aromatic hydrocarbons wax slop BRF- The miscella of one or more of the light residual oil BRF-LRVGO of HAVGO, high aromatic hydrocarbons, high aromatic hydrocarbons heavy resid BRF-HRVGO, can be with Containing solid particle, other components such as hydrogen can be contained while comprising said components.

Based on hydrofining reaction plus hydrogen occurs for the hydrogenation modification reaction process BRA of high aromatic hydrocarbons material of the present invention Reaction, it is desirable to which carbon reactant atomicity is constant, cyclic annular knot is constant, and goal response is to reduce at least part aromatic carbon rate or and de- Except at least part organic impurities such as sulphur, nitrogen, oxygen, metal, usually major part hydrogen is consumed in hydrofining reaction, still, usually The stabilized hydrogenation reaction of part heat from hydrogenation cracking reaction or heat cracking reaction or thermal cracking free radical may occur, it is also possible to Part thermal condensation reaction such as coking reaction can occur.

The hydrogenation modification reaction process BRA of high aromatic hydrocarbons material of the present invention, in order to inhibit heat cracking reaction, it is often desirable that the greatest extent It may be decreased reaction temperature, therefore, BRA is usually using the strong hydrogenation catalyst of hydrofining reaction function such as high dispersive molybdenum base Hydrogen supply hydrocarbon also can be used in catalyst,

The hydrogenation modification reaction process BRA of high aromatic hydrocarbons material of the present invention, in order to inhibit thermal condensation to react, reaction process is logical More reactive hydrogens are often desirable to provide, therefore, BRA is usually using the strong hydrogenation catalyst of hydrofining reaction function such as high score Catalyst with base of molybdenum is dissipated, hydrogen supply hydrocarbon BRDS or and dilution hydrocarbon BRPPS can be used.

High aromatic hydrocarbons material BRF of the present invention, can be the hydrocarbon ils all the way in 1 source, can be the 2 road hydrocarbon ils in 2 sources Or multiple sources multichannel hydrocarbon ils or their miscella miscella；Since the present invention can use up flow type expanded bed Reactive mode carries out the hydrogenation modification reaction of high aromatic hydrocarbons material BRF, therefore, allows high aromatic hydrocarbons material BRF to contain a certain number of solid Body, a certain amount of colloid of entrainment, asphalitine, that is to say, that high aromatic hydrocarbons material BRF can contain a large amount of high aromatic hydrocarbons heavy resid BRF- HRVGO component, in this way, be suitable for high aromatic hydrocarbons residue fraction hydrogenation modification reaction process to improve its quality and value, such as When hydrogenation modification reaction process applied to the light asphalt extracted in coal tar pitch, available suitable hydrogenation depth The hydrogenated bitumen of (aromatic moiety adds hydrogen saturation depth, hydrodesulfurization depth, hydrodenitrogeneration depth) is used as and produces high-quality carbon fiber The raw material of dimension or needle coke or other function carbon materials.

Basic imagination of the invention is: a kind of hydrogenation modification reaction method of the material of the high aromatic hydrocarbons containing higher boiling, high aromatic hydrocarbons Material BRF is hydrocarbon-bearing material of the possibility containing solid particle for the high aromatic carbon hydrocarbon for being 350~650 DEG C comprising normal boiling point, is suitable for height The light asphalt extracted in warm coal tar pitch is converted into adding for the raw material of high-quality carbon fiber or needle coke or other function carbon materials Hydrogen modified-reaction process BRA, BRA preferably use up flow type expanded bed hydrogenator, and adding based on hydrofining reaction occurs Hydrogen reaction, it is desirable to which reaction product carbon atom number is constant, cyclic annular knot is constant, reduces part aromatic carbon rate or organic miscellaneous with removing part Matter such as sulphur, nitrogen, oxygen, metal, usually major part hydrogen are consumed in hydrofining reaction；BRA often uses hydrofining reaction function strong Hydrogenation catalyst such as high dispersive catalyst with base of molybdenum, can with dilution hydrocarbon or with hydrogen supply hydrocarbon, to reduce reaction temperature, inhibit thermal cracking, Thermal condensation reaction；The rear portion reaction process BRA can carry out accurate depth with the lower reaction process BRK of tandem reaction temperature Hydrofining reaction, including eliminate heat reactivity olefins hydrogenation reaction；High aromatic hydrocarbons material BRF can carry out branch charging Hydrogenation reaction.

It is modified anti-to be applied to heavy-oil hydrogenation for a kind of hydrogenation modification reaction method of the material of the high aromatic hydrocarbons containing higher boiling of the present invention When answering process, main purpose is to obtain 1 or several in following target effects:

1. the hydrofining reaction that can carry out accurate depth to high aromatic hydrocarbons material BRF realizes hydrogenation modification, make some of which Double ring arene or with polycyclic aromatic ring be converted into fractional saturation aromatic hydrocarbons will part aromatic carbon be converted into cycloalkanes carbon, become be suitable for virtue The secondary processing of raw material of carbon rate, suitable C/Hratio, usually reduces thermal condensation reactivity, the crosslinking reactivity of product, for example applies When the hydrogenation modification reaction process of the light asphalt extracted in coal tar pitch, available suitable hydrogenation depth (aromatic hydrocarbons Partial hydrogenation saturation depth, hydrodesulfurization depth, hydrodenitrogeneration depth) hydrogenated bitumen, be used as production high-quality carbon fiber or needle The raw material of shape coke or other function carbon materials, also can be used as second heat cracked stock, the thermal polycondensation reaction raw materials of special-purpose；

The present invention can construct the extraordinary hydrofining reaction process of the accurate depth of high aromatic hydrocarbons material BRF；

2. dominating hydrogenation reaction for hydrogenation modification reaction process BRA is the anti-of aromatic carbon rate reduction for high aromatic hydrocarbons material BRF It answers, rather than complete aromatic hydrocarbons saturated reaction, it remains raw material or its conversion product to colloid, the solvability of asphalitine, because This, can process the material of high asphaltene concentration, it is easy to accomplish long period operation；

3. realizing hydrogenation modification by carrying out aromatic hydrogenation modified-reaction to high aromatic hydrocarbons material BRF, removing at least part has Machine impurity such as sulphur, nitrogen, oxygen, metal purify heavy hydrocarbon material so as to produce the purification heavy hydrocarbon material of low impurity concentration；

4. realizing hydrogenation modification by carrying out aromatic hydrogenation modified-reaction to high aromatic hydrocarbons material BRF, while controlling carbon reactant Atomicity is constant, cyclic annular knot is few as far as possible becomes, and can obtain hydrogenated bitumen in high yield, reduce gas recovery ratio, reduces hydrogen consumption；

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

6. high aromatic hydrocarbons material BRF carries out aromatic hydrogenation modified-reaction and realizes hydrogenation modification, it is conducive to inhibit thermal condensation reaction, leads to Often, the strong hydrogenation catalyst of BRA hydrofining reaction function such as high dispersive catalyst with base of molybdenum, can with dilution hydrocarbon or with hydrogen supply hydrocarbon, To reduce reaction temperature, inhibit thermal cracking, thermal condensation reaction；

7. the rear portion BRA can be high to reduce heat reactivity in final product with the lower reaction process BRK of tandem reaction temperature Component such as alkene；

It is reacted 8. high aromatic hydrocarbons material BR can be fed with branch, to reduce dilution hydrocarbon or the dosage with hydrogen supply hydrocarbon, improves process Economy；

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

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

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

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

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

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

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

For what is carried in the hot high score gas BRAP-THPV of the hydrogenation modification reaction process BRA product BRAP of high aromatic hydrocarbons The hydrocarbon component, can be applied in combination hydro-upgrading reaction process 9R, and hydro-upgrading reaction process 9R can add hydrogen positioned at high aromatic hydrocarbons The upstream or downstream for the hydrogen material that modified-reaction process BRA is used.

For the hot high score device BRAP-THPV of the hydrogenation modification reaction process BRA product BRAP of high aromatic hydrocarbons, can be set Gas phase takes off the washing and depositing section of solid.

A kind of low hydrogen content heavy oil using hydrogen supply hydrocarbon of Chinese patent ZL201210022921.9 adds hydrogen lightening method, The hydrogen-containing hydrocarbon stream that will be enriched in hydrogen supply hydrocarbon adds hydrogen lighting process for heavy oil such as coal tar pitch, has and inhibits condensation coking Speed improves coal tar heavy oil hydroconversion process liquid product yield, improves product quality, reduces reaction temperature rising, enhancing dress The effect of smooth operation and safety is set, but without proposing the similar material of the invention with the high aromatic hydrocarbons containing higher boiling Concept based on hydrogenation modification reaction and combinations thereof technique.

A kind of up flow type heat from hydrogenation cracking of high aromatic carbon rate poor quality hydrocarbon branch charging of Chinese patent ZL201610525311.9 Method is suitable for the high aromatic carbon rate poor quality hydrocarbon such as high normal boiling point of metal, polycyclic aromatic hydrocarbon, colloid, asphalt content higher than 450 DEG C coal tar heavy oil CRF floating bed hydrogenation heat cracking reaction process AR, AR include 2 or multiple serial operations first, Second sub- hydroconversion reaction zone AR1, AR2 etc., hydrocarbon CRF inferior points are two-way or demultiplex raw material CRF1, CRF2, CRF1 entrance The reaction effluent AR1P or material flow A R1PX containing its hydrogenated oil obtained by AR1 enters AR2 and contacts with CRF2, can reduce fresh Concentration of the raw material CRF2 in AR2 liquid phase is remarkably improved SHS and flows through in reaction zone when AR1 uses hydrogen-containing hydrocarbon stream SHS The ratio of " hydrogen supply hydrocarbon weight/fresh feed CRFX weight " can reduce thermal condensation coking speed but without proposing this similar hair Concept based on the hydrogenation modification reaction of the bright material with the high aromatic hydrocarbons containing higher boiling and combinations thereof technique.

A kind of low hydrogen content heavy oil using hydrogen supply hydrocarbon of above-mentioned Chinese patent ZL201210022921.9 adds hydrogen lighting A kind of up flow type heat from hydrogenation cracking side of high aromatic carbon rate poor quality hydrocarbon branch charging method, Chinese patent ZL201610525311.9 The heat from hydrogenation cracking method for adding hydrogen lightening method, heavy oil of method and other similar heavy oil, with main target of the invention Different or operating mode is different, can not achieve the purpose of the present invention, therefore be the technical solution being different from the present invention.

The light asphalt that the present invention extracts in coal tar pitch is converted into high-quality carbon fiber or needle coke or other function The technological advantage or feature shown in the hydrogenation modification reaction process BRA of the raw material of energy carbon material, highly significant, these are excellent In the hydrogenation modification reaction process for the material that point also exists in other high aromatic hydrocarbons containing higher boiling.

If normal boiling point that high aromatic hydrocarbons material BRF is included is 350~650 DEG C and is rich in from the point of view of component characteristic Double ring arene or high aromatic carbon rate hydro carbons with polycyclic aromatic hydrocarbon are the rich aromatic ring structure substances that height lacks hydrogen, have extremely strong aromatic ring Electromagnetic attraction should not or be difficult with fixed bed hydrogenation catalyst and carry out hydrofining reaction, because of its fixed bed catalyst It is difficult to optimize catalyst hydrogenation activity component and acid carrier component, such as:

1. can not be reacted if catalyst is unattractive to high aromatic carbon rate hydrocarbon；

2. can not efficiently deep reaction (be needed using abnormal a large amount of volumes if only faint or weaker attraction Catalyst causes technique uneconomical)；

3. with highly effective reaction but local reaction heat release can be caused to concentrate if having extremely strong or stronger attraction, Temperature rise is excessively high, it is necessary to use a large amount of diluent, cause uneconomical；

If having extremely strong or stronger attraction, as long as aromatic hydrocarbon molecule is not implemented complete hydrogenation and satisfies or and be not implemented deep Degree plus hydrogen saturation, the then adsorption capacity for remaining aromatic ring make reaction product be difficult to be desorbed from catalyst surface, therefore, reaction mass Diffuser efficiency in catalyst inner duct is extremely low, and the hydrogenation depth of reaction raw materials is difficult to uniform；

If having extremely strong or stronger attraction, as long as aromatic hydrocarbon molecule is not implemented complete hydrogenation and satisfies or and be not implemented deep Degree plus hydrogen saturation, the then adsorption capacity for remaining aromatic ring make reaction product be difficult to be desorbed from catalyst surface, and it is acute that hydrogen reaction is consumed in part Strong, aromatic hydrocarbons easily causes the scarce hydrogen in part to the shadowing effect of catalyst active center in addition, and induction thermal condensation coking reaction is big Amount occurs, as a result, operation cycle is short, uneconomical

5. even if can not also obtain the effect of hydrogen migration between hydrocarbon molecule using hydrogen supply dissolvent, because of hydrogen supply dissolvent equally quilt It is adsorbed with extremely strong or compared with strong attraction catalyst and carries out adding hydrogen exothermic reaction.

If normal boiling point that high aromatic hydrocarbons material BRF is included is 350~650 DEG C and is rich in from the point of view of component characteristic Double ring arene or high aromatic carbon rate hydro carbons with polycyclic aromatic hydrocarbon are the rich aromatic ring structure substances that height lacks hydrogen, have extremely strong aromatic ring Electromagnetic attraction is similarly difficult with boiling bed hydrogenation modifying process hydrofining reaction, because boiling bed hydrogenation reacted What the catalyst that journey uses inherently was evolved by fixed bed hydrogenation catalyst, composition, cellular structure, metal active The course of work in state, activity is similar with fixed bed hydrogenation catalyst, will only generate after catalyst bed boiling expansion Between some catalyst granules cross ebb interval convenient for reactionless active granule foreign in raw material by, it is difficult to have Effect prevents the coking of high aromatic carbon rate colloid, asphalitine.

Therefore, under most conditions, the hydrogenation modification reaction process of the material of the high aromatic hydrocarbons containing higher boiling, preferably selects suspension bed Hydrogenation process is especially suitable for using the strong hydrogenation catalyst of hydrofining reaction function such as high dispersive catalyst with base of molybdenum, can Inhibit thermal cracking, thermal condensation reaction with dilution hydrocarbon or with hydrogen supply hydrocarbon to reduce reaction temperature, carry out accurate depth adds hydrogen essence System reaction.

Problem andsolution proposed by the present invention be common problem existing for heavy-oil hydrogenation modified-reaction process and The technical solution generally used, since influential effect of the invention is huge, appearance of the invention is inevitable.

The present invention, can be by the Process flow of variation hydrogenation processes at different levels, can be other suitable by joint processing In the hydrocarbon material of joint processing, a variety of groups can be formed by the downstream processing methods of hydrocarbon ils in a variety of hot high score gas of joint Close technique.

For specific application, as needed, the present invention is to having hydrocarbon material hydrogen addition technology (including Chinese patent ZL201210022921.9, Chinese patent ZL201610525311.9) it can reasonably select use or be used cooperatively.

The method for being related to the coal tar suspension bed plus hydrogen production needle-shape coke raw material containing coal tar pitch has very much, but does not mention Technical solution of the present invention out.

The method of the invention has not been reported.

Therefore, the first object of the present invention is to propose a kind of hydrogenation modification reaction side of the material of high aromatic hydrocarbons containing higher boiling Method.

The second object of the present invention is to propose that a kind of hydrofinishing of the accurate depth of material of high aromatic hydrocarbons containing higher boiling is anti- Induction method, the hydrogen-carbon ratio of component is accurately adjusted to be precisely controlled aromatic hydrogenation saturation depth, or accurately reduces organic impurities Such as the content of sulphur, nitrogen, oxygen, metal.

The third object of the present invention is to propose that the light asphalt extracted in a kind of coal tar pitch is converted into high-quality carbon fiber The hydrogenation modification reaction method of the raw material of dimension or needle coke or other function carbon materials.

The fourth object of the present invention is to propose a kind of strong hydrogenation modified-reaction method of the material of high aromatic hydrocarbons containing higher boiling, is made With the strong hydrogenation catalyst of hydrofining reaction function (such as high dispersive catalyst with base of molybdenum) or and dilution hydrocarbon or with hydrogen supply hydrocarbon.

The fifth object of the present invention is to propose a kind of strong hydrogenation modified-reaction method of the material of high aromatic hydrocarbons containing higher boiling, is contained The material of the high aromatic hydrocarbons of higher boiling feeds reaction pattern using branch, to reduce dilution hydrocarbon or the dosage with hydrogen supply hydrocarbon, improves process Economy.

The sixth object of the present invention is to propose a kind of strong hydrogenation modified-reaction method of the material of high aromatic hydrocarbons containing higher boiling, high It the rear portion of the hydrogenation modification reaction process BRA of aromatic hydrocarbons BRF can be with the lower reaction process BRK of tandem reaction temperature, to reduce heat Component with high reactivity such as alkene；

The seventh object of the present invention is to propose a kind of strong hydrogenation modified-reaction method of the material of high aromatic hydrocarbons containing higher boiling, is added The generation oil distillate of hydrogen modified-reaction process BRA returns to hydrogenation modification reaction process BRA after mixing pressurization with high aromatic hydrocarbons material BRF Hydrogenation reaction is recycled, process is can simplify, reduces investment, reduces energy consumption.

The eighth object of the present invention is to propose a kind of strong hydrogenation modified-reaction method of the material of high aromatic hydrocarbons containing higher boiling, is added The generation oil distillate of hydrogen modified-reaction process BRA, the pilot process that can return to hydrogenation modification reaction process BRA are supplemented Property circulation hydrogenation reaction, serve as flux oil, quench oil, the quenching hydrogen gas consumption amount of reaction process, dedicated chilling oil consumption can be reduced Amount.

The ninth object of the present invention is to propose a kind of strong hydrogenation modified-reaction method of the material of high aromatic hydrocarbons containing higher boiling, right In the floating bed hydrogenation modified-reaction mistake using the strong hydrogenation catalyst such as high dispersive catalyst with base of molybdenum of hydrofining reaction function Enriched catalytic agent solid particle is obtained in journey BRA, autoreaction intermediate product or final reacting product or the isolate of reaction product Rich catalyst feed, then return to BRA and be recycled, can be greatly lowered fresh catalyst magnitude of recruitment, reduce catalyst Cost.

The tenth object of the present invention is to propose a kind of strong hydrogenation modified-reaction method of the material of high aromatic hydrocarbons containing higher boiling, is made The distillate that oil is generated with intermediate liquid product or final liquid product or reaction is recycled as self-control hydrogen supply dissolvent.

11st purpose of the invention is to propose a kind of strong hydrogenation modified-reaction method of the material of high aromatic hydrocarbons containing higher boiling, Hydrogen supply dissolvent reaction process DSR is applied in combination, the hydrogen supply dissolvent of production enters the hydrogenation modification reaction process BRA mistake of high aromatic hydrocarbons The hydrogen material that the hydrogenation modification reaction process BRA that Cheng Zhong, hydrogen supply dissolvent reaction process DSR can be located at high aromatic hydrocarbons is used Upstream or downstream, the hydrogenation modification reaction process BRA production oil of high aromatic hydrocarbons or its distillate can be used as hydrogen supply dissolvent reaction Process DSR raw material uses.

12nd purpose of the invention is to propose a kind of strong hydrogenation modified-reaction method of the material of high aromatic hydrocarbons containing higher boiling, It, can for the hydrocarbon component carried in the hot high score gas BRAP-TPPV of the hydrogenation modification reaction process BRA product BRAP of high aromatic hydrocarbons Hydro-upgrading reaction process 9R is applied in combination, the hydrogenation modification that hydro-upgrading reaction process 9R can be located at high aromatic hydrocarbons reacts The upstream or downstream for the hydrogen material that process BRA is used.

Summary of the invention

A kind of hydrogenation modification reaction method of the material of the high aromatic hydrocarbons containing higher boiling of the present invention, it is characterised in that:

The high aromatic hydrocarbons HAC of higher boiling refers to that normal boiling point is higher than 450 DEG C of high aromatic carbon rate aromatic component, and aromatic carbon rate is high In 50%；

The hydrogenation process BR of the material BRF of the high aromatic hydrocarbons HAC containing higher boiling, including hydrogenation modification reaction process BRA；

(1) hydrogenation process BR, including hydrogenation modification reaction process BRA；

1. in hydrogenation modification reaction process BRA, there are hydrogen, hydrocarbon liquid phase, there may be dilutions hydrocarbon or and may deposit simultaneously Hydrogen supply hydrocarbon or and there may be under the conditions of the mixed phase material of solid particle catalyst, the material of the high aromatic hydrocarbons HAC containing higher boiling BRF carries out hydrogenation modification reaction BRA-R and obtains hydrogenation modification reaction product BRA-BASE-P；Hydrogenation modification reaction product BRA- At least part alkene may be contained in BASE-P；

In hydrogenation modification reaction process BRA, using floating bed hydrogenation reactor, using in hydrogenation modification reaction process BR Body of work form is the molybdenum base dispersibility hydrogenation catalyst of molybdenum disulfide MoS2, uses hydrogen supply dissolvent；

The material BRF of the high aromatic hydrocarbons HAC containing higher boiling is the high aromatic hydrocarbons HAC group of higher boiling for being higher than 450 DEG C comprising normal boiling point The material divided；

The material BRF of the high aromatic hydrocarbons HAC containing higher boiling includes conventional liquid hydrocarbon raw material BRF-L, may be former comprising solid particle Expect BRF-S；

Hydrogenation modification reacts BRA-R, comprising the high aromatic hydrocarbons HAC component of at least part higher boiling plus hydrogen aromatic moiety saturation Reaction is anti-with at least part hydrodesulfurization reaction or at least part hydrogenation deoxidation or at least part hydrodenitrogeneration It answers, it may the also heat from hydrogenation cracking reaction comprising the high aromatic hydrocarbons HAC component of at least part higher boiling or the hot tearing generated free radicals Change reaction, the reaction of thermal cracking free radical stabilized hydrogenation；

Hydrogenation modification react BRA-R, comprising at least part hydrocarbon raw material BRF-L the high aromatic hydrocarbons HAC component of higher boiling plus Hydrogen refining reaction, may the heat from hydrogenation cracking comprising the high aromatic hydrocarbons HAC component of higher boiling at least part hydrocarbon raw material BRF-L it is anti- It answers, the hydrogenation reaction of at least part solid material BRF-S that may be present may be included；

Hydrogenation modification react BRA-R hydrofining reaction include unsaturated hydrocarbons plus hydrogen saturated reaction or with impure hydrocarbon Plus hydrogen hydrogenolysis；

Hydrogenation modification reaction BRA-R be characterized in that, hydrogenation modification react BRA-R hydrogen consumption in, at least 50% belong to plus The hydrogen of hydrogen refining reaction consumes；

Hydrogenation modification reaction process BRA may use up flow type floating bed hydrogenation to react using hydrogenator BRA-E Device BRA-E may use hydrogenation catalyst BRA-C；Hydrogenation modification reaction process BRA is reacted using up flow type floating bed hydrogenation Device BRA-E and when using hydrogenation catalyst BRA-C, the reaction compartment of the up flow type hydrogenator BRA-E used has catalyst Into the discharge of, catalyst；

There may be partial hydrogenation modified-reaction product BRA-BASE-P to deposit or stop or be circulated in hydrogenator BRA-E Inner space；

Hydrogenation modification reaction product BRA-BASE-P, to contain hydrogen, impurity composition, conventional gas hydrocarbon, conventional liq hydrocarbon The mixed phase material including at least gas phase and liquid phase of solid particle may be contained simultaneously；

Material based on hydrogenation modification reaction product BRA-BASE-P is used as hydrogenation modification reaction effluent BRA-P；

Hydrogenation modification reaction effluent BRA-P for hydrogenation modification reaction product BRA-BASE-P to be discharged, for containing hydrogen, Impurity composition, conventional gas hydrocarbon, conventional liq hydrocarbon may contain the mixed phase including at least gas phase and liquid phase of solid particle simultaneously Material；

Hydrogenation modification reaction effluent BRA-P occurs in the form of 1 tunnel or 2 tunnels or multichannel material BRA-PX, different The composition and phase of BRA-PX logistics are identical or different；

Hydrogenation modification reaction process BRA, may sub- hydroconversion reaction zone BRA-1, BRA- comprising 2 or multiple serial operations 2 etc., at this point, the logistics comprising at least part conventional liquid hydrocarbon of the reaction effluent based on upper alien hydroconversion reaction zone into Enter the adjacent sub- hydroconversion reaction zone in downstream, the sub- hydroconversion reaction zone BRA-1 of the first of hydrogenation modification reaction process BRA obtains reaction stream Object BRA-1P out, the flow B RA- comprising at least part hydrogenated oil BRA-1PO based on reaction effluent BRA-1P 1PX enters the second sub- hydroconversion reaction zone BRA-2 of hydrogenation modification reaction process BRA, the reaction of last sub- hydroconversion reaction zone Effluent is used as hydrogenation modification reaction effluent BRA-P；

What it is based on hydrogenation modification reaction effluent BRA-P includes at least part conventional liquid hydrocarbon, at least part hydrogen Material, be used as hydrogenation process BR effluent BR-ENDP

(2) it in removal process SR, separates and recovers hydrogenation process BR effluent BR-ENDP and obtains in volume mainly by hydrogen The hydrogen rich gas gas SRV of the gas composition and liquid stream SRL for mainly containing solid particle by the possibility that conventional liquid hydrocarbon forms, At least part hydrogen rich gas gas SRV returns to hydrogenation process and is recycled.

The present invention, hydrogenation modification reaction process BRA may include the front hydrogenation modification reaction process BRA of serial operation Conversion zone BRA-A and hydrogenation modification reaction process BRA rear portion conversion zone BRA-B, it is characterised in that:

1. in hydrogenation modification reaction process BRA, there are hydrogen, hydrocarbon liquid phase, there may be dilutions hydrocarbon or and may deposit simultaneously Hydrogen supply hydrocarbon or and there may be under the conditions of the mixed phase material of solid particle catalyst, the material of the high aromatic hydrocarbons HAC containing higher boiling BRF carries out hydrogenation modification reaction BRA-R and obtains hydrogenation modification reaction product BRA-BASE-P；Hydrogenation modification reaction product BRA- Contain at least part alkene in BASE-P；

Hydrogenation modification reaction process BRA, the hydrogenation modification reaction process BRA front conversion zone BRA-A comprising serial operation With hydrogenation modification reaction process BRA rear portion conversion zone BRA-B；

(a) in hydrogenation modification reaction process BRA front conversion zone BRA-A, there are hydrogen, hydrocarbon liquid phase simultaneously there may be Dilute hydrocarbon or with hydrogen supply hydrocarbon or under the conditions of the mixed phase material of solid particle catalyst, the material of the high aromatic hydrocarbons HAC containing higher boiling BRF is carried out comprising adding the front hydrogenation reaction BRA-AR of hydrogen aromatic hydrocarbons either shallow saturated reaction to obtain front hydrogenation reaction product BASE- BRA-AP；

The material BRF of the high aromatic hydrocarbons HAC containing higher boiling is the high aromatic carbon of the hydrocarbon component HD comprising normal boiling point higher than 450 DEG C Hydrocarbon material；

Front hydrogenation reaction BRA-AR, the hydrofinishing comprising the hydrocarbon component HD at least part liquid hydrocarbon feeds BRF-L BRA-A-HD-HTR is reacted, hydrofining reaction BRA-A-HD-HTR includes at least the partial hydrogenation saturated reaction of polycyclic aromatic hydrocarbon BRA-A-HD-HDAR, may comprising other unsaturated hydrocarbons plus hydrogen saturated reaction or with impure hydrocarbon plus hydrogen hydrogenolysis；

The reaction of at least part removal of ccr by hydrotreating, front hydrogenation reaction occurs in front hydrogenation process BRA-A, BRF The carbon residue of material BRF of the carbon residue of hydro carbons lower than the high aromatic hydrocarbons HAC containing higher boiling in product BASE-BRA-AP；

Front hydrogenation reaction BRA-AR is carried out under conditions of based on the liquid phase reactor, and at least part the hydrocarbon component HD occurs Polycyclic aromatic hydrocarbon partial hydrogenation saturated reaction BRA-A-HD-HDAR make at least part the hydrocarbon component HD aromatic carbon rate reduce turn The hydrocarbon component HAC is turned to, makes the aromatic ring of at least part polycyclic aromatic hydrocarbon component HDA be saturated to form methylene bridged bond, front adds hydrogen The aromatic carbon rate of material BRF of the aromatic carbon rate of hydro carbons lower than the high aromatic hydrocarbons HAC containing higher boiling in reaction product BASE-BRA-AP；

Front hydrogenation reaction BRA-AR may use hydrogenation catalyst BRA- using up flow type hydrogenator BRA-AE AC；When front hydrogenation process BRA-A uses hydrogenation catalyst BRA-AC, the up flow type hydrogenator BRA-AE that uses Reaction compartment have catalyst enter, catalyst discharge；

There may be front part hydrogenation reaction product BASE-BRA-AP to deposit or stop or be circulated in hydrogenator BRA- The inner space AE；

Front hydrogenation reaction product BASE-BRA-AP, for solid particle may be contained simultaneously containing hydrogen, conventional liq hydrocarbon Material；

Material based on front hydrogenation reaction product BASE-BRA-A is used as front hydrogenation reaction effluent BRA-AP；

BRA-AP is for being discharged BASE-BRA-AP, for that may contain solid particle simultaneously containing hydrogen, conventional liq hydrocarbon Material；

BRA-AP, in the form of 1 tunnel or 2 tunnels or multichannel material BRA-APX occur, the composition of different BRA-APX logistics and Phase is identical or different；

It is anti-that the flow B RA-AP-XO-TOBRA-B containing hydrocarbon ils in BRA-AP based on BRA-AP enters rear portion hydrogenation modification Answer process BRAB；

Flow B RA-AP-XO-TOBRA-B, the high aromatic carbon hydrocarbon material of the hydrocarbon component HAC comprising normal boiling point higher than 450 DEG C；

Flow B RA-AP-XO-TOBRA-B may include solid particulate materials BRA-AP-XO-TOBRA-BS；

(b) in hydrogenation modification reaction process BRA rear portion conversion zone BRA-B, there are hydrogen, hydrocarbon liquid phase simultaneously there may be Dilute hydrocarbon or and there may be hydrogen supply hydrocarbon or and there may be under the conditions of the mixed phase material of solid particle catalyst, flow B RA- AP-XO-TOBRA-B carries out adding hydrogen anti-comprising adding the rear portion hydrogenation reaction BRA-BR of hydrogen aromatic hydrocarbons depth saturated reaction to obtain rear portion Answer product BASE-BRA-BP；

Flow B RA-AP-XO-TOBRA-B includes conventional liquid hydrocarbon raw material BRA-AP-XO-TOBRA-BL, may be comprising solid Body particulate material BRA-AP-XO-TOBRA-BS；

Rear portion hydrogenation reaction BRA-BR may include at least part conventional liquid hydrocarbon raw material BRA-AP-XO-TOBRA-BL The heat from hydrogenation cracking reaction of middle the hydrocarbon component HAC may include at least part conventional liquid hydrocarbon raw material BRA-AP-XO-TOBRA- The hydrofining reaction of the hydrocarbon component HAC in BL；The hydrofining reaction of rear portion hydrogenation reaction BRA-BR includes adding for unsaturated hydrocarbons Hydrogen saturated reaction or with impure hydrocarbon plus hydrogen hydrogenolysis；

Hydrogenation modification reaction process BRA rear portion conversion zone BRA-B may be made using up flow type hydrogenator BRA-BE Spent hydroprocessing catalyst BRA-BC；When hydrogenation modification reaction process BRA rear portion conversion zone BRA-B uses hydrogenation catalyst BRA-BC, The reaction compartment of the up flow type hydrogenator BRA-BE used has catalyst to enter, catalyst is discharged；

There may be part rear portion hydrogenation reaction product BASE-BRA-BP to deposit or stop or be circulated in hydrogenator BRA- The inner space BE；

Rear portion hydrogenation reaction effluent BRA-BP, for rear portion hydrogenation reaction product BASE-BRA-BP to be discharged, to contain hydrogen Gas, impurity composition, conventional gas hydrocarbon, conventional liq hydrocarbon may include at least gas phase and liquid phase containing solid particle simultaneously Mixed phase material；

Rear portion hydrogenation reaction effluent BRA-BP occurs in the form of 1 tunnel or 2 tunnels or multichannel material BRA-BPX, different The composition and phase of BRA-BPX logistics are identical or different；

Material based on rear portion hydrogenation reaction product BASE-BRA-BP is used as hydrogenation modification reaction product BRA-BASE-P；

Material based on hydrogenation modification reaction product BRA-BASE-P is used as hydrogenation modification reaction effluent BRA-P.

(1) in hydrogenation modification reaction process BRA, there are hydrogen, hydrocarbon liquid phase, there may be dilution hydrocarbon or and may simultaneously There are hydrogen supply hydrocarbon or and there may be under the conditions of the mixed phase material of solid particle catalyst, the material of the high aromatic hydrocarbons HAC containing higher boiling BRF carries out hydrogenation modification reaction BRA-R and obtains hydrogenation modification reaction product BRA-BASE-P；Hydrogenation modification reaction product BRA- Contain at least part alkene in BASE-P；

Front hydrogenation reaction BRF-AR, the hydrofinishing comprising the hydrocarbon component HD at least part liquid hydrocarbon feeds BRF-L BRA-A-HD-HTR is reacted, hydrofining reaction BRA-A-HD-HTR includes at least the partial hydrogenation saturated reaction of polycyclic aromatic hydrocarbon BRA-A-HD-HDAR, may comprising other unsaturated hydrocarbons plus hydrogen saturated reaction or with impure hydrocarbon plus hydrogen hydrogenolysis；

Material based on front hydrogenation reaction product BASE-BRA-AP is used as front hydrogenation reaction effluent BRA-AP；

It is anti-that the flow B RA-AP-XO-TOBRA-B containing hydrocarbon ils in BRA-AP based on BRA-AP enters rear portion hydrogenation modification Answer process BRA-B；

The reaction compartment of hydrogenation modification reaction process BRA rear portion conversion zone BRA-B divides son according to following principles plus hydrogen is anti- Answer area: every starting point for 1 cracking intermediate liquid product circulation occur then forms the separation of 1 second son hydroconversion reaction zone, because This, there are the starting points of N number of cracking intermediate liquid product circulation, then form the separation of the sub- hydroconversion reaction zone of n times, then exist " M=N+1 " a sub- hydroconversion reaction zone BRA-BX, X=1~(N+1)；N≥2；

The reaction compartment of hydrogenation modification reaction process BRA rear portion conversion zone BRA-B is divided into 2 or multiple serial operations Sub- hydroconversion reaction zone, the thermal high point of the sub- hydroconversion reaction zone of at least one before last 1 sub- hydroconversion reaction zone BRA-BM It is anti-that hydrogenation modification is returned from the obtained cracking intermediate liquid product circulation flow B RA-BXMP-LR of process BRA-B XMP-THPS The front conversion zone BRA-A of process BRA is answered to contact generation at least part plus hydrogen saturated reaction with hydrogenation catalyst BRA-AC；

In hydrogenation modification reaction process BRA rear portion conversion zone BRA-B, produced comprising upper alien hydroconversion reaction zone conventional liquid hydrocarbon The logistics of object, into the adjacent lower alien hydroconversion reaction zone of serial operation；

The present invention may include serial operation low-temp reaction process BRK, it is characterised in that:

The logistics comprising at least part conventional liquid hydrocarbon based on hydrogenation modification reaction effluent BRA-P is used as series connection Operate the raw material BRK-FEED of the olefin-containing component containing hydrocarbon liquid phase of low-temp reaction process BRK；

Raw material BRK-FEED, the hydro-conversion object of the hydrocarbon component HAC comprising normal boiling point higher than 450 DEG C；

Raw material BRK-FEED may include solid particulate materials BRK-FEEDS；

2. in serial operation low-temp reaction process BRK, there are hydrogen, hydrocarbon liquid phase, hydrogenation catalyst simultaneously there may be Dilute hydrocarbon or and there may be under the conditions of hydrogen supply hydrocarbon mixed phase material, raw material BRK-FEED carries out low temperature hydrogenation refining reaction BRK-R Obtain low temperature hydrogenation refining reaction product BASE-BRK-P；The alkene of hydro carbons in low temperature hydrogenation refining reaction product BASE-BRK-P Hydrocarbon concentration, lower than the concentration of olefin of hydro carbons in hydrogenation modification reaction product BRA-BASE-P；

Low temperature hydrogenation refining reaction BRK-R, the hydrogenation of olefins comprising at least part the hydrocarbon component HAC in raw material BRK-FEED Saturated reaction, the hydrofining reaction comprising at least part the hydrocarbon component in raw material BRK-FEED may include raw material BRK- The heat from hydrogenation cracking reaction of at least part the hydrocarbon component in FEED；The hydrofining reaction packet of low temperature hydrogenation refining reaction BRK-R Containing unsaturated hydrocarbons plus hydrogen saturated reaction or with impure hydrocarbon plus hydrogen hydrogenolysis；

Serial operation low-temp reaction process BRK may use up flow type hydrogenator using hydrogenator BRK-E BRK-E；Serial operation low-temp reaction process BRK adds hydrogen to urge using up flow type floating bed hydrogenation reactor B RK-E and using using When agent BRK-C, the reaction compartment of the up flow type hydrogenator BRK-E used has catalyst to enter, catalyst is discharged；

There may be part low temperature hydrogenation refining reaction product BASE-BRK-P to deposit or stop or be circulated in hydrogenator The inner space BRK-E；

Low temperature hydrogenation refining reaction product BASE-BRK-P, to contain hydrogen, impurity composition, conventional gas hydrocarbon, conventional liquid Body hydrocarbon may contain the mixed phase material including at least gas phase and liquid phase of solid particle simultaneously；

Material based on low temperature hydrogenation refining reaction product BASE-BRK-P is used as low temperature hydrogenation refining reaction effluent BRK-P；

Low temperature hydrogenation refining reaction effluent BRK-P is used to that low temperature hydrogenation refining reaction product BASE-BRK-P to be discharged, and is Containing hydrogen, impurity composition, conventional gas hydrocarbon, conventional liq hydrocarbon simultaneously may containing solid particle include at least gas phase and The mixed phase material of liquid phase；

Low temperature hydrogenation refining reaction effluent BRK-P occurs in the form of 1 tunnel or 2 tunnels or multichannel material BRK-PX, different The composition and phase of BRK-PX logistics are identical or different；

The reaction compartment of serial operation low-temp reaction process BRK may add hydrogen anti-comprising the son of 2 or multiple serial operations Answer area, at this point, the logistics comprising at least part conventional liquid hydrocarbon of the reaction effluent based on upper alien hydroconversion reaction zone into Enter the adjacent sub- hydroconversion reaction zone in downstream, the first sub- hydroconversion reaction zone BRK1 of serial operation low-temp reaction process BRK is reacted Effluent BRK1-P, the logistics comprising at least part hydrogenated oil BRK1-PO based on reaction effluent BRK1-P BRK1-PX enters the second sub- hydroconversion reaction zone BRK2 of serial operation low-temp reaction process BRK, last sub- hydrogenation reaction The reaction effluent in area is used as low temperature hydrogenation refining reaction effluent BRK-P；

What it is based on low temperature hydrogenation refining reaction effluent BRK-P includes at least part conventional liquid hydrocarbon, at least part The material of hydrogen is used as hydrogenation process BR effluent BR-ENDP

(2) it in removal process SR, separates and recovers low temperature hydrogenation refining reaction effluent BRK-P and obtains in volume mainly by hydrogen The hydrogen rich gas gas SRV of the gas composition and liquid stream SRL for mainly containing solid particle by the possibility that conventional liquid hydrocarbon forms, At least part hydrogen rich gas gas SRV returns to hydrogenation process and is recycled.

The present invention, (1) can be selected from down in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling One or more of column material:

1. the hydrocarbon material based on coalite tar is coalite tar or its distillate or its extraction oil or its hot procedure Gained oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis Process；

2. the hydrocarbon material based on medium temperature coal tar is medium temperature coal tar or its distillate or its extraction oil or its hot procedure Gained oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis Process；

3. the hydrocarbon material based on high temperature coal-tar is high temperature coal-tar or its distillate or its extraction oil or its hot procedure Gained oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis Process；

4. based on the hydrocarbon material of direct hydrogenation liquefaction of coal product oil, be direct hydrogenation liquefaction of coal liquefaction process obtained by oil product or its Oil product obtained by hot procedure, direct hydrogenation liquefaction of coal liquefaction process includes the direct hydrogenation liquefaction of coal using hydrogen supply dissolvent oil Liquefaction process, oil coal refines process altogether, coal faces hydrogen thermosol liquefaction process, hot procedure be distillation process or thermal cracking process or Coking or catalytic cracking process or catalytic pyrolysis process；

5. the hydrocarbon material based on petroleum based heavy fuel oils is petroleum based heavy fuel oils or its distillate or its extraction oil or its hot procedure Gained oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis Process；

6. oil product obtained by the hydrocarbon material based on shale oil, shale oil or its distillate or its extraction oil or its hot procedure, Hot procedure is distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis process；

7. being tar sand base weight oil or its distillate or its extraction oil or its hot-working based on the hydrocarbon material of tar sand base weight oil Oil product obtained by process, hot procedure is distillation process or thermal cracking process or coking or catalytic cracking process or catalysis Cracking process；

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

The present invention, in general, (1) is normal in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling Advise the aromatic carbon rate reduction by 5~50% that boiling point is higher than 450 DEG C of hydrocarbon.

The present invention, generally, the routine in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling The aromatic carbon rate that boiling point is higher than 450 DEG C of hydrocarbon reduces by 10~30%.

The present invention, in general, (1) having in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling The extrusion rate of machine sulphur be the extrusion rate of the organic nitrogen in 5~60%, or the material BRF of the high aromatic hydrocarbons HAC containing higher boiling be 5~ 45%.

The present invention, generally, (1) having in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling The extrusion rate of machine sulphur be the extrusion rate of the organic nitrogen in 5~30%, or the material BRF of the high aromatic hydrocarbons HAC containing higher boiling be 5~ 20%.

The present invention, in general, in serial operation low-temp reaction process BRK, hydrocarbon in low temperature hydrogenation refining reaction effluent BRK-P The concentration of olefin of class, lower than 35% of the concentration of olefin of hydro carbons in hydrogenation modification reaction effluent BRA-P.

The present invention, operating condition are usual are as follows:

Normal boiling point in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is higher than 450 DEG C The aromatic carbon rate of hydrocarbon reduces by 5~50%；

The alkene of hydro carbons is dense in serial operation low-temp reaction process BRK, low temperature hydrogenation refining reaction effluent BRK-P Degree, lower than 65% of the concentration of olefin of hydro carbons in hydrogenation modification reaction effluent BRA-P.

The present invention, operating condition are general are as follows:

Normal boiling point in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is higher than 450 DEG C The aromatic carbon rate of hydrocarbon reduces by 10~35%；

The alkene of hydro carbons is dense in serial operation low-temp reaction process BRK, low temperature hydrogenation refining reaction effluent BRK-P Degree, lower than 75% of the concentration of olefin of hydro carbons in hydrogenation modification reaction effluent BRA-P.

The present invention, in general, 70~95% belong to the hydrogen consumption of hydrofining reaction in the hydrogen consumption of hydrogenation modification reaction BRA-R.

The present invention, in general, (2) are in removal process SR, the H of hydrogen rich gas gas SRV₂Volumetric concentration is greater than 75%.

The present invention, generally, (2) are in removal process SR, the H of hydrogen rich gas gas SRV₂Volumetric concentration is greater than 85%.

The present invention, in general, the operating condition of hydrogenation modification reaction process BRA are as follows:

1., using floating bed hydrogenation reactor, the hydrogenation catalyst BRA-C used is in hydrogenation modification reaction process BRA A kind of composite hydrogenation catalyst includes high-activity component and low activity component；The high-activity component metal and low activity group The weight ratio that parting belongs to is 1: 10 to 10: 1；The high-activity component is or mixtures thereof the water soluble salt compound of molybdenum；Institute It states low activity group and is divided into ferric oxide ore or iron sulfide ore, wherein iron in ore content is not less than 40wt%, catalyst BRA- C water content is lower than 2wt%；The powdered granule that BRA-C particle diameter is 1~100 μm；

The operating condition of hydrogenation modification reaction process BRA are as follows: temperature is 300~480 DEG C, pressure be 4.0~30.0MPa, Hydrogen/feedstock oil volume ratio is that weight is added as containing the high aromatic hydrocarbons HAC of higher boiling in 0.01: 1~4000: 1, hydrogenation catalyst BRA-C Material BRF weight 0.001%~8.0%, volume space velocity be 0.1~10.0hr^-1；The material of the high aromatic hydrocarbons HAC containing higher boiling BRF weight chemistry hydrogen consumption is 0.05%~4.0%.

The present invention, generally, the operating condition of hydrogenation modification reaction process BRA are as follows:

1. in hydrogenation modification reaction process BRA, using floating bed hydrogenation reactor, the hydrogenation catalyst BRA-C used, until It less include Mo element, Mo is molybdenum disulfide MoS2, hydrogenation catalyst in the body of work form of hydrogenation modification reaction process BRA The powdered granule that BRA-C is 0.0001~100 μm；

The operating condition of hydrogenation modification reaction process BRA are as follows: temperature is 360~460 DEG C, pressure be 6.0~22.0MPa, Hydrogen/feedstock oil volume ratio is that weight is added as the high aromatic hydrocarbons HAC containing higher boiling in 50: 1~2000: 1, hydrogenation catalyst BRA-C Material BRF weight 0.001%~5.0%, volume space velocity be 0.2~5.0hr^-1；The material BRF of the high aromatic hydrocarbons HAC containing higher boiling Weight chemistry hydrogen consumption is 0.25%~3.0%.

The present invention, preferably, the operating condition of hydrogenation modification reaction process BRA are as follows:

The operating condition of hydrogenation modification reaction process BRA are as follows: temperature is 360~460 DEG C, pressure be 8.0~16.0MPa, Hydrogen/feedstock oil volume ratio is that weight is added as containing the high aromatic hydrocarbons HAC of higher boiling in 200: 1~1200: 1, hydrogenation catalyst BRA-C Material BRF weight 0.001%~5.0%, volume space velocity be 0.5~3.0hr^-1；The material of the high aromatic hydrocarbons HAC containing higher boiling BRF weight chemistry hydrogen consumption is 0.25%~2.5%.

The present invention, in general, the operating condition of serial operation low-temp reaction process BRK are as follows:

(1) hydrogenation process BR, including hydrogenation modification reaction process BR and serial operation low-temp reaction process BRK；

2. serial operation low-temp reaction process BRK, uses floating bed hydrogenation reactor, operating condition are as follows: temperature be 280~ 440 DEG C, pressure be 4.0~30.0MPa, hydrogen/feedstock oil volume ratio is 30: 1~4000: 1, hydrogenation catalyst BRK-C be added Weight is the 0.001%~8.0% of the material BRF weight of the high aromatic hydrocarbons HAC containing higher boiling, volume space velocity is 0.3~10.0hr^-1；

The average reaction temperature of serial operation low-temp reaction process BRK is average anti-lower than hydrogenation modification reaction process BRA Answer at least 10 DEG C of temperature.

The present invention, generally, the operating condition of serial operation low-temp reaction process BRK are as follows:

2. serial operation low-temp reaction process BRK, uses floating bed hydrogenation reactor, operating condition are as follows: temperature be 300~ 420 DEG C, pressure be 6.0~22.0MPa, hydrogen/feedstock oil volume ratio is 30: 1~2000: 1, hydrogenation catalyst BRK-C be added Weight is the 0.001%~5.0% of the material BRF weight of the high aromatic hydrocarbons HAC containing higher boiling, volume space velocity is 0.6~5.0hr^-1；

The average reaction temperature of serial operation low-temp reaction process BRK is average anti-lower than hydrogenation modification reaction process BRA Answer at least 20 DEG C of temperature.

The present invention, preferably, the operating condition of serial operation low-temp reaction process BRK are as follows:

2. serial operation low-temp reaction process BRK, uses floating bed hydrogenation reactor, operating condition are as follows: temperature be 300~ 420 DEG C, pressure be 8.0~16.0MPa, hydrogen/feedstock oil volume ratio is 20: 1~1200: 1, hydrogenation catalyst BRK-C be added Weight is the 0.001%~3.0% of the material BRF weight of the high aromatic hydrocarbons HAC containing higher boiling, volume space velocity is 0.3~2.0hr^-1；

The average reaction temperature of serial operation low-temp reaction process BRK is average anti-lower than hydrogenation modification reaction process BRA Answer at least 25 DEG C of temperature.

The present invention, in general, the operating condition stage by stage of hydrogenation modification reaction process BRA are as follows:

1. the material BRF of the high aromatic hydrocarbons HAC containing higher boiling come from coal tar, gum asphaltic content be 10%~90% or It is 0.01%~60% with carbon residue；

The material BRF weight chemistry hydrogen consumption of hydrogenation modification reaction process BRA, the high aromatic hydrocarbons HAC containing higher boiling be 0.5%~ 4.0%,

(a) in hydrogenation modification reaction process BRA front conversion zone BRA-A, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling into Row with add hydrogen aromatic hydrocarbons either shallow saturated reaction or with removal of ccr by hydrotreating reaction based on front hydrogenation reaction BRA-AR, make material BR Gum asphalt hydrogenation and removing rate be greater than 5% or with carbon residue hydrogenation and removing rate be greater than 5%；

(b) in hydrogenation modification reaction process BRA rear portion conversion zone BRA-B, the material BRF weight of the high aromatic hydrocarbons HAC containing higher boiling Hydrogen consumption is learned in quantization, accounts for 65% or more of hydrogenation modification reaction process BRA overall weight chemical hydrogen consumption amount.

The present invention, generally, the operating condition stage by stage of hydrogenation modification reaction process BRA are as follows:

1. the material BRF of the high aromatic hydrocarbons HAC containing higher boiling come from high temperature coal-tar, gum asphaltic content be 10%~ 90% or or with carbon residue be 0.01%~60%；

The material BRF weight chemistry hydrogen consumption of hydrogenation modification reaction process BRA, the high aromatic hydrocarbons HAC containing higher boiling be 0.5%~ 3.0%,

(a) in hydrogenation modification reaction process BRA front conversion zone BRA-A, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling into Row with add hydrogen aromatic hydrocarbons either shallow saturated reaction or with removal of ccr by hydrotreating reaction based on front hydrogenation reaction BRA-AR, make material BR Gum asphalt hydrogenation and removing rate be greater than 25% or with carbon residue hydrogenation and removing rate be greater than 30%；

(b) in hydrogenation modification reaction process BRA rear portion conversion zone BRA-B, the material BRF weight of the high aromatic hydrocarbons HAC containing higher boiling Hydrogen consumption is learned in quantization, accounts for 60% or more of hydrogenation modification reaction process BRA overall weight chemical hydrogen consumption amount.

The present invention, in hydrogenation modification reaction process BRA, to intermediate reaction product or final reacting product BRAGP, Ke Yishe Set thermal high separation process BRAGP-THPS；

In thermal high separation process BRAGP-THPS, intermediate reaction product or final reacting product BRAGP are separated, is contained The hot hot high score of high score liquid for the conventional liquid hydrocarbon for thering is dissolution hydrogen, possibility of the normal boiling point higher than 350 DEG C to contain solid particle The oily BRAGP-THPS-L and hot high score oil BRAGP-THPS-PP of net product stream；

Hot high score oil BRAGP-THPS-L returns to thermal high as recycle oil BRAGP-THPS-LR and separated at least partially The reaction compartment and hydrogenation catalyst of at least part hydrogenation modification reaction process BRA is passed through in the upstream of journey BRAGP-THPS BRA-C contact or the reaction compartment and hydrogenation catalyst BRK- for passing through at least part serial operation low-temp reaction process BRK C contact.

The present invention, (1) hydrogenation process BR, including hydrogenation modification reaction process BRA；

In hydrogenation modification reaction process BRA, using floating bed hydrogenation reactor B RA-GE, can to intermediate reaction product or Thermal high separation process BRAGP-THPS is arranged in final reacting product BRAGP；

Hot high score oil BRAGP-THPS-L returns to thermal high as recycle oil BRAGP-THPS-LR and separated at least partially The reaction compartment of at least part hydrogenation modification reaction process BRA is passed through in the upstream of journey BRAGP-THPS；

Thermal high separation process BRAGP-THPS, is arranged in the upper space of floating bed hydrogenation reactor B RA-GE, with liquid The system of body collector, drain pipeline, circulating pump, liquor charging pipeline composition, makes at least part collection liquid BRAGP-THPS-LR The upstream for returning to thermal high separation process BRAGP-THPS is empty by the reaction of at least part hydrogenation modification reaction process BRA Between.

The present invention, (1) hydrogenation process BR, including hydrogenation modification reaction process BR and serial operation low-temp reaction process BRK；

Intermediate reaction product or final reacting product BRKGP can be set in serial operation low-temp reaction process BRK Thermal high separation process BRKGP-THPS；

In thermal high separation process BRKGP-THPS, intermediate reaction product or final reacting product BRKGP are separated, is contained The hot hot high score of high score liquid for the conventional liquid hydrocarbon for thering is dissolution hydrogen, possibility of the normal boiling point higher than 350 DEG C to contain solid particle The oily BRKGP-THPS-L and hot high score oil BRKGP-THPS-PP of net product stream；

Hot high score oil BRKGP-THPS-L returns to thermal high as recycle oil BRKGP-THPS-LR and separated at least partially The reaction compartment of at least part serial operation low-temp reaction process BRK is passed through in the upstream of journey BRKGP-THPS.

In serial operation low-temp reaction process BRK, using floating bed hydrogenation reactor B RK-GE, to intermediate reaction product or Thermal high separation process BRKGP-THPS can be set in final reacting product BRKGP；

Hot high score oil BRKGP-THPS-L returns to thermal high as recycle oil BRKGP-THPS-LR and separated at least partially The reaction compartment of at least part serial operation low-temp reaction process BRK is passed through in the upstream of journey BRKGP-THPS；

Thermal high separation process BRKGP-THPS, is arranged in the upper space of floating bed hydrogenation reactor B RK-GE, with liquid The system of body collector, drain pipeline, circulating pump, liquor charging pipeline composition, makes at least part collection liquid BRKGP-THPS-LR The upstream of thermal high separation process BRKGP-THPS is returned to by the anti-of at least part serial operation low-temp reaction process BRK Answer space.

In thermal high separation process BRKGP-THPS, isolated from intermediate reaction product or final reacting product BRKGP Hot high score oil BRKGP-THPSL, the hot high score oil BRKGP-THPS-L of at least part is as recycle oil BRKGP-THPS-LR- TOBRA returns to the reaction compartment that at least part hydrogenation modification reaction process BR is passed through in upstream.

In thermal high separation process BRKGP-THPS, isolated from intermediate reaction product or final reacting product BRKGP Hot high score oil BRKGP-THPSL, the hot high score oil BRKGP-THPS-L of at least part is as recycle oil BRKGP-THPS-LR- TOBRA returns to the reaction compartment that at least part hydrogenation modification reaction process BR is passed through in upstream；

Thermal high separation process BRKGP-THPS, is arranged in the upper space of floating bed hydrogenation reactor B RK-GE, with liquid The system of body collector, drain pipeline, circulating pump, liquor charging pipeline composition, makes at least part collection liquid BRKGP-THPS-LR- TOBRA returns to the reaction compartment that at least part hydrogenation modification reaction process BR is passed through in upstream.

The present invention, (1) hydrogenation process BR, including hydrogenation modification reaction process BR；

In hydrogenation modification reaction process BRA, using floating bed hydrogenation reactor B RA-GE, to intermediate reaction product or finally Thermal high separation process BRAGP-THPS can be set in reaction product BRAGP；

Hot high score oil BRAGP-THPS-L enters thermal high as collection liquid BRAGP-THPS-LP and separated at least partially End reaction in the reaction compartment of the downstream reaction process of journey BRAGP-THPS or into hydrogenation modification reaction process BRA produces In the thermal high gas-liquid separator of object；

Thermal high separation process BRAGP-THPS, is arranged in the upper space of floating bed hydrogenation reactor B RA-GE, with liquid The system of body collector, drain pipeline, circulating pump, liquor charging pipeline composition, makes at least part collection liquid BRAGP-THPS-LP Into in the reaction compartment of the downstream reaction process of thermal high separation process BRAGP-THPS or enter hydrogenation modification reaction process In the thermal high gas-liquid separator of the final reacting product of BRA.

Hot high score oil BRKGP-THPS-L enters thermal high as collection liquid BRKGP-THPS-LP and separated at least partially In the reaction compartment of the downstream reaction process of journey BRKGP-THPS or enter the final anti-of serial operation low-temp reaction process BRK It answers in the thermal high gas-liquid separator of product；

Thermal high separation process BRKGP-THPS, is arranged in the upper space of floating bed hydrogenation reactor B RK-GE, with liquid The system of body collector, drain pipeline, circulating pump, liquor charging pipeline composition, makes at least part collection liquid BRKGP-THPS-LP Into in the reaction compartment of the downstream reaction process of thermal high separation process BRKGP-THPS or enter serial operation low-temp reaction In the thermal high gas-liquid separator of the final reacting product of process BRK.

The present invention, in general, thermal high separation process THPS is arranged in removal process SR in (2)；

In thermal high separation process THPS, recycles hydrogenation process BR effluent BR-ENDP and obtain containing hydrogen, impurity Hydrogenation products, conventional gas hydrocarbon and normal boiling point are lower than the hot high score gas THPS-V of 350 DEG C of conventional liquid hydrocarbon and containing molten The hot high score liquid THPS-L that the possibility for the conventional liquid hydrocarbon that solution hydrogen, normal boiling point are higher than 350 DEG C contains solid particle；

Hot high score gas THPS-V is separated and recovered, the hydrogen rich gas gas SRV and master being mainly made of hydrogen in volume are obtained The liquid stream SRL-L that the possibility to be made of conventional liquid hydrocarbon contains solid particle, at least part hydrogen rich gas gas SRV Hydrogenation process is returned to be recycled.

Thermal high separation process THPS is arranged in removal process SR in the present invention, (2)；

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

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

The present invention is followed based on the hydrocarbon material RKKC rich in catalyst that hydrogenation process BR effluent BR-ENDP is obtained The raw material or intermediate product or final product of ring return hydrogenation modification reaction process BRA and hydrogenation modification reaction process BRA is mixed It closes；

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

1. the hot high score oil that a part is obtained in the thermal high separation process of hydrogenation process BR effluent BR-ENDP, As the hydrocarbon material RKKC containing catalyst；

2. a part is urged in the containing for destilling tower discharge of the separation fractional distillation process of hydrogenation process BR effluent BR-ENDP The hydrocarbon material of agent, as the hydrocarbon material RKKC containing catalyst；

3. a part is urged in the containing for destilling tower discharge of the separation fractional distillation process of hydrogenation process BR effluent BR-ENDP The distillation cold oil of agent, as the hydrocarbon material RKKC containing catalyst；

4. a part is urged in the containing for destilling tower discharge of the separation fractional distillation process of hydrogenation process BR effluent BR-ENDP The destilling tower base oil of agent, as the hydrocarbon material RKKC containing catalyst；

5. the hydrocarbon ils for the bituminous component that at least part separation hydrogenation process BR effluent BR-ENDP is obtained, is used The raw material VS-EF for making solvent extraction and separation process VS-EU, in the hydrocarbon containing catalyst that solvent extraction and separation process VS-EU is obtained Material, as the hydrocarbon material RKKC containing catalyst；

6. the hydrocarbon ils for the bituminous component that at least part separation hydrogenation process BR effluent BR-ENDP is obtained, is used The raw material VS-EF for making solvent extraction and separation process VS-EU, in the weight containing catalyst that solvent extraction and separation process VS-EU is obtained Matter pitch hydrocarbon material, as the hydrocarbon material RKKC containing catalyst；

7. the hydrocarbon ils for the bituminous component that at least part separation hydrogenation process BR effluent BR-ENDP is obtained, is used The raw material VS-EF for making solvent extraction and separation process VS-EU, solvent extraction and separation process VS-EU obtain containing the light of catalyst Matter pitch hydrocarbon material, as the hydrocarbon material RKKC containing catalyst；

8. the hydrocarbon ils for the bituminous component that at least part separation hydrogenation process BR effluent BR-ENDP is obtained, is used The raw material VS-EF for making solvent extraction and separation process VS-EU, solvent extraction and separation process VS-EU obtain containing in catalyst Matter pitch hydrocarbon material, as the hydrocarbon material RKKC containing catalyst.

The present invention, based on the isolated hydrocarbon material RKKC containing catalyst of hydrogenation process BR effluent BR-ENDP, It is recycled back into the raw material or intermediate product or most of serial operation low-temp reaction process BRK and serial operation low-temp reaction process BRK Final product mixing；

The material BRF of the present invention, the high aromatic hydrocarbons HAC containing higher boiling come from high temperature coal-tar, contain coal tar pitch component；

The extraction needle-shape coke raw material of containing hydrogenated coal tar pitch material based on hydrogenation process BR effluent BR-ENDP is set The solvent extraction and separation process VS-EU using solvent segregation；

Based on the hydrocarbon material RKKC rich in catalyst that hydrogenation process BR effluent BR-ENDP is obtained, it is recycled back into Hydrogenation modification reaction process BRA is mixed with the raw material of hydrogenation modification reaction process BRA or intermediate product or final product；

1. at least part is used as in the hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained containing catalyst Hydrocarbon material RKKC；

2. at least part is used as in the heavy asphalt hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained Hydrocarbon material RKKC containing catalyst；

3. at least part is used as in the light asphalt hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained Hydrocarbon material RKKC containing catalyst；

4. at least part is used as in the middle matter pitch hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained Hydrocarbon material RKKC containing catalyst；

The method that light liquid phase and heavy-fluid phase are isolated using the separation process of solvent segregation, can in following 1 Kind:

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

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

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

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

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

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

Based on the isolated hydrocarbon material RKKC containing catalyst of hydrogenation process BR effluent BR-ENDP, circulation is returned Return the raw material or intermediate product or final product of serial operation low-temp reaction process BRK and serial operation low-temp reaction process BRK Mixing；

The present invention, (1) in hydrogenation modification reaction process BRA, what it is based on hydrogenation modification reaction effluent BRA-P includes at least The original of olefin-containing component containing hydrocarbon liquid phase of the logistics of a part of conventional liquid hydrocarbon as serial operation low-temp reaction process BRK Expect BRK-FEED；

Raw material BRK-FEED, the high aromatic carbon hydrocarbon material of the hydrocarbon component HAC comprising normal boiling point higher than 450 DEG C；

Raw material BRK-FEED may include solid particulate materials BRK-FEEDS；

The logistics comprising at least part conventional liquid hydrocarbon based on hydrogenation modification reaction effluent BRA-P is used as series connection behaviour Make the working method of the raw material BRK-FEED of the olefin-containing component containing hydrocarbon liquid phase of low-temp reaction process BRK, can be selected from following In a kind or several:

1. hydrogenation modification reaction effluent BRA-P is used as the raw material BRK-FEED of olefin-containing component, low into serial operation Warm reaction process BRK；

2. hydrogenation modification reaction effluent BRA-P is used as the raw material BRK-FEED of olefin-containing component, with the material that cools Enter serial operation low-temp reaction process BRK after mixing；

3. hydrogenation modification reaction effluent BRA-P, which enters thermal high separation process BRA-P-HS, is separated into hot high score oil BRA- P-HSL and hot high score gas BRA-P-HSV, the hot high score oil BRA-P-HSL of at least part are used as the raw material BRK- of olefin-containing component FEED, into serial operation low-temp reaction process BRK；

4. hydrogenation modification reaction effluent BRA-P, which enters thermal high separation process BRA-P-HS, is separated into hot high score oil BRA- P-HSL and hot high score gas BRA-P-HSV, the hot high score oil BRA-P-HSL of at least part are used as the raw material BRK- of olefin-containing component FEED enters serial operation low-temp reaction process BRK after mixing with the material that cools；

5. hydrogenation modification reaction effluent BRA-P, which enters thermal high separation process BRA-P-HS, is separated into hot high score oil BRA- P-HSL and hot high score gas BRA-P-HSV, gained liquid B RA- after the hot high score oil BRA-P-HSL decompression of at least part, degassing The raw material BRK-FEED that P-HSLA is used as olefin-containing component enters serial operation low-temp reaction process BRK；

6. hydrogenation modification reaction effluent BRA-P, which enters thermal high separation process BRA-P-HS, is separated into hot high score oil BRA- P-HSL and hot high score gas BRA-P-HSV, gained liquid B RA- after the hot high score oil BRA-P-HSL decompression of at least part, degassing P-HSLA is used as the raw material BRK-FEED of olefin-containing component, and serial operation low-temp reaction is entered after mixing with the material that cools Process BRK.

1. the object of hydrogen supply hydrocarbon material DSF Yu the high aromatic hydrocarbons HAC containing higher boiling can be used in hydrogenation modification reaction process BRA Expect BRF or in which hydrogenation products contact.

The present invention, in general, (1) hydrogenation process BR, including hydrogenation modification reaction process BRA；

1. using the material BRF of hydrogen supply hydrocarbon material DSF and the high aromatic hydrocarbons HAC containing higher boiling in hydrogenation modification reaction process BRA Or in which hydrogenation products contact, the weight concentration absolute value of hydrogen supply the hydrocarbon component DS, which is higher than, in hydrogen supply hydrocarbon material DSF contains higher boiling The weight concentration absolute value at least 10% of hydrogen supply the hydrocarbon component DS in the material BRF of high aromatic hydrocarbons HAC.

1. using the material BRF of hydrogen supply hydrocarbon material DSF and the high aromatic hydrocarbons HAC containing higher boiling in hydrogenation modification reaction process BRA Or in which hydrogenation products contact, the weight concentration absolute value of hydrogen supply the hydrocarbon component DS is 10~65% in hydrogen supply hydrocarbon material DSF.

1. using the material BRF of hydrogen supply hydrocarbon material DSF and the high aromatic hydrocarbons HAC containing higher boiling in hydrogenation modification reaction process BRA Or in which hydrogenation products contact, hydrogen supply hydrocarbon material DSF are mainly made of the hydrocarbon component that normal boiling point is 250~350 DEG C.

1. using the material BRF of hydrogen supply hydrocarbon material DSF and the high aromatic hydrocarbons HAC containing higher boiling in hydrogenation modification reaction process BRA Or in which the contact of hydrogenation products, in hydrogen supply hydrocarbon material DSF the weight flow of hydrogen supply dissolvent component DS with it is high boiling in material BRF The ratio between the weight flow of the high aromatic hydrocarbons HAC of point is 0.05~2.0.

1. using the material BRF of hydrogen supply hydrocarbon material DSF and the high aromatic hydrocarbons HAC containing higher boiling in hydrogenation modification reaction process BRA Or in which hydrogenation products contact；

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

Based on the hydrogen material of stabilized hydrogenation reaction process MR, can enter hydrogenation modification reaction process BRA series connection makes With；

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

(2) in removal process SR, thermal high separation process THPS is set；

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

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

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

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

Recycling plus hydrogen upgrading reaction product HT66-P.

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

Recycling plus hydrogen upgrading reaction product HT66-P.

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

Recycling plus hydrogen upgrading reaction product HT66-P.

In separation fractional distillation process, at least part for the narrow fraction oil that heat of dissociation high score liquid THPS-L is obtained returns and adds The starting position or middle position of the reaction process of hydrogen reaction process BR carry out circulation plus hydrogen.

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

The present invention, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling are the higher boiling Gao Fang for being higher than 450 DEG C comprising normal boiling point The material of hydrocarbon HAC component；

The material BRF of the high aromatic hydrocarbons HAC containing higher boiling, can be selected from one or more of following materials:

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

2. the high hydrocarbon ils of content of ashes；

3. the high hydrocarbon ils of easy coking constituent content；

4. the high hydrocarbon ils of the easy reactant content of high temperature；

5. the hydrocarbon ils of the high rich polycyclic aromatic hydrocarbon of aromaticity.

1. in hydrogenation modification reaction process BRA, using dilution hydrocarbon WWF and the high aromatic hydrocarbons HAC containing higher boiling material BRF or its Intermediate hydrogenation products contact, the absolute value for diluting the aromatic carbon rate of hydrocarbon WWF are at least lower than the absolute value of the aromatic carbon rate of material BRF 0.1。

1. in hydrogenation modification reaction process BRA, using dilution hydrocarbon WWF and the high aromatic hydrocarbons HAC containing higher boiling material BRF or its Intermediate hydrogenation products contact, dilution hydrocarbon WWF are mainly made of the hydrocarbon component that normal boiling point is 250~350 DEG C.

In hydrogenation modification reaction process BRA, sub- hydroconversion reaction zone BRA-1, BRA-2 comprising 2 or multiple serial operations Deng at this point, the logistics comprising at least part conventional liquid hydrocarbon of the reaction effluent based on upper alien hydroconversion reaction zone enters The adjacent sub- hydroconversion reaction zone in downstream, the sub- hydroconversion reaction zone BRA-1 of the first of hydrogenation modification reaction process BRA obtain reaction outflow Object BRA-1P, the flow B RA-1PX comprising at least part hydrogenated oil BRA-1PO based on reaction effluent BRA-1P Into the second sub- hydroconversion reaction zone BRA-2 of hydrogenation modification reaction process BRA, the reaction stream of last sub- hydroconversion reaction zone Object is used as hydrogenation modification reaction effluent BRA-P out；

The material BRF of the high aromatic hydrocarbons HAC containing higher boiling can be divided into the string that at least 2 tunnels enter hydrogenation modification reaction process BRA The sub- hydroconversion reaction zone of difference of connection operation.

For the hot high score gas THPS-V isolated in thermal high separation process THPS, the liquid that gas phase takes off solid is set Washing and depositing section obtains the lower gas of solid content.

Specific 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 substance under an atmospheric pressure, liquid equilibrium temperature.

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

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

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

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

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

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

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

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

Diesel component of the present invention, the normal boiling point of institute's hydrocarbon-containifirst is usually 155~375 DEG C, generally 200~ 350℃。

Wax oil component of the present invention, the normal boiling point of institute's hydrocarbon-containifirst is usually 330~575 DEG C, generally 350~ 530℃。

Heavy oil component of the present invention, the normal boiling point of institute's hydrocarbon-containifirst be typically larger than 350 DEG C, generally higher than 450 DEG C, Particularly greater than 530 DEG C, more particularly greater than 575 DEG C.

Atmospheric resid component of the present invention, usually atmospheric fractional tower tower bottom oil, the normal boiling point of institute's hydrocarbon-containifirst Typically larger than 330 DEG C, generally higher than 350 DEG C, particularly greater than 370 DEG C.

Vacuum Residue Fractions of the present invention, usually vacuum fractionation tower tower bottom oil, the normal boiling point of institute's hydrocarbon-containifirst Typically larger than 450 DEG C, generally higher than 530 DEG C, particularly greater than 575 DEG C.

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

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

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

The hexa-atomic cyclic hydrocarbon of low carbon number list of the present invention, refers to C₆~C₉Benzene hydrocarbons or hexamethylene methane series hydrocarbon, normal boiling point Usually 70~180 DEG C, it is adapted for use as the raw material naphtha of catalytic reforming aromatic hydrocarbons.

Twin nuclei aromatic hydrocarbons of the present invention is referred to containing two ring structures and wherein at least one ring belongs to aromatic ring Hydro carbons, such as naphthalene, naphthane and its with the hydro carbons of side chain.

Tricyclic structure aromatic hydrocarbons of the present invention refers to the ring structure containing there are three and wherein at least one ring belongs to aromatic ring Hydro carbons, such as fluorenes, dibenzofuran, thia fluorenes, carbazole, dibenzopyridine, anthracene, phenanthrene and its with side chain hydrocarbon or part thereof adds hydrogen saturated products.

Multiring structure aromatic hydrocarbons of the present invention, is containing four or more ring structure and wherein at least one ring belongs to aromatic ring Hydro carbons.

High aromatic hydrocarbons of the present invention refers to the high hydrocarbon material of aromatic carbon rate, is commonly referred to as the hydrocarbon that aromatic carbon rate is higher than 40% Material is particularly referred to containing tricyclic structure aromatic hydrocarbons or the oil product high with the density of aromatic hydrocarbon of multiring structure aromatic hydrocarbons such as coal tar Fraction, direct hydrogenation liquefaction of coal oil distillate or the hydrogenation modification oil based on them, the heat from hydrogenation cracking process of such high aromatic hydrocarbons Primary product can be the hexa-atomic cyclic hydrocarbon of low carbon number list.

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

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

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

Up flow type hydrogenator of the present invention is described below.

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

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

Back-mixing stream expanded bed reactor of the present invention refers to reaction zone or main reaction region using expanded bed reactor Mode of operation there are liquid stream back-mixings there is circulation fluid in other words；Back-mixing stream or circulation fluid refer to the centre at flow points K At least part liquid phase XK-L in product X K or final product XK is anti-as the upstream of circulating fluid XK-LR Returning process point K Area is answered, the reaction product of circulating fluid XK-LR flows through K point and is present among XK.The mode for forming back-mixing stream can be arbitrarily Built-in inner ring flow cartridge, built-in outer ring flow cartridge, built-in liquid collecting cup+diversion pipe+circulating pump, outer is such as arranged in suitable mode Set formula circulation pipe etc..

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

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

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

It is described below and of the present invention states second level or multistage method of hydrotreating.

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

A hydrogenation reaction grade of the present invention refers to adding entering a hydrogenation process since hydrocarbon raw material to it Hydrogen product gas-liquid separation obtains at least one process section until generating the liquid product that oil forms by least part, includes The gas-liquid separation process of at least part hydrogenation reaction product of the hydrogenation process and this grade of the hydrogenation reaction grade.Therefore, Level-one method of hydrotreating refers to that the process of initial hydrocarbon feedstock only includes a hydrogenation reaction step and hydrogenation reaction step The flow model of rapid product gas-liquid separation process, a hydrogenation reaction step can be used 1 or 2 as needed Or the hydrogenator of more serial operations, therefore number of reactors and form be not determine order of reaction foundation, one or one The reaction step and its product separator common combination of a little tandem reactor compositions could form one and complete in meaning plus hydrogen Order of reaction.

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

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

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

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

The hydrogenation process BR, reaction product BASE-BRP, at least gas of the BRF of hydrocarbon ils containing coal tar pitch of the present invention Liquid two-phase logistics, most cases belong to gas, liquid, solid three-phase logistics.Hydrogenation reaction effluent BRP of the present invention is for being discharged Hydrogenation reaction product BASE-BRP occurs in the form of 1 tunnel or 2 tunnels or multichannel material, be gas phase or liquid phase or gas-liquid mixed phase or Gas-liquid-solid three-phase logistics.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

4. the understanding energy of molecular hydrogen can be reduced, accelerate the rate of dissociation of molecular hydrogen；

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

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

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

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

3. reaction overall temperature rise can be reduced；

4. the retention rate of pyrolysis molecule can be improved while reducing thermal condensation object such as coke yield, i.e. raising light-end products produce Rate is saved to be separated by solid-liquid separation and be consumed energy；

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

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

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

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

Stabilized hydrogenation reaction process MR, can using beaded catalyst bed (down-flow fixed bed, it is upflow fixed bed, Up flow type slight expanded-bed) reactive mode, usually temperature is 280~440 DEG C, pressure is 6.0~20.0MPa, hydrogenation catalyst MR-CAT volume space velocity is 0.05~10.0hr^-1, hydrogen/feedstock oil volume ratio be 300: 1~3000: 1 reaction condition under grasp Make.

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

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

The aromatic hydrogenation fractional saturation that the hydroconversion reaction zone MR of the present invention for being prepared as target with hydrogen supply hydrocarbon occurs is anti- It answers, refers to depositing in hydrogen and suitable hydrogenation catalyst MR-CAT (catalyst with aromatic hydrogenation fractional saturation function) The reaction process for the consumption hydrogen that hydrocarbon material SHSBF under conditions rich in double ring arene and/or polycyclic aromatic hydrocarbon occurs is minimum Reaction depth should have the industrial significance of bottom line: i.e. to the hydrocarbon material SHSBF rich in double ring arene and/or polycyclic aromatic hydrocarbon Expected aromatic hydrogenation fractional saturation is completed, which should be according to aromatic component structure in SHSBF and expected virtue Hydrocarbon fractional saturation degree determines, hydrogen supply in the hydrocarbon-fraction that the normal boiling point in hydrogenation reaction effluent MRP is 350~480 DEG C The higher the better for hydrocarbon weight concentration value SHN expectation, and SHN is the same as often greater than greater than 6 weight %, generally higher than 10 weight %.

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

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

The hydroconversion reaction zone MR that target is prepared as with hydrogen supply hydrocarbon, the hydrogenation catalyst MR-CAT used are included at least Hydrocatalyst for saturating arylhydrocarbon, usually also comprising Hydrodemetalation catalyst, olefins hydrogenation catalyst, (workflow position is logical It is frequently located in front of hydrocatalyst for saturating arylhydrocarbon bed).

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

Hydrogen supply dissolvent is used in the up flow type hydrogenation process of heavy oil, free radical can be quickly eliminated, can be improved and add hydrogen Reaction product hydrogen content, therefore heat cracking reaction can be inhibited i.e. reduce thermal cracking conversion ratio, reduce gas yield, thermal condensation object Yield, to improve the economy of process.

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

Typically there is the residue slurry-bed hydrocracking technology of industrialization operating achievement, there is Canadian CANMET residual oil to suspend Bed hydroprocessing thermocracking process, Italian eni company EST hydrogenation of residual oil suspended bed thermocracking process.It is other dreg-oil suspension bed Hydrocracking technology has the BPVCC technology path of British Petroleum Company, there is the BPVCC technology of British Petroleum Company, auspicious in committee The HDHPLUS technology of National Oil Company (PDVSA) of drawing, the Uniflex technology of Uop Inc., the U.S., U.S. Chevron VRSH technology etc..

The shortcomings that in order to overcome beaded catalyst hydrogen addition technology, floating bed hydrogenation technology has casted off once and for all " is urged using particle The flood tide inner surface of agent is as hydrogenation reaction place " mode, be characterized in that " using high degree of dispersion particle catalyst Outer surface as hydrogenation reaction place ", thus completely eliminate gum asphalt reach hydrogenation reaction place diffusion path Problem, can handle that tenor is higher, the higher inferior heavy oil of carbon residue content, and certainly, tenor is high, carbon residue The most handy coking process of the high inferior heavy oil of content such as delay coking process is handled；The reaction of floating bed hydrogenation reactor is empty Between, bed expansion rate has reached maximum, and solid catalyst additional amount is usually less than 10% (with feedstock oil poidometer), Form " having the advantages that coking material bearer capabilities " and " the discharge clear passage of suspended particulate impurity ".However it is in fact, outstanding Floating bed hydrogenator does not have bed concept, and reaction compartment thoroughly loses " high activity, height of fixed bed hydrogenation catalyst Interception rate, material hydro-conversion depth are uniform " the advantages of, then pair of " backmixing of liquid phase " with height and " liquid phase short circuit " Weight feature, therefore, product quality had declined compared with bed technology it is extremely more, so floating bed hydrogenation technology can only be used as it is bad The preprocessing process of matter oil, and high quality of products can not be produced.

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

The reaction efficiency of the catalyst surface of floating bed hydrogenation reactor, also by the polar impurity in gas phase in reactor The influence that occupies of absorption, coal tar hydrogenating process, tar and coal refine altogether process generate a large amount of polar impurity such as H2O, NH3, CO, CO2 can be strongly adsorbed in catalyst surface and form shadowing effect, therefore international well-known oil product technology suppliers CHEVRON Company is arranged the scheme of the timely impurity removal gas of gas-liquid separator and in subsequent floating bed hydrogenation between proposing in the reactor The lower part of reactor introduces high-purity hydrogen, but independent gas-liquid separator is arranged and invests big, Liquid level difficulty, operation Risk is big；For this purpose, this project recommends that " gas short route " technology can be used, under conditions of not increasing gas-liquid separator, The space that gas-liquid mixed phase material containing gas introduces at the top of suspended-bed reactor is subjected to gas-liquid separation, gas phase is expelled directly out, and The major part of liquid phase enters liquid phase reactor space by circulation pipe, in the lower part of subsequent floating bed hydrogenation reactor, introduces high-purity Hydrogen gas stream is spent, the gaseous environment of extremely low impurity is formed, the highly concentrated condition of hydrogen volume has been formed simultaneously, to give full play to Catalyst activity creates condition, and is conducive to reduce device stagnation pressure, improves conversion per pass, reduce thermal cracking gas making reaction, reduce Thermal condensation reaction；The scheme of above-mentioned timely impurity removal gas also has and low boiling hydrocarbon component is discharged in time, reduces its hot tearing The advantages of solution rate, is conducive to improve liquid receipts, reduces hydrogen consumption.

The typical heavy oil lighting reaction that the floating bed hydrogenation inside reactor of inferior heavy oil occurs, is substantially one The double-bond hydrogenation of the liquid phase macromolecular carried out in the liquid phase is cracked into the string of free radical, free radical stabilized hydrogenation at singly-bound, singly-bound Connection process, high thermal cracking temperature (400~480 DEG C) generate a large amount of free radicals and relatively uniform in entire state of aggregation liquid phase It is distributed in entire liquid Space, in order to prevent thermal condensation that prestissimo is needed to make free radical stabilized hydrogenation, it is evident that rely on and urge The reactive hydrogen on agent surface is unable to reach purpose (because the probability of the liquid phase hydrocarbon molecule of catalyst contact is too low, reactive hydrogen is mobile Process also can group be combined into inactive hydrogen molecule), preferably reactive hydrogen and free radical uniformly adjacent presence, and being produced in free radical Synchronous release when raw, to realize efficiently for reactive hydrogen.Boiling point is added in due course suitable hydrogen supply agent, which can just be crossed, to be met this and wants It asks, prevents thermal condensation, improves light product retention rate, these effects have been the Shenhua coal hydrogenation using hydrogen supply agent for running 8 years The successful longtime running result of direct liquefaction device is confirmed., pole huge higher than 530 DEG C of molecular dimension for normal boiling point Property strong heavy end, if reactive hydrogen cannot be provided in due course, a large amount of colloids, asphalitine thermal cracking free radical will be condensed compared with The bigger condensation product of its cracking precursor is received to reduce heat from hydrogenation cracked distillate oil (normal boiling point is lower than 530 DEG C of hydro carbons) Rate, in addition generate can dissolve beyond reaction process liquid phase, the thermal condensation the object such as coke or precursors of coke that carry lead to device It quickly stops work, these effects are confirmed by abundant experimental results.The present invention uses the operation mode of enough hydrogen supply agents, mesh Be that thermal cracking conversion ratio or the working properties for providing residual oil are more severe by providing reactive hydrogen enough inhibition cokings in due course The feed residue at quarter expands the scope of application of technique, improves operational stability, the economy of process.

For the hydrogenation modification reaction process BRA of the hydrocarbon containing organochlorine, Organic fluoride, in order to reduce hydrogenator rear portion System corrosion, it may be necessary to inject sodium carbonate, into final reacting product to neutralize corrosive component such as hydrogen chloride, fluorine Change hydrogen, hydrogen sulfide etc., its anion is fixed.

For the purpose of the present invention, the main purpose of the up flow type hydrogenation process of the material containing coal tar pitch is to carry out being suitable for deep The hydrodesulfurization of degree or and hydrodesulfurization, while carrying out a degree of hydrodemetallization reaction, while carrying out a degree of High boiling hydrocarbon component adds hydrogen aromatic moiety saturated reaction, also with a part of heat from hydrogenation cracking reaction of generation, heat cracking reaction It is reacted with the stabilized hydrogenation of thermal cracking free radical, it is more to produce low sulfur content, low-metal content, needle coke Suitable ingredients Then floating bed hydrogenation product drips coal after obtain plus hydrogen accordingly, it may be desirable to which floating bed hydrogenation product is fractionated first Blueness is separated into a hydrofining pitch and primary hydrogenation heavy asphalt, then will once hydrogenate heavy asphalt and return to suspension bed Hydro-upgrading process carries out secondary operation, such as the accumulative high concentration for forming catalyst in reaction process liquid phase of catalyst circulation Condition, to improve beneficial overall hydrogenation depth.

The heat from hydrogenation again of heat from hydrogenation cracking tail oil of the heat from hydrogenation cracking of middle low temperature coal tar pitch and coal tar pitch is split For the general effect of change, overall heat from hydrogenation cracking conversion rate can effectively improve using hydrogen supply dissolvent, outer get rid of is effectively reduced and contains Gu the yield of tail oil, to improve the economy of process.

With regard to the totality of the hydrofinishing again of hydrofinishing tail oil of hydrofinishing of coal tar pitch and coal tar pitch For effect, it can effectively improve overall plus hydrogen saturation factor using hydrogen supply dissolvent, be effectively reduced and get rid of the yield containing solid tail oil outside, To improve the economy of process.

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

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

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

The essential attribute of the appropriate catalysts of the hydrogenation process BRA of the BRF of hydrocarbon ils containing coal tar pitch described in detail below.

As previously mentioned, the main purpose of the up flow type hydrogenation modification reaction process BRA of the BRF of hydrocarbon ils containing coal tar pitch is to be fitted The aromatic moiety of suitable depth adds hydrogen to be saturated, while carrying out a degree of plus hydrogen removing impurities matter (sulphur, nitrogen, oxygen, metal) reaction, together The stabilized hydrogenation of a degree of heat from hydrogenation cracking reaction of Shi Jinhang (association), heat cracking reaction and thermal cracking free radical reacts, It is more to produce suitable aromatic carbon rate, low sulfur content, low nitrogen content, low oxygen content, low-metal content, needle coke Suitable ingredients Therefore floating bed hydrogenation modified product proposes catalyst claimed below naturally:

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

2. high degree of dispersion, i.e. granularity are small, the external surface area of Unit Weight catalyst is improved, is reduced using proportion, conducive to taking Take reactor out of；To reduce the carrying amount in refined bitumen；

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

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

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

The up flow type hydrogenation modification reaction process BRA of material BRF of the invention described in detail below, hydrogenation modification reaction It is meant that, in overall hydrogenation reaction, the partial hydrogenation saturated reaction of aromatic hydrocarbons is desired leading reaction.

Material BRF of the present invention, usually high aromatic carbon rate hydrocarbon, carbon residue or coking value are very high, therefore, in general, Under the conditions of hydrogen supply dissolvent, material BRF coking tendency in high-temperature hydrogenation reaction process is serious, than hydrocarbon ils containing coal tar pitch Coking tendency of the identical fraction of boiling range during heat from hydrogenation cracking reaction in BRF is more serious.

In group technology of the invention, the of the up flow type hydrogenation modification reaction process BRA of material BRF of the present invention One reaction task be carry out heavy hydrocarbon inferior removal of ccr by hydrotreating reaction i.e. heavy arene or colloid, asphalitine plus hydrogen saturation instead Answer, certainly, while can occur hydrofining reaction (including demetalization plus hydrogen hydrogenolysis, olefins hydrogenation reaction plus Hydrogen removing impurities matter (oxygen, sulphur, nitrogen) reaction adds hydrogen aromatic hydrocarbons full or reacts with fractional saturation reaction, removal of ccr by hydrotreating) or and hydrogen is added to split Change reaction.The typical feedstock of the up flow type hydrogenation modification reaction process BRA of material BRF be exactly the BRF of hydrocarbon ils containing coal tar pitch plus hydrogen Product residual oil in reaction process BR, in general, in the tower bottom residual oil that it is enriched in vacuum fractionation tower in product fractionation process, this Kind residual oil THC-VR usually contains catalyst conversion product such as molybdenum sulfide of addition etc., the BR from the BRFL of hydrocarbon ils containing coal tar pitch is produced Object metal sulfide, the coke that may be accumulated.

When material BRF includes the normal boiling point height in the hydrogenation process BR product BRP from the BRF of hydrocarbon ils containing coal tar pitch When 530 DEG C of fractionation tail oil hydro carbons BR-VR, the carbon residue content of part heavy oil BR-VR is usually above boiling range in raw material BRF The carbon residue content of identical fraction, in other words the liquid phase in hydrocarbon material hydrogenation process BR be adapted as material BRF plus hydrogen The colloid of reaction process, asphalitine, liquid phase coke dispersion solution, therefore, the up flow type of material BRF is added hydrogen to change by the present invention Property reaction process BRA reaction product in heavy hydrocarbon introduce the BRF of hydrocarbon ils containing coal tar pitch hydrogenation process BR second half section carry out Appropriate hydrogenation reaction can control the hydrogenation depth of hydrocarbon material BRF simultaneously, prevent excessively high hot tearing rate from leading to thermal condensation The yield of object such as asphalitine is more than the generation for limiting the quantity and causing second liquid phase (pitch phase).

In the up flow type hydrogenation modification reaction process BRA of material BRF, when reactive hydrogen is supplied not in time, colloid, drip Condensation reaction, production molecular weight bigger molecule or structure group, repeatedly dehydrogenation will occur for the thermal cracking free radical of green matter Final result with condensation reaction is to generate coke, and certainly, this is the negative reaction for needing inhibition or reduction.

The reactor types of the up flow type hydrogenation modification reaction process BRA of material BRF of the present invention, can be any conjunction Suitable form can be the group of one or more of combination cot reactor of suspended-bed reactor, ebullated bed and suspension bed It closes.

The up flow type hydrogenation modification reaction process BRA of material BRF of the present invention, the reactor used can be 1 or 2 Platform or more, reactor working method can be any suitable form, and usually up flow type expanded bed reactor or carrying liqs produce The up flow type expanded bed reactor of object circulation, the W-response area of separate unit up flow type expanded bed reactor can artificially be divided For 2 or multiple reaction zones.The control mode of the inlet temperature of any reaction zone of up flow type expanded bed reactor of the present invention, Can be adjust hydrogen temperature or and flow, can be adjust oil product temperature or and flow, naturally it is also possible to using heat exchange Device brief introduction heat exchange cooling.

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

In order to adjust reaction feed property, or in order to control reaction process property of liquid phase, it can will contain coal tar pitch hydrocarbon ils A part of product liquid of the intermediate liquid product of the hydrogenation process BR of BRF such as front conversion zone or final liquid produce A part of product liquid of object such as rear portion conversion zone, the up flow type that direct circulation returns to upstream under high-temperature high-pressure state add hydrogen The reaction compartment of modified-reaction process BRA.

The residue fraction in up flow type hydro-upgrading reaction product BRP in order to shorten the BRF of hydrocarbon ils containing coal tar pitch enters object The path for expecting the up flow type hydrogenation modification reaction process BRA of BRF, when the distillate that the liquid phase of reaction product BRP contains is (conventional Boiling point is lower than 530 DEG C of hydro carbons) when being rich in hydrogen supply agent or precursor of hydrogen donor, it can be directly by the liquid of part reaction product BRP The up flow type hydrogenation modification reaction process BRA for mutually introducing material BRF, at this point, foring tail oil high-pressure delivery short path；When anti- The distillate (normal boiling point is lower than 530 DEG C of hydro carbons) for answering the liquid phase of product BRP to contain only contains a small amount of hydrogen supply agent or hydrogen supply agent When precursor, it usually needs obtain the mixed of residual oil or residual oil and wax slop in the oily separation and recovery system of generation of reaction product BRP Oil is closed as heavy hydrocarbon inferior and introduces up flow type hydrogenation modification reaction process BRA, at this point, foring the long conveying path of conventional tail oil Diameter.

A free-revving engine of the invention is that as needed, (circulation makes hydrogen supply dissolvent component in reuse reaction product With, series circulation use), the heavy oil component in reaction product can be made in the up flow type hydrogenation modification of the BRF of hydrocarbon ils containing coal tar pitch Reaction process BRA (such as rear portion conversion zone) carries out Unionfining.

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

The up flow type hydrogenation modification reaction process BRA of the BRF of hydrocarbon ils containing coal tar pitch of the present invention refers to that up flow type expands Bed hydroprocessing reaction process, such as floating bed hydrogenation reaction process, suspension bed and ebullated bed combined type hydrogenation process.

In fact, the present invention program be using high-output qulified needle-shape coke raw material oil as target, therefore, hydrocarbon ils containing coal tar pitch Conversion per pass excessively high of coal tar pitch component HDS in BRF will increase light fraction oil yield, reduce target asphalt component Quantity is substantially contradictory with present subject matter target, unfavorable.

In fact, the present invention program be using high-output qulified needle-shape coke raw material oil as target, therefore, hydrocarbon ils containing coal tar pitch The one way of coal tar pitch component HDS in BRF adds under hydrogen saturation depth the same terms, and the higher the better for desulfurization degree, denitrification percent, cracking The lower rate the better, can reduce hydrogen consumption cost in this way, improve target product yield, therefore, typically, up flow type expanded bed The higher the better for the selectivity of the hydrofining reaction of hydrogenation modification reaction process BR, such high-selective and hydrogenating catalysts Just at the condition of important optimization operation.Present invention preferably uses catalyst with base of molybdenum, especially nanoscale catalyst with base of molybdenum.

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

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

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

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

The first light diesel fuel (180~220 DEG C of fractions of conventional boiling range) BRP-Y-N02 in products therefrom of the present invention or its add hydrogen Stablize oil, be often unsuitable for enter hydrogenation process BR because boiling point too it is low be easy to vaporize be difficult to serve as liquid phase solvent group Point；If the product of further heat cracking reaction is exactly to generate bulk gas and uneconomical into hydrogenation process BR；Cause This, unless carburet hydrogen Huge value, the first light diesel fuel (180~220 DEG C of fractions of conventional boiling range) BRP-Y-N02 usually should not be into Enter hydrogenation process BR or Special hydrogenation thermal cracking process or hydrocracking process or other thermal cracking processes processed, Hydrofining reaction process can usually be entered and carry out desulfurization, denitrogenation, production cleaning light diesel fuel.

The second light diesel fuel (220~265 DEG C of conventional boiling range in group technology direct hydrogenation liquefaction of coal products therefrom of the present invention Fraction) BRP-Y-N03, stabilized hydrogenation oil product, the boiling point that can be used as hydrogenation process BR needs is suitable, hydrogen supply capacity Excellent hydrogen supply dissolvent oil can add hydrogen in addition for hydrogenation process BR, the second light diesel fuel or its stabilized hydrogenation oil Play a part of the basic solvent composition of liquid phase in the front reaction process of reaction process BR, but hydrogenation process BR's It is most of in the reaction process of rear portion to have vaporized, and usually hydrogenation process BR there are the resource of surplus therefore belongs to and adds The product of hydrogen reaction process BR, therefore, the second light diesel fuel (220~265 DEG C of fractions of conventional boiling range) BRP-Y-N03 or its add hydrogen Stable oil, it may be necessary to partially be used as lightweight hydrogen supply dissolvent oil and be used for hydrogenation process BR, partially be used as and add hydrogen upgraded material For adding hydrogen upgrading reaction process to produce final products.

(265~350 DEG C of conventional boiling range evaporates heavy diesel fuel in group technology direct hydrogenation liquefaction of coal products therefrom of the present invention Point) BRP-Y-N04, stabilized hydrogenation oil product, can be used as hydrogenation process BR needs boiling point is suitable, hydrogen supply capacity is excellent Good hydrogen supply dissolvent oil, in addition for hydrogenation process BR, heavy diesel fuel or its stabilized hydrogenation oil, in hydrogenation process BR Whole process in can play the role of the basic solvent composition of liquid phase, and usually there are surpluses by hydrogenation process BR Resource therefore the major product for belonging to hydrogenation process BR, therefore, heavy diesel fuel (265~350 DEG C of fractions of conventional boiling range) BRP-Y- N04 or its stabilized hydrogenation oil, it may be necessary to partially be used as heavy hydrogen supply dissolvent oil and be used for hydrogenation process BR, partially be used as Add hydrogen upgraded material for plus hydrogen upgrading reaction process produce final products.

Light wax oil (350~480 DEG C of fractions of conventional boiling range) BRP-Y-N05 in products therefrom of the present invention, as long as its impurity Content meets the needs as needle-shape coke raw material, and should not usually return is hydrogenation process BR bis- times plus hydrogen.Present invention combination Light wax oil (350~480 DEG C of fractions of conventional boiling range) BRP-Y-N05 in technique direct hydrogenation liquefaction of coal products therefrom or its add Stabilized hydrogen oil product, can also return as needed is hydrogenation process BR bis- times plus hydrogen.

Wax slop (480~530 DEG C of fractions of conventional boiling range) BRP-Y-N06 in products therefrom of the present invention, as long as its impurity Content meets the needs as needle-shape coke raw material, should not usually return to hydrogenation process BR bis- times plus hydrogen.The present invention combines work Light wax oil (350~480 DEG C of fractions of conventional boiling range) BRP-Y-N05 in skill direct hydrogenation liquefaction of coal products therefrom or its add hydrogen Stablize oil product, can also return as needed is hydrogenation process BR bis- times plus hydrogen.In general, wax slop (conventional boiling range 480 ~530 DEG C of fractions) BRP-Y-N06 can carry a small amount of solid particle such as free carbon, and the carbon residue content for belonging to serious scarce hydrogen is high Material, excessive thermal cracking will generate thermal condensation object and even forms coke.

Due to normal boiling point residual oil (normal boiling point is higher than 530 DEG C of hydro carbons) BRP-Y-N07 in products therefrom of the present invention, lead to It is normally present in vacuum tower tower bottom heavy bitumen logistics, typically at least a part of discharge system no longer cyclic process, certainly, according to It needs that hydrogenation process BR can also be partially recycled back to.

As previously mentioned, it is a principal object of the present invention to produce the hydro-upgrading drip for being suitable as needle-shape coke raw material light asphalt Green component, therefore, in the separation fractional distillation process of the product BRP of hydrogenation process BR, normal boiling point is higher than 350 DEG C of difference The cutting scheme of fraction can according to need adjustment, for example can be the light fraction for being separated into 350~400 DEG C of conventional boiling range The mainly tower bottom oil of the remaining fractional composition by normal boiling point higher than 400 DEG C, can be and be separated into conventional boiling range 350~450 DEG C light fraction and the main tower bottom oil by normal boiling point higher than 450 DEG C of remaining fractional composition, can be and be separated into routine The tower bottom oil of the light fraction that 350~500 DEG C of boiling range and the mainly remaining fractional composition by normal boiling point higher than 500 DEG C, can be with It is to be separated into the light fraction of 350~530 DEG C of conventional boiling range and 530 DEG C of remaining fractional composition is mainly higher than by normal boiling point Tower bottom oil, naturally it is also possible to be to directly obtain the mainly tower bottom oil by normal boiling point higher than 350 DEG C of remaining fractional composition, Feasibility and stability, the mobility of tower bottom oil that above-mentioned separation scheme needs to consider to extract needle-shape coke raw material operating process etc. Related Technical Issues.

The air lift process 1HBM of thermal high separation process S10 of the invention described in detail below.

Air lift process 1HBM of the present invention, liquid hydrocarbon separate number with the counter current contacting of air lift hydrogen 1BH: generally 1 ~8 times, usually 2~4 times；The quantity of air lift hydrogen 1BH, according to air lift process 1HBM component separate target it needs to be determined that； The operating pressure of air lift process 1HBM, the operating pressure of the hydrogenation process of slightly less than high aromatic hydrocarbons；The behaviour of air lift process 1HBM Make temperature, according to air lift process 1HBM component separate target it needs to be determined that, usually 220~400 DEG C, generally 280~380 ℃。

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

Hydrogen upgrading reaction process HT66, the fixed bed reactors HT66-E used is added to can be 1 or 2 or more；Add Hydrogen grading process HT66 catalyst bed working method, can be any suitable form, can be two or more different types Reactor combination, can be down-type fixed-bed reactor, be also possible to upflow fixed bed reactor, it might even be possible to It is up flow type slight expanded-bed, catalyst bed working method is usually down-flow fixed bed.Use fixed bed hydrogenation reactor Plus hydrogen upgrading reaction process can be 1,2 or multiple beds using fixed bed catalyst bed, second and its subsequent Catalyst bed inlet temperature control mode, can be using cold hydrogen or and cold oil.

Fixed bed hydrogenation reactor adds hydrogen upgrading reaction process HT66, and use plus hydrogen upgrading catalyst HT66-C can Tandem compound to be 1,2 or multiple kinds plus hydrogen upgrading catalyst uses, along the flow direction of reaction stream, The hydrogenation activity that the hydrogenation activity of downstream hydrogenation upgrading catalyst, generally equal to or higher than upstream add hydrogen upgrading catalyst.

Fixed bed hydrogenation reactor plus hydrogen upgrading reaction process HT66, the reactor used, liquid in catalyst bed The volume ratio of phase, gas phase (or vapour phase), can be with liquid phase be it is main the case where, definition plus hydrogen upgrading catalyst bed in " liquid Phase actual volume/(liquid phase actual volume+gas phase actual volume) " be bed liquid phase fraction KL, divide rate KL can be greater than 0.75, Even greater than 0.95, actual liquid-phase hydrogenatin mode is formed, in order to keep adding the hydrogen partial pressure in hydrogen upgrading catalyst bed It is sufficiently high, it may be necessary to add hydrogen in the entrance of each upgrading catalyst bed.

High power and ultra high power graphite electrode made of needle coke, with resistivity is small, thermal expansion coefficient is small, heat-resisting punching Outstanding advantages of hitting property is strong, high mechanical strength, antioxygenic property are good can shorten electric furnace steel making smelting compared with ordinary electrode steel-making The time 50%~70% is refined, power consumption can reduce by 20%~50%, and production capacity can increase by 1.3 times.Therefore, high-quality needle coke is A kind of function carbon material of high value.

Needle coke preparation is using liquid-phase charring process, and coking raw material is during liquid carbonized gradually through pyrolysis and polycondensation Form mesophasespherule.Mesophasespherule again through sufficiently grown up, melt simultaneously, orientation, final curing for fibrous structure charcoal Product, i.e. needle coke.The production technology of needle coke includes 3 parts of pretreatment of raw material, delayed coking and calcining.

Coal-based needle coke of the present invention refers to needle coke made from the material obtained using coal as resource, the present invention Refer to needle coke made from the oil product based on coal tar.

About the feedstock property of coal-based needle coke, processing method, product performance index information, one for recording this kind of data Document is shown in document A01: 1. publication title: " coal tar chemical science ", page 262 to page 268；2. retrieval is encoded with books: ISBN Coding: 7-5024-2975-1, Chinese depository library CIP data core word (2002) the 014400th；3. writing: Xiao Ruihua； 4. publishing house: metallurgical industry publishing house.

As the feedstock oil of production needle coke, active component therein affects the forming process and as a result, drip of interphase Contain the reactive component (including olefin component) of a small amount of high activity in blueness, then cross-linking reaction can be carried out smoothly, and to take To crosslinking and condensation, be easy to get to anisotropic mosaic texture and fibrous structure.If high activity group present in pitch Sub-control crosslinking, then be the crosslinking of No yield point, then obtain isotropism carbon and fine mosaic texture.With low temperature distillation coal tar , often there is latter case in raw material of the oil as liquid phase carbonation, reason first is that containing more alkene, and hydrocarbon thermal cracking is anti- Process (including heat from hydrogenation cracking reaction process) is answered to generally produce alkene.Normally, the high temperature coal tar containing gluey pitch shape component The heat from hydrogenation cracking reaction process of oil can also generate a certain amount of olefin component, and the amount of carbon atom of these alkene is widely distributed, Normal boiling point is in the hydrocarbon component of needle-shape coke raw material light asphalt range and usually contains heat from hydrogenation crackate alkene.

Coal tar is described below.

Coal tar of the present invention refers to the processes such as the pyrolysis step from pyrolysis of coal or the dry distillation of coal or coal generating gas process Coal tar or its fraction, can be the by-product coalite tar or its fraction of coal generating gas, be also possible to coal coking pyrolysis of coal Process (including semicoke, medium temperature coking, high-temperature coking process) by-product coal tar or its fraction, can be above-mentioned coal tar Oil miscella, can be above-mentioned coal tar through light hydrocarbon solvent extract extract oil obtained such as depitching coal tar or Its distillate.

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: light oil (topping tar), carbolic oil, naphthalene in primary distillation process The products 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 is washed 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 in a certain range, the property of coal tar is also one Determine variation in range.The process conditions and product requirement of coal tar primary distillation process also change in a certain range, therefore coal tar The property of oily light fraction also changes in a certain range.The property of coal tar light fraction, specific gravity are usually 0.92~1.25, often It is usually 120~460 DEG C that rule boiling point, which is generally 60~500 DEG C, usual tenor is 5~80PPm, sulfur content be 0.4%~ 0.8%, nitrogen content is 0.6%~1.4%, oxygen content is 0.4%~9.0%, and usual water content is 0.2%~5.0%, residual Carbon content is usually 0.5%~13%.

Middle coalite tar of the present invention refers to producing from pyrolysis of coal or coal generating gas or the coal tar of other processes Product can be the medium temperature of coalite tar or medium temperature process of coking from semicoke process (pyrolysis temperature is lower than 700 DEG C) Coal tar (pyrolysis temperature is between 700~950 DEG C) or their miscella, usually contain coal tar heavy duty oil ingredient.Due to raw coal Property and coking or gas-making process condition change in a certain range, and the property of middle coalite tar is also in a certain range Variation.The property specific gravity of middle coalite tar of the present invention is usually 0.89~1.15, usual tenor be 5~ 200PPm, sulfur content are 0.1%~0.7%, nitrogen content is 0.6%~1.6%.Middle coalite tar of the present invention, sometimes Inorganic water content is 0.2%~5.0%, sometimes organic oxygen content be usually 2.5%~18%, in particular 3.5%~ 10%, more particularly 5%~10%.

Coal tar of the present invention is usually that 120~450 DEG C of the hydrocarbon components and normal boiling point are higher than comprising conventional boiling range The mixture of 450 DEG C of the hydrocarbon components, the light fraction FD1 fraction containing double ring arene that conventional boiling range is 120~260 DEG C, conventional boiling range are 260~370 DEG C of middle fraction FD2 contains bicyclic, thrcylic aromatic hydrocarbon fraction, and the heavy distillat FD3 that conventional boiling range is 370~450 DEG C is containing double For ring to Fourth Ring aromatic fraction, residue oil fraction FD4 of the conventional boiling range higher than 450 DEG C is coal tar pitch fraction.

Coal tar light fraction of the present invention oil, refer to normal boiling point be generally 60~480 DEG C, be usually 60~ 450 DEG C of coal tar distillate oil usually can carry out hydro-upgrading using fixed bed hydrogenation technology.

Coal tar heavy fraction of oil of the present invention refers to normal boiling point usually above 370 DEG C, generally greater than 400 DEG C Middle coalite tar fraction, their heat from hydrogenation cracking process, refer to occur at least part hydrocracking reaction production Molecular weight is lower than the process of cracked stock molecular weight, which generally comprises parallel hydrodemetallization, hydrofinishing plus hydrogen Heat cracking reaction, suitable reactor types are up flow type expanded bed such as suspended-bed reactors or fluidized bed reactor.

Residue oil fraction FD4 is generally difficult to realize long period using conventional bed technology, adds hydrogen lighting in high yield therefore adopt With up flow type expanded bed such as suspension bed or boiling bed hydrogenation technical transform it, gum asphalt is reunited in order to prevent, and cause need not The coking reaction wanted, it is often necessary to there is the solvent hydro carbons for ability of well dissolving each other to dissolve dispersion shape to it using with cinder oil distillate The weak solution of collagen asphalitine, solvent hydro carbons can be the heavy distillat FD3 that conventional boiling range is 370~450 DEG C, be also possible to The conversion product for adding hydrogen aromatic moiety saturation of heavy distillat FD3 and residue oil fraction FD4, be also possible to middle fraction FD2 adds hydrogen aromatic hydrocarbons The conversion product of fractional saturation.The conversion product for adding hydrogen aromatic moiety saturation of middle fraction FD2 belongs to excellent hydrogen supply dissolvent, is rich in Hydrogen supply hydrocarbon.

High aromatic carbon rate poor quality hydrocarbon HDS of the present invention, can be a kind of high aromatic hydrocarbons of long distillate, be also possible to 2 kinds or it is a variety of not With the high aromatic hydrocarbons of boiling range；The hydrogenation process that the hydrogenation modification reaction process BRA of high aromatic hydrocarbons of the present invention is carried out, can be with 1 kind of hydrocarbon HDS inferior is processed, the high aromatic carbon rate poor quality hydrocarbon HDS of 2 kinds or a variety of different boiling ranges can also be processed；Height of the present invention When the hydrogenation modification reaction process BRA of aromatic hydrocarbons processes the high aromatic hydrocarbons of 2 kinds or a variety of different boiling ranges, can be 2 tunnels or multichannel into Material, the catalyst bed or reaction compartment that the raw material that do not go the same way flows through can be identical or different, can be in parallel plus hydrogen relationship, Be also possible to respectively enter the relationship of the serial hydrogenation process of multi-reaction-area one after another, naturally it is also possible to be first front-end hydrogenation in parallel, Then the relationship of Unionfining again after front-end hydrogenation product converges, is also possible to other more complicated syntagmatics.

According to the present invention, before the coal tar carries out hydrotreating or before being fractionated, generally went through and filtered out admittedly The process of body particle.

Coal tar of the present invention usually contains the high valuable compound such as phenol, naphthalene, anthracene, can before entering hydrogenation process To extract high value compound therein.

The processing flow range of the material BRF of the high aromatic hydrocarbons HAC containing higher boiling, the hydrogenation modification reaction process including high aromatic hydrocarbons The separation fractional distillation process of the product of BRA, the rear portion serial hydrogenation reaction process BRK that may be used, hydrogenation process BR, can The hydro-upgrading process of hydrocarbon ils (it is high can to combine processing heat in the hot high score gas of the product for the hydrogenation process BR that can be used The distillate that point oil separates out), the stabilized hydrogenation reaction process MR of hydrogen supply dissolvent oil that may use, also may include producing The separation process of needle-shape coke raw material, the coking for producing needle coke, the calcination process of needle coke and other subsequent correlations add The process of work process or upstream initial coal tar.

The olefin(e) centent of fraction of the usual coal tar light fraction such as normal boiling point lower than 350 DEG C is high, phenol content is high, colloid Content is high and contains the more component easily reacted under the conditions of mitigation, therefore, the pre-add hydrogen mistake of the coal tar light fraction Journey, usually using hydrogenation protecting agent, olefins hydrogenation agent, hydrogenation deoxidation agent, removal of ccr by hydrotreating agent, hydrogen desulfurization agent etc. The tandem compound or mixed loading combination of single dose or double agent or multi-agent, usually using down-flow fixed bed hydrogenator.

The deep hydrogenation upgrading processes of coal tar light fraction, or logistics fraction obtained by the product of separation hydrogenation process BR Oil, progress plus hydrogen upgrading react to obtain plus hydrogen upgrading reaction product, hydrogen desulfurization agent, hydrodenitrogeneration agent, aromatic hydrocarbons may be used Add hydrogen saturator and cycloalkane add hydrogen ring opening catalyst, hydroisomerisation catalysts, hydrocracking catalyst etc. single dose or The tandem compound or mixed loading combination of double agent or multi-agent, usually using down-flow fixed bed hydrogenator.

The production process of coal tar and coal-based needle coke described in detail below.

Coal tar is the product of coal coking or coal generating gas or pyrolysis of coal or other coal hot procedures, since raw coal property exists Variation, coking or gas making or pyrolysis or other coal heat processing technique conditions change in a certain range in a certain range, therefore, The property of coal tar also changes in a certain range.The property specific gravity of coal tar of the present invention is usually 0.89~1.30, is led to Normal tenor is 5~1200PPm, sulfur content is 0.1%~1.2%, nitrogen content is 0.1%~1.8%, arene content is 50%~99%.Coal tar of the present invention, inorganic water content is 0.2%~5.0% sometimes, and organic oxygen content is sometimes 0.05%~12%, in particular 0.5%~10%.Coal tar of the present invention, usual content of ashes be 0.005%~ 5.00%.

The coal tar pitch or the other spices of addition for being suitable for using composition and property, can be made the needle coke haveing excellent performance.

About the feedstock property of coal-based needle coke, processing method, product performance index information, one for recording this kind of data Document is shown in document A02: 1. publication title: " delay coking process and engineering ", page 57~64, page 351~372；2. retrieval is used Books coding: ISBN coding: 978-7-80229-456-1, Chinese depository library CIP data core word (2007) the 168082nd Number；3. chief editor: Qu Guohua；4. publishing house: Sinopec publishing house.

About the feedstock property of coal-based needle coke, processing method, product performance index information, one for recording this kind of data Document is shown in document A03: 1. publication title: " Modern Coal-based Chemical technical manual ", page 1408 to page 1411；2. books are used in retrieval Coding: ISBN coding: 978-7-122-09636-4, Chinese depository library CIP data core word (2010) the 197010th； 3. chief editor: He Yongde；4. publishing house: Chemical Industry Press.

As the feedstock oil of production needle coke, wherein influencing the compositional factors that interphase is formed mainly has:

1. active component

Contain the reactive component of a small amount of high activity in pitch, then cross-linking reaction can be carried out smoothly, and to there is orientation Crosslinking and condensation, are easy to get to anisotropic mosaic texture and fibrous structure；If high-activity component control present in pitch Crosslinking is made, then is the crosslinking of No yield point, then obtains isotropism carbon and fine mosaic texture.With low temperature distillation coal tar work For the raw material of liquid phase carbonation, often there is latter case；

2. quinoline insolubles

Quinoline insolubles mentioned here refer to a quinoline insolubles, such as free carbon and carbon black.Their presence is led Reaction activity is caused to reduce, rate constant increases.Although the presence of quinoline insolubles is conducive to nucleation process mistake Journey, but be unfavorable for the growth of bead and melt simultaneously；When their mass fraction is more than 5%, the diameter of bead only has several microns, It and is in onion type structure.This structure is not easy to be graphitized；

3. oxygen, sulphur, nitrogen and its heterocyclic compound

There is a document announcement, the oxygen in pitch containing 7% or more leads to the conversion for completely inhibiting interphase, two obtained non-graphite The coke of change.Sulphur is added in pitch then can promote the rapid conversion of interphase, and additional amount is more than 7%, will cause interphase It is widely crosslinked between molecule, ultimately producing cannot graphited glass-like carbon.In addition sulphur can also cause brilliant swollen.Oxygen-containing, sulphur, nitrogen Heterocyclic compound heat reactivity it is high, participate in the nascent of mesophasespherule, and be enriched in wherein, and generate particulate and inlay knot Structure；

4. metallic element

Na, K, Mg, Ca, Fe, Cu, Al, V, Ni etc. are mainly contained in pitch, they can be such that asphaltene molecule activates, in acceleration Between mutually spherular generation and melt simultaneously, and form mosaic texture, will increase the thermalizing collision coefficient of needle coke.

The purpose of pretreatment of raw material process of coal-based needle coke, main technique is the quinoline insolubles removed in coal tar pitch (QI).The composition of coal tar pitch to interphase formation has a certain impact, for example, active component, quinoline insolubles, metallic element, Heterocyclic compound and nitrogen, sulphur, oxygen etc..The main component of coal tar pitch is aromatic hydrocarbon, but wherein contains a certain amount of quinoline non-soluble Object, wherein the agraphitic carbon that certain macromolecule resin shape substances are generated by thermal condensation when not only having coal tar distillation, also from refining The coal dust and coke powder that coke oven chambers are brought out with coal gas.They are attached to around interphase, hinder growing up, melting simultaneously for spherulite. The good needle coke of fibre structure can not be obtained after coking to prevent.Therefore, it is necessary to remove the primary quinoline for interfering spherula growth Insoluble moiety object (QI), then carries out compositional modulation again, and to obtain the raw material for meeting needle coke production and needing, this is to use coal tar pitch Produce the steps necessary of needle coke.Coal-based needle coke pretreatment of raw material process, mainly by filtration method, centrifugal separation, solvent Method, vacuum distillation method.Solvent method is divided into solvent-sedimentation, solvent-centrifugal process, solvent-filtration method, solvent-flocculence, molten again Agent-extraction process, supercritical extraction etc..

Production process of needle coke UT1 based on the coal tar pitch for not removing quinoline insolubles, generally includes pretreatment of raw material Journey UT1, delayed coking UT20, calcination process UT30.The spent hydroprocessing catalyst BRC's of material BRF containing coal tar pitch Floating bed hydrogenation upgrading processes BR obtains the floating bed hydrogenation product BRP containing BRC, and separation floating bed hydrogenation product BRP is contained The oil plant BRP-HS-VS of the floating bed hydrogenation upgraded product bituminous component of BRC；According to Conventional solvents method separation method, molten Agent method separation process UT1, the oil plant BRP-HS-VS of floating bed hydrogenation upgraded product bituminous component are separated into containing BRC containing solvent Light asphalt UT1-10-L and the solvent-laden heavy asphalt UT1-10-H containing BRC；Light asphalt UT1-10-L is in fractional distillation process UT1-20 is separated into Solvents Solvent UT1-10-L-S, the needle-shape coke raw material light asphalt tower bottom oil UT1-10-L-MIXP containing BRC, The separating resulting of this distillating method is needle-shape coke raw material light asphalt tower bottom oil UT1-10-L-MIXP containing a large amount of BRC, thus Reduction needle coke quality, which even results in, is unable to get needle coke, while the needle-shape coke raw material light asphalt tower bottom oil UT1- containing BRC 10-L-MIXP carries a large amount of catalyst BRC, has increased considerably the fresh catalyst consumption of BR.

Production process of needle coke UT based on the coal tar pitch for not removing quinoline insolubles, generally includes pretreatment of raw material process UT1, delayed coking UT2, calcination process UT3.

In the Materials Solvents method preprocessing process of coal-based needle coke, usually it is with the mixed solvent that aromatic hydrocarbons and aliphatic hydrocarbon are prepared Extractant removes the quinoline insolubles in raw material coal tar pitch by sedimentation separation.Pitch pre-processes to obtain needle-shape coke raw material essence There are many published methods of pitch and heavy asphalt processed, any one suitable method, typical method can be used in the present invention Have following several:

1. the production method of 200510136738.1 tar needle-shape coke of Chinese Patent Application No., uses aromatic hydrocarbons and aliphatic hydrocarbon Mixed proportion be 1: 0.6~1: 1.2 mixed solvent be extractant；

2. the production method and system of Chinese patent ZL200910198177.6 coal-based needle coke, in the solvent method that it is stated clearly In preprocessing process process conditions, the mass ratio of the coal tar asphalt and the solvent is 1: 0.6-1: 2.0；The solvent It is mixed by aliphatic hydrocarbon and aromatic hydrocarbon, the mass ratio of the aliphatic hydrocarbon and the aromatic hydrocarbon is 1: 0.6-1.4；The solvent Initial boiling point >=150 DEG C under normal pressure, quantity of distillate w/w >=95% before 310 DEG C；The aliphatic hydrocarbon is petroleum hydrocarbon solvent；It is described Aromatic hydrocarbon is one of Process of Tar Processing fraction or is mixed by several fractions in Process of Tar Processing, the fragrance Quantity of distillate w/w of the hydrocarbon under normal pressure, between 235-250 DEG C is 50%-85%；

3. a kind of technique for preparing needle-shape coke raw material using coal tar asphalt of Chinese patent ZL201110284485.8, at it In the solvent method preprocessing process process conditions stated clearly, after pitch and solvent are sufficiently mixed, removed using the method for physical separation Remove the insoluble matter in the mixed liquor；The physical separation is centrifuge separation, the viscosity for the mixed liquor being centrifuged For 40~90mpas；The solvent is fragrant for the mixture or BTX and coal measures of coal measures light oil and coal measures aromatic oil The mass ratio of the mixture of fragrant race's oil, the coal measures light oil or BTX and coal measures aromatic oil is 20: 80-95: 5；It is described The mass ratio of solvent and the pitch is 0.5-10；

4. Chinese patent ZL 201110339693.3 is a kind of to prepare needle-shape coke raw material using coal tar combination heavy phase recycle Technique, in the solvent method preprocessing process process conditions that it is stated clearly, comprising:

Coal tar and the first solvent are sufficiently mixed by step 1, are removed in the mixture using the method for physical separation First solvent insolubles obtain the first clarified solution；

First solvent is coal measures light oil, and the mass ratio of first solvent and the coal tar is 0.05-10；

Step 2, the first solvent being separated off in first clarified solution, to remove after first solvent it is remaining at Divide and carry out adding hydrogen, obtains refined bitumen；

First solvent insolubles obtained in step (1) are sufficiently mixed, using physical separation by step 3 with the second solvent Method remove the second solvent insolubles in the mixture, obtain the second clarified solution；

Second solvent is matter oil in coal measures, and the mass ratio of matter oil and the coal measures light oil is 1 in the coal measures: 0.1-1: 2, the mass ratio of second solvent and first solvent insolubles is 0.5-50；

Step 4, the second solvent being separated off in second clarified solution obtain purification heavy ingredient；

Step 5 mixes the refined bitumen and the purification heavy ingredient to get to the original for being used to prepare needle coke Material；

5. a kind of technique for producing needle coke of Chinese patent ZL 201310231391.3, locates in advance in the solvent method that it is stated clearly It manages in process conditions, the solvent is the mixture or BTX and coal measures of coal measures light oil and coal measures aromatic oil The mass ratio of the mixture of aromatic oil, the coal measures light oil or BTX and coal measures aromatic oil is 0.25-19；It is described molten The mass ratio of agent and the pitch is 0.5-10；The coal measures light oil is gas light oil, in tar light oil, naphtha light oil One or more, the coal measures aromatic oil is washing oil, absorbs oil, cresols oil, one or more of carbolineum；

6. Chinese Patent Application No. 201711084211.8 is compound with washing oil, carbolineum and asphalt component in middle coalite tar The technique for deploying raw material production needle coke, in the solvent method preprocessing process process conditions that it is stated clearly, the solvent extraction institute The mixture that the extractant used is formed for aromatic hydrocarbon and alkane according to the ratio that mass ratio is 1.2~1.8: 1, virtue therein Fragrant hydrocarbon is one of toluene, furfural, N-Methyl pyrrolidone or a variety of, and alkane is n-hexane, in normal heptane, hexamethylene It is any；Extractant employed in solvent extraction and the asphalt quality ratio in middle coalite tar are 1~3: 1, extraction temperature It is 60~80 DEG C, extraction time is 6~8h；

7. Chinese Patent Application No. 201711084214.1 is a kind of to produce coal measures needle by raw material of middle coalite tar pitch The technique of shape coke, in the solvent method preprocessing process process conditions that it is stated clearly, it is 1: 1~5 that extractant, which is by aralkyl mass ratio, : 1 aromatic hydrocarbon and alkane composition, wherein aromatic hydrocarbon is toluene, dimethylbenzene, any one in washing oil, alkane be n-hexane, Any one in normal heptane, hexamethylene；

8. the pretreatment of raw material solvent extraction system of 201810300971.6 needle coke industrialized production of Chinese Patent Application No. System and its method use the hybrid extraction of aromatic hydrocarbons and aliphatic hydrocarbon in the solvent method preprocessing process process conditions that it is stated clearly Agent, the aromatic hydrocarbon be washing oil, removal phenol carbolic oil or be washing oil and removal phenol carbolic oil mixture；The aliphatic hydrocarbon is aviation coal Oil.

There are many published methods that needle coke is prepared using coal tar pitch, any one suitable side can be used in the present invention Method, typical method have following 2 kinds:

1. Chinese patent ZL200510136737.7 is described using coal tar soft asphalt as the technique of waste needle coke, It is characterized in that, 320 DEG C of coking heater inlet temperature；420~520 DEG C of outlet temperature, raw material enters coking tower, start with 5 DEG C of heating rate rises to 440~450 DEG C by 420 DEG C per hour, and then constant temperature is fed 2~4 hours, then, is rapidly heated To 460~470 DEG C, constant temperature is fed 4~6 hours, then, is rapidly heated to 490~520 DEG C, the combined feed time 4~36 hours, Its advantage is that: needle coke thermal expansion coefficient obtained is low；Equipment uses existing equipment, does not have to improve；Needle coke heat obtained The technical requirements of manufacture high power electrodes and ultra-high power graphite electrode can be met, and manufacturing cost is lower.

2. Chinese patent ZL201510015130.7 describes the coproduction work of needle coke, mesocarbon microspheres, high-quality asphalt Process, the heavy phase pitch and material asphalt mixture generated using material asphalt pretreatment produces mesocarbon microspheres, in production Between the by-product pitch of phase carbon microspheres mixed with the refined bitumen that material asphalt pre-processes as needle-shape coke raw material, including original Expect pitch pretreatment, polymerization reaction, polymerizate separation and dry, by-product pitch processing, coking and calcine technology.With it is existing Technology is compared, the beneficial effects of the present invention are: 1) coal tar asphalt processing stage is high, at low cost, wide in variety and added value of product Height realizes maximization of economic benefit；2) overall process no waste discharge is produced, realizes that environmental benefit optimizes；3) technique spirit It is living, it is easy to operate, realize the efficient combination of needle coke, mesocarbon microspheres and high-quality asphalt production technology；4) product index spirit Work it is adjustable, can timely adaptation to market variations, improve enterprise resist market risk ability.

In the Materials Solvents method preprocessing process of coal-based needle coke, usually it is with the mixed solvent that aromatic hydrocarbons and aliphatic hydrocarbon are prepared Extractant removes the quinoline insolubles in raw material coal tar pitch, principle is the quinoline of fines in raw material by sedimentation separation The impurity such as insoluble moiety object occur flocking settling under mixed solvent effect, become larger in the moment, are 2 parts through sedimentation separation, clear Clear liquid (light phase) is substantially free of quinoline insolubles, and sedimentation liquid (heavy phase) has accumulated almost all quinoline insolubles, two-phase mixtures One distillation mode of material obtains refined bitumen (light asphalt) and heavy asphalt after solvent is separately recovered.The original of coal-based needle coke Expect pre-treatment solvents method, although complex process, investment are big, refined bitumen high income, needle coke be high-quality, stable operation, Therefore it is widely used, nippon, Mitsubishi's chemical conversion, Chinese Anshan Research Inst. of Heat Energy, China Iron & Steel Group use this method.

The usually raw material of production needle coke is the refined bitumen (light asphalt) for pre-processing coal tar pitch and obtaining, usually excellent Needle-shape coke raw material index be shown in Table 1, table 1 is needle-shape coke raw material technical indicator.

1 needle-shape coke raw material technical indicator of table

Project	General indicator	Excellent measure
			Arene content, % (mass fraction) >=	60
Conradson carbon residue, % (mass fraction)≤	10
			Ash content, % (mass fraction)≤	0.3	0.05
Sulphur content, % (mass fraction)≤	0.6	0.50
			Density, (g/cm³)≥		1.02
Quinoline insolubles QI≤		1.0
			Vanadium, PPm (weight)≤		50
Nickel, PPm (weight)≤		50
			Related coefficient BMCI >=		120

Coal-based needle coke feedstock oil of the present invention refers to the raw material hydrocarbon ils for preparing needle coke based on coal tar, it Can be the distillation fraction oil that fractionating coal tar obtains, can be light components that separation coal tar pitch obtains i.e. usually described in Light asphalt can be the hydro-upgrading oil product of the hydrocarbon ils based on coal tar.

Suitable coal-based needle coke feedstock oil routine boiling point range, usually 330~550 DEG C, that is, mainly by 3 ring knots Structure aromatic hydrocarbons, 4 ring structure aromatic hydrocarbons, 5 ring structure aromatic hydrocarbons composition, are preferably mainly made of 3 ring structure aromatic hydrocarbons, 4 ring structure aromatic hydrocarbons, and And the higher the better for the aromaticity of the hydrocarbon component, is conducive to improve the needle-shaped yield of coke of coking.

Coal-based needle coke feedstock oil of the present invention is commonly referred to as the raw material for preparing needle coke from high temperature coal-tar Hydrocarbon ils, it can be the distillation fraction oil that fractionation high temperature coal-tar obtains, can be what separating high-temp coal tar coal tar pitch obtained Light components are the usually described light asphalt, can be after the hydro-upgrading of the hydrocarbon ils based on high temperature coal-tar oil product or its Isolate.

In the delayed coking of coal-based needle coke, raw material is converted into gas, gasoline, kerosene, diesel oil, wax oil and coke. The delay coking process process and equipment of needle coke and the delayed coking of common petroleum coke are essentially identical, and capital equipment has heating Furnace, coke drum, fractionating column, but certain necessary measures are taken in individual plants, coking condition and operation, such as control The heating rate of charging, coking pressure tower, gas injection rate and adjustment recycle ratio, make oil plant is maintained in coking tower one relatively surely Fixed state makes full use of the Plastic Flow of mesophase material and the order of molecules align, while cuts gas-phase product generation Shear force creates the condition of so-called " air-flow draws burnt ", ultimately forms the needle coke of stream linear structure.Delayed coking production Needle coke contain higher moisture and volatile component, referred to as green coke, need to carry out high-temperature calcination in the case where completely cutting off air conditions Processing could be as high power, the raw material of ultra high power graphite electrode.

In the calcination process of coal-based needle coke, a series of variation occurs for structure and the element composition of needle coke, thus Improve the physicochemical property of needle coke.The purpose of calcining is the moisture and volatile matter removed in green coke, improves the carbon containing of coke Amount, density, intensity, electric conductivity and chemical stability.Needle coke calcination usually carries out in rotary kiln or rotary furnace, green coke from One end of kiln enters, the exhaust gas contact with high-temperature calcination, has combustion gas meeting oil burner in outlet end, calcining belt temperature can be high Up to 1500 DEG C.The rotation speed of kiln body determines residence time and heating speed of the coke in kiln, and needle coke is very close after calcining Degree is an important evaluation index for calcining effect, and needle coke belongs to after calcining of the real density greater than 2.130 grams/cc High-quality needle coke.

Table 2 is National Standard of the People's Republic of China GB/T 32158-2015 coal-based needle coke technical indicator.

2 coal-based needle coke technical indicator of table (GB/T 32158-2015)

As can also be seen from Table 2, content of ashes rises to 0.4% (mass fraction) by 0.3% (mass fraction), will make needle It is that primes therefore, be as little as possible in the upgrading processes of coal tar pitch that the product hierarchy of shape coke, which reduces class by top grade product, Introduce outer next life gray matter such as inorganic solid particles.That is, coal-based needle coke is effectively reduced using method appropriate Content of ashes in feedstock oil has great economy meaning.

Higher temperature is needed in the releasing of the calcination process of coal-based needle coke, sulphur, makes C-S chemical bond rupture, usually recognizes For in 1200~1500 DEG C of high temperature range sulphur could largely release, the high-sulfur of such high sulfur content feed coal asphalt production The sulfur content of needle coke product is high after the calcining of needle coke (green coke), high power and ultra high power graphite electrode made of it The coefficient of expansion it is higher, it may occur that beyond puffing as defined in SC service ceiling, to significantly influence to use function, from table 2 As can be seen that sulfur content by 0.4% (mass fraction) rise to 0.5% (mass fraction) will make the product hierarchy of needle coke by It is seconds that primes, which reduces class, and price is greatly reduced.Therefore, using method appropriate, coal-based needle coke original is effectively reduced Sulfur content in material oil has great economy meaning.

Currently, flash method, solvent method are had based on the industrial method that coal tar pitch produces needle-shape coke raw material oil, it is main Target is to control the quinoline insolubles content of needle-shape coke raw material oil.Flash method is cut from coal tar asphalt by vacuum distillation One section of raw material for being suitable for producing needle coke, isolates residue (including quinoline insolubles QI), which is process letter List, technological parameter are easily controllable, the disadvantage is that target product needle-shape coke raw material (fine fodder) yield is low.Solvent method aliphatic hydrocarbon and virtue Fragrant hydrocarbon is prepared into mixed solvent by a certain percentage, the boiling point of mixed solvent be generally below the boiling point of coal tar pitch to be processed so as to The distillation lock out operation in later period handles coal tar pitch with mixed solvent, removes quinoline insolubles, and advantage is needle-shape coke raw material (essence Material) high income, needle coke good product quality, the disadvantage is that the control of complex process, operating parameter requires, high, cost of investment is higher.

Either flash method or solvent method belong to the physical separation method for not changing molecular structure, accordingly, it is difficult to greatly The sulfur content of amplitude reduction coal-based needle coke feedstock oil, also can not be the suitably middle matter asphaltene molecule of the slightly larger structure of molecular weight Being changed into is suitable for small coal-based needle coke feedstock oil light asphalt, so both because sulfur content limits the high-quality needle coke of production High temperature coal-tar source, can not also improve that sulfur content is low, tenor is low, content of ashes is low, quinoline insolubles content is low High temperature coal-tar high boiling component in matter pitch utilization rate.

The property of typical branded oil system needle-shape coke raw material is shown in Table 3, by taking catalytic cracking clarified oil as an example, fragrant volume content Only 61.7%, far below the arene content in high-quality coal measures needle-shape coke raw material, this explanation, the coal-based needle coke of high arene content Raw material under conditions of it is suitable for low for guaranteeing aromatic hydrocarbons saturation depth, to the greatest extent may be used by adding hydrogen removing impurities matter (desulfurization, denitrogenation) reaction process Impurity (sulphur, nitrogen) content can be reduced, the more excellent needle-shape coke raw material of comprehensive performance can be prepared.Record this kind of data One document is shown in document A02: 1. publication title: " delay coking process and engineering ", page 57 to page 58；2. retrieval figure Book coding: ISBN coding: 978-7-80229-456-1, Chinese depository library CIP data core word (2007) the 168082nd； 3. chief editor: Qu Guohua；4. publishing house: Sinopec publishing house.

Table 3 is the property of typical branded oil system needle-shape coke raw material.,

The property of 3 typical branded oil system needle-shape coke raw material of table

Project	Catalytic cracking clarified oil	No. 1 thermal cracking tars	No. 1 thermal cracking tars
				Arene content, % (volume fraction) >=	61.7	89.8	66.1
Conradson carbon residue, % (mass fraction)≤	0.48	0.07	0.56
				Sulphur content, % (mass fraction)≤	5.7	9.4	8.6

The present invention, can combine processing component is suitable for, property is suitable medium temperature coal tar fraction or with medium temperature coal tar coal Pitch, for example, jet coal fluid bed fast pyrolysis process generate medium temperature coal tar coal tar pitch.

Since the operation target of hydrogenation modification reaction process BRA is that expectation obtains aromaticity height, low-sulfur content hydro carbons, because This ideal hydrogenation depth is that a kind of appropriateness adds hydrogen, needs the raw material according to specific floating bed hydrogenation modified-reaction process BR Product property (such as sulfur content, virtue of property (such as sulfur content, aromatic carbon rate) and desired floating bed hydrogenation modified-reaction process BR Carbon rate), select operating condition (such as catalyst type, catalytic amount, reaction pressure, reaction temperature, reaction time, the hydrogen of optimization Gas/oil volume ratio, way of operation).

Due to containing more colloid, asphalitine in high temperature coal-tar or high temperature coal-tar coal tar pitch, and only containing less The saturated hydrocarbons of amount, therefore, the adequate operation mode of hydro-upgrading reaction process BR are floating bed hydrogenation processes.

Since the operation target of hydrogenation modification reaction process BRA is that expectation obtains the suitable boiling range of property higher than 330 DEG C Modified heavy component, in order to reduce addition other materials separating energy consumption, the dilution hydrocarbon of addition or preferably main with hydrogen supply hydrocarbon It is lower than 330 DEG C of the hydrocarbon component by normal boiling point, and boiling point difference between the two is the bigger the better；In order to reduce the stream of cycle stock Journey range reduces investment and energy consumption, and the present invention recommends short route circulation technology.

As it is a kind of optimization operation method, in order to improve reduce it is undesirable chemical reaction (excessive hydrogenation saturated reaction, Excessive heat cracking reaction, excessive thermal condensation reaction), needing to shorten the reaction time shortens the heat effect time, it is therefore desirable to make With high-efficient effective catalyst (high activated catalyst of high degree of dispersion), it may be necessary to (be discharged using catalyst efficiency is improved Inhibit catalyst activity reaction product) flow technologies.

The method of the present invention produces needle while producing the raw material of high-quality high price carbon material such as needle coke of high value The coking of shape coke obtains coking distillate, can be with high temperature coal-tar fractional distillation process or with floating bed hydrogenation product BRP's The distillate that fractional distillation process obtains carries out combination hydrogenation modified together；The coking of production needle coke obtains heavy oil, can be with Into hydrogenation process BRA Unionfining.

In order to the delayed coking raw material of flexible modulation production needle coke sulfur content or and nitrogen content, can will at least one Point light asphalt or its component oil introduce fixed bed hydrogenation upgrading processes R600, carry out the suitable hydro-upgrading of hydrogenation depth into Row hydrodesulfurization reaction, hydrodenitrogeneration reaction, then separate hydro-upgrading process R600 product obtain production needle coke plus hydrogen Modify raw material R600-KP or reconciliation raw material.

The rear portion of hydrogenation modification reaction process BRA that may be present in high aromatic hydrocarbons BRF described in detail below is used in series The lower post-refining reaction process BRK of reaction temperature obtain alkene to reduce the high component of heat reactivity such as alkene The higher hydrogenation products BRKP of the lower stability of content, such as separation hydrogenation products BRKP obtain that olefin(e) centent is low, thermal response The low asphalt component of activity is used as high-quality needle-shape coke raw material pitch；Usual post-refining reaction process BRK is needed using high plus hydrogen Refine active disperse type catalyzer such as catalyst with base of molybdenum or with hydrogen supply hydrocarbon；The average behaviour of usual post-refining reaction process BRK Make the average operating temperature that temperature is significantly lower than hydrogenation modification reaction process BRA；It can also be arranged hydrogenation products BRKP's The gas phase hydrogenation olefin saturation section R70 of hot high score gas reduces the olefin(e) centent of hydro carbons in hot high score gas；Serial flow letter It is single, have the advantages that investment is low.

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

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

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

1. floating bed hydrogenation reactor；

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

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

4. slight expanded-bed.

Hydrocarbon catalytic heat cracking reaction process of the present invention, refers to the raw material hydrocarbon under hot cracking catalyst existence condition Occur with carbon-carbon bond fracture heat cracking reaction process as the main purpose, including usually described catalytic cracking reaction process or Catalytic cracking reaction process, the body material oil usually processed are wax oil, reduced crude, record a document of this kind of technology T001 is: 1. publication title: " catalytic cracking process and engineering "；2. retrieval is encoded with books: ISBN coding: 7-80043- 537-7；Chinese depository library CIP data core word: (2004) No. 131193；3. chief editor: Chen Junwu；4. publishing house: China Petrochemical industry publishing house.Pages 459 to page 488 of document T001 " catalytic cracking process and engineering ", it is light to describe typical catalytic cracking Diesel oil (light cycle oil), catalytic cracking recycle oil (heavy-cycle oil), catalytic cracking clarified oil physical data.According to specific dress The difference of the operating condition and product separation scheme set, catalytic cracking light diesel fuel (light cycle oil), catalytic cracking recycle oil (weight Recycle oil), the boiling point range of catalytic cracking clarified oil fluctuate in a certain range, and based on the present invention, catalytic thermal can be improved Cracking reaction generates the yield of the heavy wax oil of oil, and up flow type hydrogenation modification process is then gone to carry out hydrogenation reaction.

Coking heavy oil reaction process of the present invention is referred to the mink cell focus of poor hydrogen (such as decompression residuum, cracked residue Deng) it is raw material, under the conditions of high temperature and long reaction time, carry out the hot procedure of depth thermal cracking and condensation reaction, raw material It is converted into gas, naphtha, gasoline, diesel oil, heavy distillate (coking light wax oil, coking wax slop) and coke.Coking Technology type include autoclave coking, open hearth coking, delayed coking, contact coking, fluid coking, flexicoking.Modern heavy The techniques such as oily coking, including delayed coking, contact coking, fluid coking, flexicoking.One for recording this kind of technology Document T002 is: 1. publication title: " delay coking process and engineering "；2. retrieval is encoded with books: ISBN coding: 978- 7-80229-456-1；Chinese depository library CIP data core word: (2007) No. 168082；3. chief editor: Qu Guohua；4. going out Version society: Sinopec publishing house.Pages 188 to page 254 of document T002 " delay coking process and engineering " describe typical The physical data of delayed coking wax oil.According to the difference of the operating condition of specific device and product separation scheme, wax tailings Boiling point range fluctuates in a certain range, and based on the present invention, the yield that coking generates the heavy wax oil of oil can be improved, so After go up flow type hydrogenation modification process carry out hydrogenation reaction.

Due to catalytic cracking recycle oil (heavy-cycle oil), catalytic cracking clarified oil, wax tailings poor quality, it is difficult to directly Catalytic cracking is hydrocracked, and it is excellent to use the present invention then to realize into high aromatic hydrocarbons wax slop hydrogenation modification reaction process BRA Change processing.

Characteristic of the invention described in detail below.

The reaction of at least part removal of ccr by hydrotreating, front hydrogenation reaction occurs in front hydrogenation process BRA-A, BRF The carbon residue of material BRF of the carbon residue of hydro carbons lower than the high aromatic hydrocarbons RAC containing higher boiling in product BASE-BRA-AP；

Front hydrogenation reaction BRA-AR is carried out under conditions of based on the liquid phase reactor, and at least part the hydrocarbon component HD occurs Polycyclic aromatic hydrocarbon partial hydrogenation saturated reaction BRA-A-HD-HDAR make at least part the hydrocarbon component HD aromatic carbon rate reduce turn The hydrocarbon component HAC is turned to, makes the aromatic ring of at least part polycyclic aromatic hydrocarbon component HDA be saturated to form methylene bridged bond, front adds hydrogen The aromatic carbon rate of material BRF of the aromatic carbon rate of hydro carbons lower than the high aromatic hydrocarbons RAC containing higher boiling in reaction product BASE-BRA-AP；

Raw material BRK-FEED may include solid particulate materials BRK-FEEDS；

2. in serial operation low-temp reaction process BRK, there are hydrogen, hydrocarbon liquid phase, hydrogenation catalyst simultaneously there may be Dilute hydrocarbon or and there may be under the conditions of hydrogen supply hydrocarbon mixed phase material, raw material BRK-FEED carries out low temperature hydrogenation refining reaction BRK-R Obtain low temperature hydrogenation refining reaction product BASE-BRK-P；The alkene of hydro carbons in low temperature hydrogenation refining reaction product BASE-BRK-P Hydrocarbon concentration, lower than the concentration of olefin of hydro carbons in hydrogenation modification reaction product BRA-RASE-P；

The present invention, operating condition are usual are as follows:

The present invention, operating condition are general are as follows:

Raw material BRK-FEED may include solid particulate materials BRK-FEEDS；

1. using the material BRF of hydrogen supply hydrocarbon material DSF and the high aromatic hydrocarbons HAG containing higher boiling in hydrogenation modification reaction process BRA Or in which hydrogenation products contact；

(2) in removal process SR, thermal high separation process THPS is set；

Recycling plus hydrogen upgrading reaction product HT66-P.

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

2. the high hydrocarbon ils of content of ashes；

3. the high hydrocarbon ils of easy coking constituent content；

4. the high hydrocarbon ils of the easy reactant content of high temperature；

The general control principle of the gas-phase presulfiding hydrogen concentration of hydrogenation process of the invention described in detail below.

As needed, any hydrogenation process can be added in any supplement sulphur, but be typically incorporated into most upstream Hydrogenation process entrance, to guarantee reaction process necessary minimum concentration of hydrogen sulfide such as 500PPm (v) or 1000PPm (v) or the expected specified value such as 3000PPm (v), with guarantee the necessary hydrogen sulfide sectional pressure of catalyst not less than minimum specified value, To guarantee the necessary vulcanization kenel of catalyst.The supplement sulphur can be sulfide hydrogen or can be converted into pair of hydrogen sulfide Material of the hydroconversion process without ill-effect, such as hydrogen sulfide containing gas or oil product, or generated after being contacted with high-temperature hydrogen The molten sulfur or carbon disulfide of hydrogen sulfide or dimethyl disulfide etc..

The rule of the high pressure separation process of hydrogenation reaction effluent of the invention described in detail below.

The high pressure separation process of hydrogenation reaction effluent generally comprises cold high pressure separator, when hydrocarbon in hydrogenation reaction effluent When oil density big (such as close with water density) or viscosity are difficult to separate or contain solid particle greatly or with water emulsification, it is also necessary to The high pressure hot separator that operation temperature is usually 150~450 DEG C is set, and hydrogenation reaction effluent enters thermal high separation at this time Device is separated into the hot high score gas gas that one is mainly made of hydrogen in volume and one mainly by conventional liq hydrocarbon and can The hot high score oil liquid body of the composition of solid existing for energy, hot high score gas enter the cold anticyclone point that operation temperature is usually 20~80 DEG C It is separated into cold high score oil and cold high score gas from device, since a large amount of high boiling components enter in hot high score oil liquid body, is realized following Target: cold high score oil density becomes smaller or viscosity becomes smaller or is easily isolated with water.The high pressure separation process of hydrogenation reaction effluent is set High pressure hot separator is set, the advantages of reducing thermal loss is also equipped with, because hot high score oil liquid body can undergo to avoid hot high score gas The process that cools using air cooler or water cooler.Meanwhile part hot high score oil liquid body return upstream can be added into hydrogen Reaction process is recycled, to improve the overall raw material property for the hydrogenation process for receiving the recycle oil, or to the cycling hot High score oil carries out circulation plus hydrogen.

Between thermal high separate section and cold anticyclone separate section, as needed, warm high pressure separate section can be set, At this time after hot high score air cooling become gas-liquid two-phase material, be separated into warm high-pressure separator one in volume mainly by The warm high score gas gas of hydrogen composition and the warm high score oil being mainly made of conventional liq hydrocarbon and solid that may be present Liquid, warm high score gas gas enter cold anticyclone separate section and carry out cooling and gas-liquid separation.

Hydrogenation reaction effluent or hot high score gas or warm high score gas enter before cold anticyclone separate section, usually first reduce temperature (temperature should be higher than that the hydrogenation reaction effluent gas phase to degree (usually with reactive moieties feed exchange heat) to about 220~100 DEG C Middle sulphur hydrogenates crystallization temperature, the crystallization temperature of sal-ammoniac of ammonia), then usually injection washing water adds after forming water filling thereto Hydrogen reaction effluent, it may be necessary to which 2 or multiple injection points be set, and washing water is for absorbing ammonia and issuable other miscellaneous Matter such as hydrogen chloride etc., and the aqueous solution after absorbing ammonia necessarily absorbs hydrogen sulfide.Add after cold anticyclone separate section, the water filling Hydrogen reaction effluent separation are as follows: the cold high score gas being mainly made of hydrogen in volume, one mainly by conventional liq hydrocarbon Cold high score oil, a cold high score water be mainly made of water and dissolved with ammonia, hydrogen sulfide with dissolved hydrogen composition.It is described cold High score water, wherein the content of ammonia is generally 0.5~15% (w), preferably 1~8% (w).One purpose of note washing water is to inhale The ammonia and hydrogen sulfide in hydrogenation reaction effluent are received, prevents from forming sulphur hydrogenation ammonia or more sulphur ammonia Crystallization Plugging heat exchanger channels, increase Adding system pressure drop.The injection rate of the washing water should be determined according to following principles: on the one hand, washing water injects hydrogenation reaction It is divided into vapour phase water and liquid phase water after effluent, liquid phase water has to be larger than zero, preferably washs 30% or more of water inventory； In another aspect, washing water is used to absorb the ammonia in hydrogenation reaction effluent, prevent the ammonia density of high score gas too high, reduces catalysis Agent activity, the lower the ammonia volumetric concentration of usual high score gas the better, generally no greater than 200PPm (v), desirably no more than 50PPm (v).The cold high pressure separator operating pressure is that hydrogenation reaction partial pressure subtracts actual pressure drop, cold anticyclone separation unit The difference of point operating pressure and hydrogenation reaction pressure, it is unsuitable too low or excessively high, generally 0.35~3.2MPa, usually 0.5~ 1.5MPa.The hydrogen volume concentration value of the cold high score gas, should not too low (cause device operating pressure rise), generally answer Not less than 70% (v), preferably it is not less than 80% (v), preferably not below 85% (v).As previously described at least part, be usually 85 ~100% cold high score gas is returned to be recycled in hydrogenation reaction part, with provide the necessary amounts of hydrogen in hydrogenation reaction part and Hydrogen concentration；In order to improve plant investment efficiency, it is necessary to assure circulation hydrogen concentration is not less than lower limit value above-mentioned, for this purpose, according to tool The feedstock property of body, reaction condition, product distribution can exclude a part of cold high score gas to exclude the first that reaction generates Alkane, ethane.It, can be using conventional membrane separation process or pressure swing adsorption technique or oil wash technique for the cold high score gas of discharge It realizes hydrogen and the separation of non-hydrogen gas component, and the hydrogen of recycling is used as new hydrogen.It, can for the cold high score gas of recycling To realize hydrogen and the separation of non-hydrogen gas component using conventional membrane separation process or pressure swing adsorption technique or oil wash technique, and The hydrogen of recycling is used as new hydrogen

New hydrogen enters plus hydrogen partial is to supplement the hydrogen that hydrogenation process consumes, and the higher the better for new hydrogen hydrogen concentration, generally Not preferably less than 95% (v), preferably not below 99% (v).All new hydrogen can be introduced any hydrogenation reaction part, be preferably introduced First hydrogenator.

The present invention, in any reaction process, it can be entirely recycle hydrogen that the hydrogen gas stream used, which can be entirely new hydrogen, It can be the gaseous mixture of new hydrogen and recycle hydrogen.

For conventional gas hydrocarbon, CO, CO₂The hydrogenation modification reaction process BRA of the huge high aromatic hydrocarbons of yield, it is usually most of Cold high score gas of the cold high score gas than such as from about 70~100%, after being purified as membrane separation process obtained by permeated hydrogen pressurization after return Hydrogenation process does not permeate gas by PSA and mentions hydrogen or pressurization return plus hydrogen after " steam reforming hydrogen manufacturing+PSA mentions hydrogen " Reaction process is recycled.

Embodiment

Embodiment one

High temperature coal-tar feedstock property is shown in Table 4~table 9.

The general aspects that table 4 is high temperature coal-tar A is analyzed.

Table 5 is the yield of each narrow fraction of high temperature coal-tar A.

Table 6 is the property of 180 DEG C of fractions of < of high temperature coal-tar A.

Table 7 is the narrow fraction property 1 of high temperature coal-tar A.

Table 8 is the narrow fraction property 2 of high temperature coal-tar A.

Table 9 is the property analysis of the tar asphalt of high temperature coal-tar A.

The yield of the coal tar pitch of 450 DEG C of > of high temperature coal-tar A is 44.31% as can be seen from Table 5.

Using the present invention, target is that (yield is height to the destilling tower tower bottom coal tar pitch BSK of 420 DEG C of > of high temperature coal-tar A The 46% of warm coal tar A) hydro-upgrading is carried out, suspension bed is carried out using the coal tar pitch of the diluted high temperature coal-tar A of hydrogen supply dissolvent Hydrogenation modification reaction produces high-quality needle-shape coke raw material and carries out hydrogenation modification (increase hydrogen content, increase flowing to heavy asphalt Property, reduce viscosity, reduce softening point), while as far as possible reduce heavy asphalt in catalyst content, i.e., it is part is primary Heavy asphalt component is converted into the high-quality needle-shape coke raw material component of small molecule.

Using the present invention, and use a kind of similar low hydrogen content heavy oil using hydrogen supply hydrocarbon of patent ZL201210022921.9 Plus method, that is, coal tar heavy end that hydrogen lightening method is recorded carry out suspension bed (or the bubbling bed of heterogeneous catalysis Or slurry bed system) hydrocracking reaction, wherein hydrogen supply dissolvent is the fixation for the high temperature tar fraction that normal boiling point is 260~320 DEG C Hydrogen supply agent (hydrogen content is 8.5%~9.0%) after bed hydroprocessing, the weight flow of hydrogen supply dissolvent is the weight flow of coal tar pitch 0.65~0.75 times (by 0.7 calculate), steps are as follows:

A, coal tar pitch, hydrogen supply dissolvent, molybdenum base disperse type catalyzer, vulcanizing agent step with slurry: a certain amount of ingredients oil (is supplied Hydrogen solvent), granularity between 0.10~3.0 μm of powdered granule catalyst and vulcanizing agent (molten sulfur) together at 80 DEG C~200 DEG C It is uniformly mixed obtained oil-catalyst slurry under stirring condition, controls the solid concentration of oil-catalyst slurry in 20%~35% range, sulphur Agent enters in coal tar pitch slurry oil furnace charge coal tar pitch slurry oil after can also individually pressurizeing；

B, the hydrogenation modification reaction process BRA of high aromatic hydrocarbons；

Oil-catalyst slurry and remaining floating bed hydrocracking mixed raw material BRF and the recycle oil (catalyst containing catalyst Recycling internal circulating load is about 0.3~0.5 times of additive amount) to mix be mixture, mixture is through the boosting of raw material pump, mixed hydrogen, heating furnace Enter suspension bed (or bubbling bed or slurry bed system) hydrogenator after heating and carries out hydrocracking reaction, the additional amount of catalyst 500~the 550PPm for accounting for floating bed hydrogenation reactor feedstocks slurry is calculated with the fluidisation state compound by weight of metal molybdenum, with On the basis of 500PPm；

In the hydrogenation modification reaction process BRA of high aromatic hydrocarbons, floating bed hydrogenation reaction temperature is 420~440 DEG C, reaction pressure For 13~16MPa, 0.45~0.5h of volume space velocity^-1, hydrogen to oil volume ratio 500~800；

C, serial operation low-temp reaction process BRK；

The temperature of reaction effluent BRAP is 440 DEG C, reduces temperature to after 390 DEG C using chilling hydrogen, grasps into series connection Make the floating bed hydrogenation reactor of low-temp reaction process BRK, carries out postposition hydrofining reaction；

At 390~400 DEG C of reaction temperature of serial operation low-temp reaction process BRK, 13~16MPa of reaction pressure, volume 1.5~1.6h of air speed^-1, hydrogen to oil volume ratio 400~600；The concentration of olefin of hydro carbons in hydrogenation reaction product BRK-P is lower than first The 75% of the concentration of olefin of hydro carbons in hydrogenation reaction product BASE-BRP；To which the higher needle-shape coke raw material of thermal stability be made Manage light component；

Hydrogenation reaction product BRK-P obtains low point of liquid-solid phase heat after high-temperature high-pressure separator, high-temperature low-pressure separator Two part of oil mixture stream and hydrogen-rich gas.Hydrogen-rich gas is used as recycle hydrogen.Liquid-solid phase low point of oil mixture of heat flows through fractionating column After fractionation, normal boiling point is obtained lower than 360 DEG C of light distillates, tower bottom obtains the bottom of tower heavy oil containing catalyst and (is greater than 350 DEG C Distillate), fraction bottom of tower heavy oil can be used as recycle oil and be recycled directly to further progress in floating bed hydrogenation reactor Hydrogen lighting is added to react；It is most of to be used to whole bottom of tower heavy oil as maltha, as needed, it may be adjusted with carbolineum The softening point and mobility of maltha；

Light distillate of the normal boiling point less than 360 DEG C enters special plus hydrogen grading process in floating bed hydrogenation reaction product Produce the products such as gas, liquefied gas, naphtha, diesel component.

D, needle-shape coke raw material purification drip is separated into pitch preprocessing part UT1, the oil plant BRP-HS-VS of bituminous component The quinoline insolubles concentration of green UT1-LP and heavy asphalt UT1-HP, needle-shape coke raw material refined bitumen UT1-LP are lower than heavy asphalt The average normal boiling point of the quinoline insolubles concentration of UT1-HP, needle-shape coke raw material refined bitumen UT1-LP is lower than heavy asphalt UT1- The average normal boiling point of HP；

Pitch preprocessing part UT1 working method is solvent-sedimentation, includes solvent extraction and separation step UT1-10, extraction Take the distilation steps UT1-20 of separation discharge light liquid and the distilation steps UT1-30 of extraction and separation discharge heavy-fluid；

It is carried out in solvent extraction and separation step UT1-10, the oil plant BRP-HS-VS and solvent UT1-10-SF of bituminous component It is continuously mixed sedimentation separation, solvent UT1-10-SF extracts the light components in the oil plant BRP-HS-VS of bituminous component And light liquid phase is formed, the heavy component in the oil plant BRP-HS-VS of bituminous component forms heavy-fluid phase, light liquid phase and heavy-fluid phase It is discharged respectively after sedimentation separation, obtains the solvent-laden light asphalt UT1-10-L of BRC containing catalyst for hydro-upgrading and containing adding hydrogen to change The solvent-laden heavy asphalt UT1-10-H of matter catalyst BRC；

It is solvent-laden light in distillation the separating step UT1-20, BRC containing catalyst for hydro-upgrading of light asphalt UT1-10-L Matter pitch UT1-10-L is separated into the light asphalt distilled oil of solvent UT1-10-L-S, low catalyst for hydro-upgrading BRC content The liquid material UT1-10-L-HP of UT1-10-L-LP and enrichment catalyst for hydro-upgrading BRC；

Material based on solvent UT1-10-L-S returns to solvent extraction and separation step UT1-10 and is recycled, as solvent UT1- When 10-L-S loss amount is obvious, need to be interrupted supplementing solvent UT1-10-L-S；

The liquid material UT1-10-L-HP for being enriched with catalyst for hydro-upgrading BRC all returns to BR and BRF or its hydro-conversion object connects Touching, can return in the low pressure raw material coal tar pitch of BR, then enter reaction process BR together and be recycled；

The liquid material UT1-10-L-HP of a part enrichment catalyst for hydro-upgrading BRC can be returned into agent extraction and separation step UT1-10 and the oil plant BRP-HS-VS of bituminous component and are contacted with UT1-10-SF；

The material of whole light asphalt distilled oil UT1-10-L-LP based on low catalyst for hydro-upgrading BRC content, as Refined bitumen UT1-LP, the raw material UT2-TF as production needle coke, yield is 33% that yield is high temperature coal-tar A, is coal The 72% of pitch BSK.

In the solvent-laden heavy drip of the distilation steps UT1-30, BRC containing catalyst for hydro-upgrading of heavy asphalt UT1-10-H Green UT1-10-H is separated into the heavy asphalt UT1-10-H-HP of solvent UT1-10-H-S, the BRC containing catalyst for hydro-upgrading；

Material based on solvent UT1-10-H-S returns to solvent extraction and separation step UT1-10 and is recycled；

The heavy asphalt UT1-10-H-HP of part part BRC containing catalyst for hydro-upgrading can be returned BR and BRF or its The contact of hydro-conversion object, makes catalyst circulation amount be approximately equal to the additive amount of catalyst；

Can part the BRC containing catalyst for hydro-upgrading heavy asphalt UT1-10-H-HP return agent extraction and separation step UT1-10 and the oil plant BRP-HS-VS of bituminous component and are contacted with UT1-10-SF；

The heavy asphalt UT1-10-H-HP of 35%~100% BRC containing catalyst for hydro-upgrading is used as heavy asphalt UT1-HP is used as other coal pitch materials.

The quantity of catalyst for hydro-upgrading BRC accounts for hydro-upgrading in light asphalt UT1-10-L in liquid material UT1-10-L-HP Weight ratio SK100 >=0.98 of catalyst BRC quantity.

Hydro carbons weight accounts for the weight ratio SK300 of hydro carbons weight in light asphalt UT1-10-L in liquid material UT1-10-L-HP ≤0.05。

Weight ratio SK500 >=0.005 of catalyst for hydro-upgrading BRC in liquid material UT1-10-L-HP.

Extractant UT1-10-SF is the mixing that the weight ratio of aliphatic hydrocarbon and aromatic hydrocarbon is 1.0: 1.0~1.0: 1.2 Oil, wherein aliphatic solvent be normal heptane or and aviation kerosine, wherein aromatic hydrocarbon solvent be benzene or with toluene or with dimethylbenzene or And washing oil；

In solvent extraction and separation step UT1-10, extraction temperature is 60~80 DEG C, and extraction time is 8~10h, solvent UT1- The ratio of the weight flow of the oil plant BRP-HS-VS of the weight flow and bituminous component of 10-SF is 1.0~1.2.

For the floating bed hydrogenation device of 300,000 tons/year of coal tar pitch processing capacities, hydrogen supply agent flux is 210,000 tons/year, control Floating bed hydrogenation feeds the concentration 250PPm of catalyst metals in total slurry, then need 125 tons of catalyst (being calculated with metal)/ Year, it is about 30% of additive amount or more i.e. 37.5 ton/year or more that catalyst, which recycles internal circulating load,.

The present invention is conducive to micron order or nanoscale high activated catalyst (catalyst with base of molybdenum) using high degree of dispersion, can reduce Floating bed hydrogenation modified-reaction process BR gas yield significantly improves floating bed hydrogenation product heavy bitumen property and limits final Heavy bitumen product in catalyst amounts, as far as possible reduce pollutant introducing.

Embodiment two

It is shown in Table the high temperature coal-tar of 4~table 9, based on property in order to reduce the rule of floating bed hydrogenation modified-reaction process BRA Mould and reduction feed colloid, the concentration of asphalitine in BRF, and light asphalt, rear suspension bed hydro-upgrading system is made using first extracting It is processed for hydrogenated bitumen, finally with the route that hydrogenated bitumen prepares needle coke.

Maltha is made in the first step, separating high-temp coal tar；

Second step isolates light asphalt using the extracting process for being similar to embodiment one；

Third step prepares hydrogenated bitumen using floating bed hydrogenation modified technique of the present invention.

Using floating bed hydrogenation modified technique of the present invention, the step of preparing hydrogenated bitumen, operating procedure and condition are as follows:

A, using suspension bed (or bubbling bed or slurry bed system) hydrogenation modification reaction process, wherein hydrogen supply dissolvent is normal boiling point For the hydrogen supply agent (hydrogen content is 8.5%~9.0%) after the fixed bed hydrogenation of 260~320 DEG C of high temperature tar fraction, hydrogen supply The weight flow of solvent is 0.65~0.75 times (calculating by 0.7) of the weight flow of light asphalt；

B, light asphalt, hydrogen supply dissolvent, molybdenum base disperse type catalyzer, vulcanizing agent step with slurry: by a certain amount of ingredients oil (hydrogen supply dissolvent), granularity are between 0.10~3.0 μm of powdered granule catalyst and vulcanizing agent (molten sulfur) together 80 DEG C~200 DEG C stirring condition under be uniformly mixed obtained oil-catalyst slurry, control the solid concentration of oil-catalyst slurry in 20%~35% model It encloses, vulcanizing agent enters in light asphalt slurry oil furnace charge light asphalt slurry oil after can also individually pressurizeing；

C, the hydrogenation modification reaction process BRA of high aromatic hydrocarbons；

Oil-catalyst slurry and remaining floating bed hydrocracking mixed raw material BRF and the recycle oil (catalyst containing catalyst Recycling internal circulating load is about 1~2 times of additive amount) to mix be mixture, mixture heats up through the boosting of raw material pump, mixed hydrogen, heating furnace Enter suspension bed (or bubbling bed or slurry bed system) hydrogenator afterwards and carry out hydrocracking reaction, the additional amount of catalyst is with gold The fluidisation state compound by weight for belonging to molybdenum calculates the 230~250PPm for accounting for floating bed hydrogenation reactor feedstocks slurry, is with 250PPm Benchmark；

D, serial operation low-temp reaction process BRK；

Hydrogenation reaction product BRK-P obtains low point of liquid-solid phase heat after high-temperature high-pressure separator, high-temperature low-pressure separator Two part of oil mixture stream and hydrogen-rich gas.Hydrogen-rich gas is used as recycle hydrogen.Liquid-solid phase low point of oil mixture of heat flows through fractionating column After fractionation, normal boiling point is obtained lower than 360 DEG C of light distillates, normal boiling point between 360~530 DEG C of heavy distillates, tower bottom obtains To the bottom of tower heavy oil (normal boiling point is greater than 520 DEG C of distillate) containing catalyst, can partially make to most of bottom of tower heavy oil Being recycled directly to further progress in floating bed hydrogenation reactor for recycle oil adds hydrogen lighting to react, and makes catalyst circulation amount It is approximately equal to 2~3 times of the additive amount of catalyst；Part bottom of tower heavy oil is used as other pitch articles raw materials；

The general aspects of 4 high temperature coal-tar A of table is analyzed

The yield of each narrow fraction of 5 high temperature coal-tar A of table

Boiling range range DEG C	Narrow fraction yield, m%	Accumulative yield, m%
			< 180	1.85	1.85
180~210	3.34	5.19
			210~230	16.84	22.03
230~280	5.71	27.74
			280~330	6.60	34.34
330~360	4.66	39.00
			360~450	16.20	55.20
> 450	44.31	99.51
			Loss	0.49	100.00

The property of 180 DEG C of fractions of < of 6 high temperature coal-tar A of table

The narrow fraction property 1 of 7 high temperature coal-tar A of table

The narrow fraction property 2 of 8 high temperature coal-tar A of table

The property analysis of the tar asphalt of 9 high temperature coal-tar A of table

Claims

1. a kind of hydrogenation modification reaction method of the material of the high aromatic hydrocarbons containing higher boiling, it is characterised in that:

The high aromatic hydrocarbons HAC of higher boiling refers to that normal boiling point is higher than 450 DEG C of high aromatic carbon rate aromatic component, and aromatic carbon rate is higher than 50%；

1. in hydrogenation modification reaction process BRA, there are hydrogen, hydrocarbon liquid phase, there may be dilution hydrocarbon or and there may be confessions simultaneously Hydrogen hydrocarbon or and there may be under the conditions of the mixed phase material of solid particle catalyst, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is carried out Hydrogenation modification reaction BRA-R obtains hydrogenation modification reaction product BRA-BASE-P；In hydrogenation modification reaction product BRA-BASE-P At least part alkene may be contained；

The main body in hydrogenation modification reaction process BR is used using floating bed hydrogenation reactor in hydrogenation modification reaction process BRA Working morphology is the molybdenum base dispersibility hydrogenation catalyst of molybdenum disulfide MoS2, uses hydrogen supply dissolvent；

The material BRF of the high aromatic hydrocarbons HAC containing higher boiling is the high aromatic hydrocarbons HAC component of higher boiling for being higher than 450 DEG C comprising normal boiling point Material；

The material BRF of the high aromatic hydrocarbons HAC containing higher boiling includes conventional liquid hydrocarbon raw material BRF-L, may include solid particulate materials BRF-S；

Hydrogenation modification reacts BRA-R, comprising the high aromatic hydrocarbons HAC component of at least part higher boiling plus hydrogen aromatic moiety saturated reaction Or reacted at least part hydrodesulfurization reaction or at least part hydrogenation deoxidation or at least part hydrodenitrogeneration, it can It can also include that the heat from hydrogenation cracking reaction of the high aromatic hydrocarbons HAC component of at least part higher boiling or the thermal cracking generated free radicals are anti- It answers, the reaction of thermal cracking free radical stabilized hydrogenation；

Hydrogenation modification react BRA-R, comprising at least part hydrocarbon raw material BRF-L the high aromatic hydrocarbons HAC component of higher boiling plus hydrogen essence System reaction, may be comprising the heat from hydrogenation cracking reaction of the high aromatic hydrocarbons HAC component of higher boiling at least part hydrocarbon raw material BRF-L, can The hydrogenation reaction of at least part solid material BRF-S that may be present can be included；

Hydrogenation modification reaction BRA-R be characterized in that, hydrogenation modification react BRA-R hydrogen consumption in, at least 50% belong to plus hydrogen essence The hydrogen consumption of system reaction；

Hydrogenation modification reaction process BRA may use up flow type floating bed hydrogenation reactor using hydrogenator BRA-E BRA-E may use hydrogenation catalyst BRA-C；Hydrogenation modification reaction process BRA uses up flow type floating bed hydrogenation reactor BRA-E and when using hydrogenation catalyst BRA-C, the reaction compartment of the up flow type hydrogenator BRA-E used have catalyst into Enter, catalyst discharge；

There may be partial hydrogenation modified-reaction product BRA-BASE-P to deposit or stop or be circulated in inside hydrogenator BRA-E Space；

Hydrogenation modification reaction product BRA-BASE-P, for containing hydrogen, impurity composition, conventional gas hydrocarbon, conventional liq hydrocarbon simultaneously The mixed phase material including at least gas phase and liquid phase of solid particle may be contained；

Hydrogenation modification reaction effluent BRA-P is for being discharged hydrogenation modification reaction product BRA-BASE-P, to contain hydrogen, impurity Component, conventional gas hydrocarbon, conventional liq hydrocarbon may contain the mixed phase material including at least gas phase and liquid phase of solid particle simultaneously；

Hydrogenation modification reaction effluent BRA-P occurs, different BRA-PX in the form of 1 tunnel or 2 tunnels or multichannel material BRA-PX The composition and phase of logistics are identical or different；

Hydrogenation modification reaction process BRA, may include 2 or sub- hydroconversion reaction zone BRA-1, BRA-2 of multiple serial operations etc., At this point, the logistics comprising at least part conventional liquid hydrocarbon of the reaction effluent based on upper alien hydroconversion reaction zone enters downstream Adjacent sub- hydroconversion reaction zone, the sub- hydroconversion reaction zone BRA-1 of the first of hydrogenation modification reaction process BRA obtain reaction effluent BRA- 1P, the flow B RA-1PX comprising at least part hydrogenated oil BRA-1PO based on reaction effluent BRA-1P enters plus hydrogen The sub- hydroconversion reaction zone BRA-2 of the second of modified-reaction process BRA, the reaction effluent of last sub- hydroconversion reaction zone, which is used as, to be added Hydrogen modified-reaction effluent BRA-P is used；

The object comprising at least part conventional liquid hydrocarbon, at least part hydrogen based on hydrogenation modification reaction effluent BRA-P Material is used as hydrogenation process BR effluent BR-ENDP

(2) it in removal process SR, separates and recovers hydrogenation process BR effluent BR-ENDP and obtains in volume mainly by hydrogen group At hydrogen rich gas gas SRV and mainly contain the liquid stream SRL of solid particle by the possibility that conventional liquid hydrocarbon forms, at least one Part hydrogen rich gas gas SRV returns to hydrogenation process and is recycled.

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

1. in hydrogenation modification reaction process BRA, there are hydrogen, hydrocarbon liquid phase, there may be dilution hydrocarbon or and there may be confessions simultaneously Hydrogen hydrocarbon or and there may be under the conditions of the mixed phase material of solid particle catalyst, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is carried out Hydrogenation modification reaction BRA-R obtains hydrogenation modification reaction product BRA-BASE-P；In hydrogenation modification reaction product BRA-BASE-P Contain at least part alkene；

Hydrogenation modification reaction process BRA, the hydrogenation modification reaction process BRA front conversion zone BRA-A comprising serial operation and plus Hydrogen modified-reaction process BRA rear portion conversion zone BRA-B；

(a) in hydrogenation modification reaction process BRA front conversion zone BRA-A, there are hydrogen, hydrocarbon liquid phase, there may be dilutions simultaneously Hydrocarbon or with hydrogen supply hydrocarbon or under the conditions of the mixed phase material of solid particle catalyst, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is carried out Comprising adding the front hydrogenation reaction BRA-AR of hydrogen aromatic hydrocarbons either shallow saturated reaction to obtain front hydrogenation reaction product BASE-BRA-AP；

The material BRF of the high aromatic hydrocarbons HAC containing higher boiling is the high aromatic carbon hydrocarbon material of the hydrocarbon component HD comprising normal boiling point higher than 450 DEG C；

Front hydrogenation reaction BRA-AR, the hydrofining reaction comprising the hydrocarbon component HD at least part liquid hydrocarbon feeds BRF-L BRA-A-HD-HTR, hydrofining reaction BRA-A-HD-HTR include at least the partial hydrogenation saturated reaction BRA-A- of polycyclic aromatic hydrocarbon HD-HDAR, may comprising other unsaturated hydrocarbons plus hydrogen saturated reaction or with impure hydrocarbon plus hydrogen hydrogenolysis；

The reaction of at least part removal of ccr by hydrotreating, front hydrogenation reaction product occurs in front hydrogenation process BRA-A, BRF The carbon residue of material BRF of the carbon residue of hydro carbons lower than the high aromatic hydrocarbons HAC containing higher boiling in BASE-BRA-AP；

Front hydrogenation reaction BRA-AR is carried out under conditions of based on the liquid phase reactor, and at least part the hydrocarbon component HD occurs more The partial hydrogenation saturated reaction BRA-A-HD-HDAR of cycloaromatics makes the aromatic carbon rate reduction of at least part the hydrocarbon component HD be converted into hydrocarbon Component HAC makes the aromatic ring of at least part polycyclic aromatic hydrocarbon component HDA be saturated to form methylene bridged bond, and front hydrogenation reaction produces The aromatic carbon rate of material BRF of the aromatic carbon rate of hydro carbons lower than the high aromatic hydrocarbons HAC containing higher boiling in object BASE-BRA-AP；

Front hydrogenation reaction BRA-AR may use hydrogenation catalyst BRA-AC using up flow type hydrogenator BRA-AE；Before When portion hydrogenation process BRA-A uses hydrogenation catalyst BRA-AC, the reaction of the up flow type hydrogenator BRA-AE used Space has catalyst to enter, catalyst is discharged；

There may be front part hydrogenation reaction product BASE-BRA-AP to deposit or stop or be circulated in hydrogenator BRA-AE Portion space；

Front hydrogenation reaction product BASE-BRA-AP, for the object of solid particle may be contained simultaneously containing hydrogen, conventional liq hydrocarbon Material；

BRA-AP is for being discharged BASE-BRA-AP, for that may contain the object of solid particle simultaneously containing hydrogen, conventional liq hydrocarbon Material；

BRA-AP occurs, the composition and phase of different BRA-APX logistics in the form of 1 tunnel or 2 tunnels or multichannel material BRA-APX It is identical or different；

The flow B RA-AP-XO-TOBRA-B containing hydrocarbon ils in BRA-AP based on BRA-AP enters rear portion hydrogenation modification and reacted Journey BRAB；

(b) in hydrogenation modification reaction process BRA rear portion conversion zone BRA-B, there are hydrogen, hydrocarbon liquid phase, there may be dilutions simultaneously Hydrocarbon or and there may be hydrogen supply hydrocarbon or and there may be under the conditions of the mixed phase material of solid particle catalyst, flow B RA-AP-XO- TOBRA-B is carried out comprising adding the rear portion hydrogenation reaction BRA-BR of hydrogen aromatic hydrocarbons depth saturated reaction to obtain rear portion hydrogenation reaction product BASE-BRA-BP；

Flow B RA-AP-XO-TOBRA-B includes conventional liquid hydrocarbon raw material BRA-AP-XO-TOBRA-BL, may include solid Grain raw material BRA-AP-XO-TOBRA-BS；

Rear portion hydrogenation reaction BRA-BR may include hydrocarbon at least part conventional liquid hydrocarbon raw material BRA-AP-XO-TOBRA-BL The heat from hydrogenation cracking reaction of component HAC, may be comprising at least part conventional liquid hydrocarbon raw material BRA-AP-XO-TOBRA-BL The hydrofining reaction of the hydrocarbon component HAC；The hydrofining reaction of rear portion hydrogenation reaction BRA-BR adds hydrogen full comprising unsaturated hydrocarbons With reaction or with impure hydrocarbon plus hydrogen hydrogenolysis；

Hydrogenation modification reaction process BRA rear portion conversion zone BRA-B may be used and be added using up flow type hydrogenator BRA-BE Hydrogen catalyst BRA-BC；When hydrogenation modification reaction process BRA rear portion conversion zone BRA-B uses hydrogenation catalyst BRA-BC, use Up flow type hydrogenator BRA-BE reaction compartment have catalyst enter, catalyst discharge；

There may be part rear portion hydrogenation reaction product BASE-BRA-BP to deposit or stop or be circulated in hydrogenator BRA-BE Portion space；

Rear portion hydrogenation reaction effluent BRA-BP, for rear portion hydrogenation reaction product BASE-BRA-BP to be discharged, for containing hydrogen, Impurity composition, conventional gas hydrocarbon, conventional liq hydrocarbon may contain the mixed phase including at least gas phase and liquid phase of solid particle simultaneously Material；

Rear portion hydrogenation reaction effluent BRA-BP occurs, different BRA- in the form of 1 tunnel or 2 tunnels or multichannel material BRA-BPX The composition and phase of BPX logistics are identical or different；

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

(1) in hydrogenation modification reaction process BRA, there are hydrogen, hydrocarbon liquid phase simultaneously there may be dilution hydrocarbon or and there may be Hydrogen supply hydrocarbon or and there may be under the conditions of the mixed phase material of solid particle catalyst, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling into Row hydrogenation modification reaction BRA-R obtains hydrogenation modification reaction product BRA-BASE-P；Hydrogenation modification reaction product BRA-BASE-P In contain at least part alkene；

Front hydrogenation reaction BRF-AR, the hydrofining reaction comprising the hydrocarbon component HD at least part liquid hydrocarbon feeds BRF-L BRA-A-HD-HTR, hydrofining reaction BRA-A-HD-HTR include at least the partial hydrogenation saturated reaction BRA-A- of polycyclic aromatic hydrocarbon HD-HDAR, may comprising other unsaturated hydrocarbons plus hydrogen saturated reaction or with impure hydrocarbon plus hydrogen hydrogenolysis；

The flow B RA-AP-XO-TOBRA-B containing hydrocarbon ils in BRA-AP based on BRA-AP enters rear portion hydrogenation modification and reacted Journey BRA-B；

The reaction compartment of hydrogenation modification reaction process BRA rear portion conversion zone BRA-B divides sub- hydrogenation reaction according to following principles Area: every starting point for 1 cracking intermediate liquid product circulation occur then forms the separation of 1 second son hydroconversion reaction zone, therefore, There are the starting points of N number of cracking intermediate liquid product circulation, then form the separation of the sub- hydroconversion reaction zone of n times, then there is " M=N + 1 " a sub- hydroconversion reaction zone BRA-BX, X=1~(N+1)；N≥2；

The reaction compartment of hydrogenation modification reaction process BRA rear portion conversion zone BRA-B, the son for being divided into 2 or multiple serial operations add Hydroformylation reaction zone, the thermal high separation process of the sub- hydroconversion reaction zone of at least one before last 1 sub- hydroconversion reaction zone BRA-BM The cracking intermediate liquid product circulation flow B RA-BXMP-LR that BRA-B XMP-THPS is obtained returns to hydrogenation modification reaction process The front conversion zone BRA-A of BRA contacts generation at least part plus hydrogen saturated reaction with hydrogenation catalyst BRA-AC；

In hydrogenation modification reaction process BRA rear portion conversion zone BRA-B, include upper alien hydroconversion reaction zone conventional liquid hydrocarbon products Logistics, into the adjacent lower alien hydroconversion reaction zone of serial operation；

4. according to claim 1 or 2 or 3 the methods, it is characterised in that:

The logistics comprising at least part conventional liquid hydrocarbon based on hydrogenation modification reaction effluent BRA-P is used as serial operation The raw material BRK-FEED of the olefin-containing component containing hydrocarbon liquid phase of low-temp reaction process BRK；

Raw material BRK-FEED may include solid particulate materials BRK-FEEDS；

2. in serial operation low-temp reaction process BRK, there are hydrogen, hydrocarbon liquid phase, hydrogenation catalyst simultaneously there may be dilutions Hydrocarbon or and there may be under the conditions of hydrogen supply hydrocarbon mixed phase material, raw material BRK-FEED carries out low temperature hydrogenation refining reaction BRK-R and obtains Low temperature hydrogenation refining reaction product BASE-BRK-P；The alkene of hydro carbons is dense in low temperature hydrogenation refining reaction product BASE-BRK-P Degree, lower than the concentration of olefin of hydro carbons in hydrogenation modification reaction product BRA-BASE-P；

Low temperature hydrogenation refining reaction BRK-R, the olefins hydrogenation comprising at least part the hydrocarbon component HAC in raw material BRK-FEED Reaction, the hydrofining reaction comprising at least part the hydrocarbon component in raw material BRK-FEED may be comprising in raw material BRK-FEED The heat from hydrogenation cracking reaction of at least part the hydrocarbon component；The hydrofining reaction of low temperature hydrogenation refining reaction BRK-R includes insatiable hunger With hydrocarbon plus hydrogen saturated reaction or with impure hydrocarbon plus hydrogen hydrogenolysis；

Serial operation low-temp reaction process BRK may use up flow type hydrogenator BRK- using hydrogenator BRK-E E；Serial operation low-temp reaction process BRK is using up flow type floating bed hydrogenation reactor B RK-E and uses hydrogenation catalyst When BRK-C, the reaction compartment of the up flow type hydrogenator BRK-E used has catalyst to enter, catalyst is discharged；

There may be part low temperature hydrogenation refining reaction product BASE-BRK-P to deposit or stop or be circulated in hydrogenator BRK-E Inner space；

Low temperature hydrogenation refining reaction product BASE-BRK-P, to contain hydrogen, impurity composition, conventional gas hydrocarbon, conventional liq hydrocarbon The mixed phase material including at least gas phase and liquid phase of solid particle may be contained simultaneously；

Low temperature hydrogenation refining reaction effluent BRK-P for low temperature hydrogenation refining reaction product BASE-BRK-P to be discharged, for containing Hydrogen, impurity composition, conventional gas hydrocarbon, conventional liq hydrocarbon may include at least gas phase and liquid phase containing solid particle simultaneously Mixed phase material；

Low temperature hydrogenation refining reaction effluent BRK-P occurs, different BRK- in the form of 1 tunnel or 2 tunnels or multichannel material BRK-PX The composition and phase of PX logistics are identical or different；

The reaction compartment of serial operation low-temp reaction process BRK, may the sub- hydrogenation reaction comprising 2 or multiple serial operations Area, at this point, the logistics comprising at least part conventional liquid hydrocarbon of the reaction effluent based on upper alien hydroconversion reaction zone enters First sub- hydroconversion reaction zone BRK1 of the adjacent sub- hydroconversion reaction zone in downstream, serial operation low-temp reaction process BRK obtains reaction stream Object BRK1-P out, the flow B RK1-PX comprising at least part hydrogenated oil BRK1-PO based on reaction effluent BRK1-P Into the second sub- hydroconversion reaction zone BRK2 of serial operation low-temp reaction process BRK, the reaction of last sub- hydroconversion reaction zone Effluent is used as low temperature hydrogenation refining reaction effluent BRK-P；

What it is based on low temperature hydrogenation refining reaction effluent BRK-P includes at least part conventional liquid hydrocarbon, at least part hydrogen Material, be used as hydrogenation process BR effluent BR-ENDP

(2) it in removal process SR, separates and recovers low temperature hydrogenation refining reaction effluent BRK-P and obtains in volume mainly by hydrogen group At hydrogen rich gas gas SRV and mainly contain the liquid stream SRL of solid particle by the possibility that conventional liquid hydrocarbon forms, at least one Part hydrogen rich gas gas SRV returns to hydrogenation process and is recycled.

5. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(1) in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling be selected from one of following materials or It is several:

1. the hydrocarbon material based on coalite tar is obtained by coalite tar or its distillate or its extraction oil or its hot procedure Oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis process；

2. the hydrocarbon material based on medium temperature coal tar is obtained by medium temperature coal tar or its distillate or its extraction oil or its hot procedure Oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis process；

3. the hydrocarbon material based on high temperature coal-tar is obtained by high temperature coal-tar or its distillate or its extraction oil or its hot procedure Oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis process；

4. being that oil product obtained by direct hydrogenation liquefaction of coal liquefaction process or its heat add based on the hydrocarbon material of direct hydrogenation liquefaction of coal product oil Oil product obtained by work process, direct hydrogenation liquefaction of coal liquefaction process includes the direct hydrogenation liquefaction of coal liquefaction mistake using hydrogen supply dissolvent oil Journey, coal refines process to oil altogether, coal faces hydrogen thermosol liquefaction process, and hot procedure is distillation process or thermal cracking process or coking Or catalytic cracking process or catalytic pyrolysis process；

5. the hydrocarbon material based on petroleum based heavy fuel oils is obtained by petroleum based heavy fuel oils or its distillate or its extraction oil or its hot procedure Oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis process；

6. oil product obtained by the hydrocarbon material based on shale oil, shale oil or its distillate or its extraction oil or its hot procedure, heat adds Work process is distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis process；

7. being tar sand base weight oil or its distillate or its extraction oil or its hot procedure based on the hydrocarbon material of tar sand base weight oil Gained oil product, hot procedure are distillation process or thermal cracking process or coking or catalytic cracking process or catalytic pyrolysis mistake Journey；

6. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(1) normal boiling point in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is higher than 450 DEG C The aromatic carbon rate of hydrocarbon reduces by 5~50%.

7. according to claim 1 or 2 or 3 the methods, it is characterised in that:

Normal boiling point in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is higher than 450 DEG C of hydrocarbon Aromatic carbon rate reduces by 10~30%.

8. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(1) extrusion rate of the organic sulfur in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is 5 The extrusion rate of organic nitrogen in~60%, or the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is 5~45%.

9. according to claim 1 or 2 or 3 or 4 the methods, it is characterised in that:

(1) extrusion rate of the organic sulfur in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is 5 The extrusion rate of organic nitrogen in~30%, or the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is 5~20%.

10. method according to claim 4, it is characterised in that:

The concentration of olefin of hydro carbons, low in serial operation low-temp reaction process BRK, low temperature hydrogenation refining reaction effluent BRK-P The 35% of the concentration of olefin of hydro carbons in hydrogenation modification reaction effluent BRA-P.

11. according to claim 1 or 2 or 3 the methods, it is characterised in that:

Normal boiling point in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is higher than 450 DEG C of hydrocarbon Aromatic carbon rate reduces by 5~50%；

The concentration of olefin of hydro carbons, low in serial operation low-temp reaction process BRK, low temperature hydrogenation refining reaction effluent BRK-P The 65% of the concentration of olefin of hydro carbons in hydrogenation modification reaction effluent BRA-P.

12. according to claim 1 or 2 or 3 the methods, it is characterised in that:

Normal boiling point in hydrogenation modification reaction process BRA, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is higher than 450 DEG C of hydrocarbon Aromatic carbon rate reduces by 10~35%；

The concentration of olefin of hydro carbons, low in serial operation low-temp reaction process BRK, low temperature hydrogenation refining reaction effluent BRK-P The 75% of the concentration of olefin of hydro carbons in hydrogenation modification reaction effluent BRA-P.

13. according to claim 1 or 2 or 3 the methods, it is characterised in that:

Hydrogenation modification reacts in the hydrogen consumption of BRA-R, and 70~95% belong to the hydrogen consumption of hydrofining reaction.

14. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(2) in removal process SR, the H of hydrogen rich gas gas SRV₂Volumetric concentration is greater than 75%.

15. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(2) in removal process SR, the H of hydrogen rich gas gas SRV₂Volumetric concentration is greater than 85%.

16. according to claim 1 or 2 or 3 the methods, it is characterised in that:

1., using floating bed hydrogenation reactor, the hydrogenation catalyst BRA-C used is a kind of in hydrogenation modification reaction process BRA Composite hydrogenation catalyst includes high-activity component and low activity component；The high-activity component metal and low activity group parting The weight ratio of category is 1: 10 to 10: 1；The high-activity component is or mixtures thereof the water soluble salt compound of molybdenum；It is described low Active component is ferric oxide ore or iron sulfide ore, and wherein iron in ore content is not less than 40wt%, and catalyst BRA-C water contains Amount is lower than 2wt%；The powdered granule that BRA-C particle diameter is 1~100 μm；

The operating condition of hydrogenation modification reaction process BRA are as follows: temperature is 300~480 DEG C, pressure is 4.0~30.0MPa, hydrogen/ Feedstock oil volume ratio is the material that 0.01: 1~4000: 1, hydrogenation catalyst BRA-C is added that weight is the high aromatic hydrocarbons HAC containing higher boiling BRF weight 0.001%~8.0%, volume space velocity be 0.1~10.0hr^-1；The material BRF weight of the high aromatic hydrocarbons HAC containing higher boiling Chemical hydrogen consumption amount is 0.05%~4.0%.

17. according to claim 1 or 2 or 3 the methods, it is characterised in that:

1., using floating bed hydrogenation reactor, the hydrogenation catalyst BRA-C used is at least wrapped in hydrogenation modification reaction process BRA Element containing Mo, Mo are molybdenum disulfide MoS2, hydrogenation catalyst BRA-C in the body of work form of hydrogenation modification reaction process BRA For 0.0001~100 μm of powdered granule；

The operating condition of hydrogenation modification reaction process BRA are as follows: temperature is 360~460 DEG C, pressure is 6.0~22.0MPa, hydrogen/ Feedstock oil volume ratio is the material that 50: 1~2000: 1, hydrogenation catalyst BRA-C is added that weight is the high aromatic hydrocarbons HAC containing higher boiling BRF weight 0.001%~5.0%, volume space velocity be 0.2~5.0hr^-1；The material BRF weight of the high aromatic hydrocarbons HAC containing higher boiling Chemical hydrogen consumption amount is 0.25%~3.0%.

18. according to claim 1 or 2 or 3 the methods, it is characterised in that:

The operating condition of hydrogenation modification reaction process BRA are as follows: temperature is 360~460 DEG C, pressure is 8.0~16.0MPa, hydrogen/ Feedstock oil volume ratio is the material that 200: 1~1200: 1, hydrogenation catalyst BRA-C is added that weight is the high aromatic hydrocarbons HAC containing higher boiling BRF weight 0.001%~5.0%, volume space velocity be 0.5~3.0hr^-1；The material BRF weight of the high aromatic hydrocarbons HAC containing higher boiling Chemical hydrogen consumption amount is 0.25%~2.5%.

19. method according to claim 4, it is characterised in that:

2. serial operation low-temp reaction process BRK, uses floating bed hydrogenation reactor, operating condition are as follows: temperature is 280~440 DEG C, pressure be 4.0~30.0MPa, hydrogen/feedstock oil volume ratio is 30: 1~4000: 1, hydrogenation catalyst BRK-C be added weight For the material BRF weight of the high aromatic hydrocarbons HAC containing higher boiling 0.001%~8.0%, volume space velocity be 0.3~10.0hr^-1；

The average reaction temperature of serial operation low-temp reaction process BRK is lower than the average response temperature of hydrogenation modification reaction process BRA At least 10 DEG C of degree.

20. method according to claim 4, it is characterised in that:

2. serial operation low-temp reaction process BRK, uses floating bed hydrogenation reactor, operating condition are as follows: temperature is 300~420 DEG C, pressure be 6.0~22.0MPa, hydrogen/feedstock oil volume ratio is 30: 1~2000: 1, hydrogenation catalyst BRK-C be added weight For the material BRF weight of the high aromatic hydrocarbons HAC containing higher boiling 0.001%~5.0%, volume space velocity be 0.6~5.0hr^-1；

The average reaction temperature of serial operation low-temp reaction process BRK is lower than the average response temperature of hydrogenation modification reaction process BRA At least 20 DEG C of degree.

21. method according to claim 4, it is characterised in that:

2. serial operation low-temp reaction process BRK, uses floating bed hydrogenation reactor, operating condition are as follows: temperature is 300~420 DEG C, pressure be 8.0~16.0MPa, hydrogen/feedstock oil volume ratio is 20: 1~1200: 1, hydrogenation catalyst BRK-C be added weight For the material BRF weight of the high aromatic hydrocarbons HAC containing higher boiling 0.001%~3.0%, volume space velocity be 0.3~2.0hr^-1；

The average reaction temperature of serial operation low-temp reaction process BRK is lower than the average response temperature of hydrogenation modification reaction process BRA At least 25 DEG C of degree.

22. according to Claims 2 or 3 the method, it is characterised in that:

1. the material BRF of the high aromatic hydrocarbons HAC containing higher boiling come from coal tar, gum asphaltic content be 10%~90% or with it is residual Charcoal is 0.01%~60%；

(a) in hydrogenation modification reaction process BRA front conversion zone BRA-A, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling carry out with Add hydrogen aromatic hydrocarbons either shallow saturated reaction or with removal of ccr by hydrotreating reaction based on front hydrogenation reaction BRA-AR, make the colloid of material BR Asphalitine hydrogenation and removing rate is greater than 5% or is greater than 5% with carbon residue hydrogenation and removing rate；

(b) in hydrogenation modification reaction process BRA rear portion conversion zone BRA-B, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is re-quantization Hydrogen consumption is learned, 65% or more of hydrogenation modification reaction process BRA overall weight chemical hydrogen consumption amount is accounted for.

23. according to Claims 2 or 3 the method, it is characterised in that:

1. the material BRF of the high aromatic hydrocarbons HAC containing higher boiling come from high temperature coal-tar, gum asphaltic content be 10%~90% or Or with carbon residue be 0.01%~60%；

(a) in hydrogenation modification reaction process BRA front conversion zone BRA-A, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling carry out with Add hydrogen aromatic hydrocarbons either shallow saturated reaction or with removal of ccr by hydrotreating reaction based on front hydrogenation reaction BRA-AR, make the colloid of material BR Asphalitine hydrogenation and removing rate is greater than 25% or is greater than 30% with carbon residue hydrogenation and removing rate；

(b) in hydrogenation modification reaction process BRA rear portion conversion zone BRA-B, the material BRF of the high aromatic hydrocarbons HAC containing higher boiling is re-quantization Hydrogen consumption is learned, 60% or more of hydrogenation modification reaction process BRA overall weight chemical hydrogen consumption amount is accounted for.

24. according to claim 1 or 2 or 3 the methods, it is characterised in that:

Are arranged by thermal high and was separated by intermediate reaction product or final reacting product BRAGP in hydrogenation modification reaction process BRA Journey BRAGP-THPS；

In thermal high separation process BRAGP-THPS, intermediate reaction product or final reacting product BRAGP are separated, is obtained containing molten Solution hydrogen, normal boiling point are higher than the hot high score oil of the hot high score liquid for the conventional liquid hydrocarbon that 350 DEG C of possibility contains solid particle The BRAGP-THPS-L and hot high score oil BRAGP-THPS-PP of net product stream；

Hot high score oil BRAGP-THPS-L returns to thermal high separation process as recycle oil BRAGP-THPS-LR at least partially The reaction compartment and hydrogenation catalyst BRA-C of at least part hydrogenation modification reaction process BRA is passed through in the upstream of BRAGP-THPS Contact is contacted by the reaction compartment of at least part serial operation low-temp reaction process BRK with hydrogenation catalyst BRK-C.

25. according to claim 1 or 2 or 3 the methods, it is characterised in that:

In hydrogenation modification reaction process BRA, using floating bed hydrogenation reactor B RA-GE, to intermediate reaction product or end reaction Thermal high separation process BRAGP-THPS is arranged in product BRAGP；

Hot high score oil BRAGP-THPS-L returns to thermal high separation process as recycle oil BRAGP-THPS-LR at least partially The reaction compartment of at least part hydrogenation modification reaction process BRA is passed through in the upstream of BRAGP-THPS；

Thermal high separation process BRAGP-THPS, is arranged in the upper space of floating bed hydrogenation reactor B RA-GE, is received with liquid The system of storage, drain pipeline, circulating pump, liquor charging pipeline composition, makes at least part collection liquid BRAGP-THPS-LR return to heat The reaction compartment of at least part hydrogenation modification reaction process BRA is passed through in the upstream of high pressure separation process BRAGP-THPS.

26. method according to claim 4, it is characterised in that:

Thermal high point is arranged to intermediate reaction product or final reacting product BRKGP in serial operation low-temp reaction process BRK From process BRKGP-THPS；

In thermal high separation process BRKGP-THPS, intermediate reaction product or final reacting product BRKGP are separated, is obtained containing molten Solution hydrogen, normal boiling point are higher than the hot high score oil of the hot high score liquid for the conventional liquid hydrocarbon that 350 DEG C of possibility contains solid particle The BRKGP-THPS-L and hot high score oil BRKGP-THPS-PP of net product stream；

Hot high score oil BRKGP-THPS-L returns to thermal high separation process as recycle oil BRKGP-THPS-LR at least partially The reaction compartment of at least part serial operation low-temp reaction process BRK is passed through in the upstream of BRKGP-THPS.

27. according to claim 1 or 2 or 3 the methods, it is characterised in that:

In serial operation low-temp reaction process BRK, using floating bed hydrogenation reactor B RK-GE, to intermediate reaction product or finally Thermal high separation process BRKGP-THPS is arranged in reaction product BRKGP；

Hot high score oil BRKGP-THPS-L returns to thermal high separation process as recycle oil BRKGP-THPS-LR at least partially The reaction compartment of at least part serial operation low-temp reaction process BRK is passed through in the upstream of BRKGP-THPS；

Thermal high separation process BRKGP-THPS, is arranged in the upper space of floating bed hydrogenation reactor B RK-GE, is received with liquid The system of storage, drain pipeline, circulating pump, liquor charging pipeline composition, makes at least part collection liquid BRKGP-THPS-LR return to heat The reaction compartment of at least part serial operation low-temp reaction process BRK is passed through in the upstream of high pressure separation process BRKGP-THPS.

28. method according to claim 4, it is characterised in that:

In thermal high separation process BRKGP-THPS, hot height is isolated from intermediate reaction product or final reacting product BRKGP Oil BRKGP-THPSL, the hot high score oil BRKGP-THPS-L of at least part is divided to return as recycle oil BRKGP-THPS-LR-TOBRA Return the reaction compartment that at least part hydrogenation modification reaction process BR is passed through in upstream.

29. according to claim 1 or 2 or 3 the methods, it is characterised in that:

In thermal high separation process BRKGP-THPS, hot height is isolated from intermediate reaction product or final reacting product BRKGP Oil BRKGP-THPSL, the hot high score oil BRKGP-THPS-L of at least part is divided to return as recycle oil BRKGP-THPS-LR-TOBRA Return the reaction compartment that at least part hydrogenation modification reaction process BR is passed through in upstream；

Thermal high separation process BRKGP-THPS, is arranged in the upper space of floating bed hydrogenation reactor B RK-GE, is received with liquid The system of storage, drain pipeline, circulating pump, liquor charging pipeline composition, makes at least part collection liquid BRKGP-THPS-LR-TOBRA Return to the reaction compartment that at least part hydrogenation modification reaction process BR is passed through in upstream.

30. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(1) hydrogenation process BR, including hydrogenation modification reaction process BR；

Hot high score oil BRAGP-THPS-L enters thermal high separation process as collection liquid BRAGP-THPS-LP at least partially In the reaction compartment of the downstream reaction process of BRAGP-THPS or enter the final reacting product of hydrogenation modification reaction process BRA In thermal high gas-liquid separator；

Thermal high separation process BRAGP-THPS, is arranged in the upper space of floating bed hydrogenation reactor B RA-GE, is received with liquid The system of storage, drain pipeline, circulating pump, liquor charging pipeline composition, makes at least part collection liquid BRAGP-THPS-LP enter heat In the reaction compartment of the downstream reaction process of high pressure separation process BRAGP-THPS or enter hydrogenation modification reaction process BRA most In the thermal high gas-liquid separator of end reaction product.

31. method according to claim 4, it is characterised in that:

Hot high score oil BRKGP-THPS-L enters thermal high separation process as collection liquid BRKGP-THPS-LP at least partially End reaction in the reaction compartment of the downstream reaction process of BRKGP-THPS or into serial operation low-temp reaction process BRK produces In the thermal high gas-liquid separator of object；

Thermal high separation process BRKGP-THPS, is arranged in the upper space of floating bed hydrogenation reactor B RK-GE, is received with liquid The system of storage, drain pipeline, circulating pump, liquor charging pipeline composition, makes at least part collection liquid BRKGP-THPS-LP enter heat In the reaction compartment of the downstream reaction process of high pressure separation process BRKGP-THPS or enter serial operation low-temp reaction process BRK Final reacting product thermal high gas-liquid separator in.

32. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(2) in removal process SR, thermal high separation process THPS is set；

In thermal high separation process THPS, recycles hydrogenation process BR effluent BR-ENDP and obtain adding hydrogen containing hydrogen, impurity Product, conventional gas hydrocarbon and normal boiling point are lower than the hot high score gas THPS-V of 350 DEG C of conventional liquid hydrocarbon and contain dissolved hydrogen The possibility of the conventional liquid hydrocarbon of gas, normal boiling point higher than 350 DEG C contains the hot high score liquid THPS-L of solid particle；

Separate and recover hot high score gas THPS-V, obtain in volume the hydrogen rich gas gas SRV being mainly made of hydrogen and mainly by The possibility of conventional liquid hydrocarbon composition contains the liquid stream SRL-L of solid particle, and at least part hydrogen rich gas gas SRV, which is returned, to be added Hydrogen reaction process is recycled.

33. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(2) in removal process SR, thermal high separation process THPS is set；

Hot high score liquid THPS-L is separated and recovered, the distillation being mainly made of the hydrocarbon component that normal boiling point is 250~530 DEG C is obtained Oily BR-P-ML, at least part distilled oil BR-P-ML enter hydrogenation process BRA or and BRK.

34. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(2) in removal process SR, thermal high separation process THPS is set；

Hot high score liquid THPS-L is separated and recovered, the hydrocarbon component mainly by normal boiling point higher than 530 DEG C forms plus hydrogen tail is obtained Oily BR-P-VS, at least part tail oil BRK-P-VS do not enter hydrogenation process.

35. according to claim 1 or 2 or 3 the methods, it is characterised in that:

Based on the hydrocarbon material RKKC rich in catalyst that hydrogenation process BR effluent BR-ENDP is obtained, it is recycled back into and adds hydrogen Modified-reaction process BRA is mixed with the raw material of hydrogenation modification reaction process BRA or intermediate product or final product；

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

1. the hot high score oil that a part is obtained in the thermal high separation process of hydrogenation process BR effluent BR-ENDP, is used as Hydrocarbon material RKKC containing catalyst；

2. a part contains catalyst what the destilling tower of the separation fractional distillation process of hydrogenation process BR effluent BR-ENDP was discharged Hydrocarbon material, as the hydrocarbon material RKKC containing catalyst；

3. a part contains catalyst what the destilling tower of the separation fractional distillation process of hydrogenation process BR effluent BR-ENDP was discharged Distillation cold oil, as the hydrocarbon material RKKC containing catalyst；

4. a part contains catalyst what the destilling tower of the separation fractional distillation process of hydrogenation process BR effluent BR-ENDP was discharged Destilling tower base oil, as the hydrocarbon material RKKC containing catalyst；

5. the hydrocarbon ils for the bituminous component that at least part separation hydrogenation process BR effluent BR-ENDP is obtained, is used as molten The raw material VS-EF of agent extraction separation process VS-EU, in the hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained, As the hydrocarbon material RKKC containing catalyst；

6. the hydrocarbon ils for the bituminous component that at least part separation hydrogenation process BR effluent BR-ENDP is obtained, is used as molten The raw material VS-EF of agent extraction separation process VS-EU, in the heavy drip containing catalyst that solvent extraction and separation process VS-EU is obtained Green hydrocarbon material, as the hydrocarbon material RKKC containing catalyst；

7. the hydrocarbon ils for the bituminous component that at least part separation hydrogenation process BR effluent BR-ENDP is obtained, is used as molten The raw material VS-EF of agent extraction separation process VS-EU, in the lightweight drip containing catalyst that solvent extraction and separation process VS-EU is obtained Green hydrocarbon material, as the hydrocarbon material RKKC containing catalyst；

8. the hydrocarbon ils for the bituminous component that at least part separation hydrogenation process BR effluent BR-ENDP is obtained, is used as molten The raw material VS-EF of agent extraction separation process VS-EU, in the middle matter drip containing catalyst that solvent extraction and separation process VS-EU is obtained Green hydrocarbon material, as the hydrocarbon material RKKC containing catalyst.

36. method according to claim 4, it is characterised in that:

Based on the isolated hydrocarbon material RKKC containing catalyst of hydrogenation process BR effluent BR-ENDP, it is recycled back into string Connection operation low-temp reaction process BRK is mixed with the raw material of serial operation low-temp reaction process BRK or intermediate product or final product；

37. method according to claim 1, it is characterised in that:

The material BRF of the high aromatic hydrocarbons HAC containing higher boiling comes from high temperature coal-tar, contains coal tar pitch component；

Adopting for the extraction needle-shape coke raw material of containing hydrogenated coal tar pitch material based on hydrogenation process BR effluent BR-ENDP is set With the solvent extraction and separation process VS-EU of solvent segregation；

1. at least part is used as the hydrocarbon containing catalyst in the hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained Material RKKC；

It is urged 2. at least part is used as to contain in the heavy asphalt hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained The hydrocarbon material RKKC of agent；

It is urged 3. at least part is used as to contain in the light asphalt hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained The hydrocarbon material RKKC of agent；

It is urged 4. at least part is used as to contain in the middle matter pitch hydrocarbon material containing catalyst that solvent extraction and separation process VS-EU is obtained The hydrocarbon material RKKC of agent；

The method for isolating light liquid phase and heavy-fluid phase using the separation process of solvent segregation, can a kind in following:

38. method according to claim 1, it is characterised in that:

39. method according to claim 1, it is characterised in that:

(1) conventional comprising at least part based on hydrogenation modification reaction effluent BRA-P in hydrogenation modification reaction process BRA The raw material BRK-FEED of olefin-containing component containing hydrocarbon liquid phase of the logistics of liquid hydrocarbon as serial operation low-temp reaction process BRK；

Raw material BRK-FEED may include solid particulate materials BRK-FEEDS；

It is low that the logistics comprising at least part conventional liquid hydrocarbon based on hydrogenation modification reaction effluent BRA-P is used as serial operation The working method of the raw material BRK-FEED of the olefin-containing component containing hydrocarbon liquid phase of warm reaction process BRK, a kind in following or It is several:

1. hydrogenation modification reaction effluent BRA-P is used as the raw material BRK-FEED of olefin-containing component, anti-into serial operation low temperature Answer process BRK；

2. hydrogenation modification reaction effluent BRA-P is used as the raw material BRK-FEED of olefin-containing component, material is mixed with cooling Enter serial operation low-temp reaction process BRK afterwards；

3. hydrogenation modification reaction effluent BRA-P, which enters thermal high separation process BRA-P-HS, is separated into hot high score oil BRA-P- HSL and hot high score gas BRA-P-HSV, the hot high score oil BRA-P-HSL of at least part are used as the raw material BRK- of olefin-containing component FEED, into serial operation low-temp reaction process BRK；

4. hydrogenation modification reaction effluent BRA-P, which enters thermal high separation process BRA-P-HS, is separated into hot high score oil BRA-P- HSL and hot high score gas BRA-P-HSV, the hot high score oil BRA-P-HSL of at least part are used as the raw material BRK- of olefin-containing component FEED enters serial operation low-temp reaction process BRK after mixing with the material that cools；

5. hydrogenation modification reaction effluent BRA-P, which enters thermal high separation process BRA-P-HS, is separated into hot high score oil BRA-P- HSL and hot high score gas BRA-P-HSV, gained liquid B RA-P- after the hot high score oil BRA-P-HSL decompression of at least part, degassing The raw material BRK-FEED that HSLA is used as olefin-containing component enters serial operation low-temp reaction process BRK；

6. hydrogenation modification reaction effluent BRA-P, which enters thermal high separation process BRA-P-HS, is separated into hot high score oil BRA-P- HSL and hot high score gas BRA-P-HSV, gained liquid B RA-P- after the hot high score oil BRA-P-HSL decompression of at least part, degassing HSLA is used as the raw material BRK-FEED of olefin-containing component, and serial operation low-temp reaction process is entered after mixing with the material that cools BRK。

40. according to claim 1 or 2 or 3 the methods, it is characterised in that:

1. in hydrogenation modification reaction process BRA, using the material BRF of hydrogen supply hydrocarbon material DSF and the high aromatic hydrocarbons HAC containing higher boiling or its Intermediate hydrogenation products contact.

41. according to claim 1 or 2 or 3 the methods, it is characterised in that:

1. in hydrogenation modification reaction process BRA, using the material BRF of hydrogen supply hydrocarbon material DSF and the high aromatic hydrocarbons HAC containing higher boiling or its Intermediate hydrogenation products contact, and the weight concentration absolute value of hydrogen supply the hydrocarbon component DS is higher than Gao Fang containing higher boiling in hydrogen supply hydrocarbon material DSF The weight concentration absolute value at least 10% of hydrogen supply the hydrocarbon component DS in the material BRF of hydrocarbon HAC.

42. according to claim 1 or 2 or 3 the methods, it is characterised in that:

1. in hydrogenation modification reaction process BRA, using the material BRF of hydrogen supply hydrocarbon material DSF and the high aromatic hydrocarbons HAC containing higher boiling or its Intermediate hydrogenation products contact, and the weight concentration absolute value of hydrogen supply the hydrocarbon component DS is 10~65% in hydrogen supply hydrocarbon material DSF.

43. according to claim 1 or 2 or 3 the methods, it is characterised in that:

1. in hydrogenation modification reaction process BRA, using the material BRF of hydrogen supply hydrocarbon material DSF and the high aromatic hydrocarbons HAC containing higher boiling or its Intermediate hydrogenation products contact, hydrogen supply hydrocarbon material DSF are mainly made of the hydrocarbon component that normal boiling point is 250~350 DEG C.

44. according to claim 1 or 2 or 3 the methods, it is characterised in that:

1. in hydrogenation modification reaction process BRA, using the material BRF of hydrogen supply hydrocarbon material DSF and the high aromatic hydrocarbons HAC containing higher boiling or its Intermediate hydrogenation products contact, the weight flow of hydrogen supply dissolvent component DS and higher boiling Gao Fang in material BRF in hydrogen supply hydrocarbon material DSF The ratio between weight flow of hydrocarbon HAC is 0.05~2.0.

45. according to claim 1 or 2 or 3 the methods, it is characterised in that:

1. in hydrogenation modification reaction process BRA, using the material BRF of hydrogen supply hydrocarbon material DSF and the high aromatic hydrocarbons HAC containing higher boiling or its Intermediate hydrogenation products contact；

Based on the hydrogen material of stabilized hydrogenation reaction process MR, it is used in series into hydrogenation modification reaction process BRA；

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

46. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(2) in removal process SR, thermal high separation process THPS is set；

Based on the hydrogen material of hot high score gas THPS-V, it is used in series into stabilized hydrogenation reaction process MR；

47. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(2) in removal process SR, thermal high separation process THPS is set；

Hydrogen, hydrocarbonaceous oil material based on hot high score gas THPS-V, into adding hydrogen upgrading reaction process HT66 to carry out plus hydrogen HT66-R is reacted in upgrading, is converted into and adds hydrogen upgrading reaction product HT66-P；

Hydrogen upgrading is added to react HT66-R, including hydrogenated olefin saturated reaction, hydrodesulfurization reaction, hydrodenitrogeneration reaction plus hydrogen virtue One or more of hydrocarbon saturated reaction, hydrocracking reaction, hygrogenating isomerization reaction；

Recycling plus hydrogen upgrading reaction product HT66-P.

48. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(2) in removal process SR, thermal high separation process THPS is set；

Condense and separate the degassing hydrocarbonaceous oil material that hot high score gas THPS-V is obtained, into add hydrogen upgrading reaction process HT66 carry out Add hydrogen upgrading to react HT66-R, is converted into and adds hydrogen upgrading reaction product HT66-P；

Recycling plus hydrogen upgrading reaction product HT66-P.

49. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(2) in removal process SR, thermal high separation process THPS is set；

Recycling plus hydrogen upgrading reaction product HT66-P.

50. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(2) in removal process SR, thermal high separation process THPS is set；

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

51. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(2) in removal process SR, thermal high separation process THPS is set；

In separation fractional distillation process, what what heat of dissociation high score liquid THPS-L was obtained mainly formed by wax oil component or with residue fraction At least part of narrow fraction hydrocarbon material returns to the starting position or middle position of the reaction process of hydrogenation process BR, carries out Circulation plus hydrogen.

52. according to claim 1 or 2 or 3 the methods, it is characterised in that:

The material BRF of the high aromatic hydrocarbons HAC containing higher boiling, selected from one or more of following materials:

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

2. the high hydrocarbon ils of content of ashes；

3. the high hydrocarbon ils of easy coking constituent content；

4. the high hydrocarbon ils of the easy reactant content of high temperature；

53. according to claim 1 or 2 or 3 the methods, it is characterised in that:

1. in hydrogenation modification reaction process BRA, using dilution the hydrocarbon WWF and high aromatic hydrocarbons HAC containing higher boiling material BRF or in which Hydrogenation products contact, the absolute value for diluting the aromatic carbon rate of hydrocarbon WWF are at least lower by 0.1 than the absolute value of the aromatic carbon rate of material BRF.

54. according to claim 1 or 2 or 3 the methods, it is characterised in that:

1. in hydrogenation modification reaction process BRA, using dilution the hydrocarbon WWF and high aromatic hydrocarbons HAC containing higher boiling material BRF or in which Hydrogenation products contact, dilution hydrocarbon WWF are mainly made of the hydrocarbon component that normal boiling point is 250~350 DEG C.

55. according to claim 1 or 2 or 3 the methods, it is characterised in that:

In hydrogenation modification reaction process BRA, comprising 2 or sub- hydroconversion reaction zone BRA-1, BRA-2 of multiple serial operations etc., this When, the logistics comprising at least part conventional liquid hydrocarbon of the reaction effluent based on upper alien hydroconversion reaction zone enters downstream phase Adjacent sub- hydroconversion reaction zone, the sub- hydroconversion reaction zone BRA-1 of the first of hydrogenation modification reaction process BRA obtain reaction effluent BRA- 1P, the flow B RA-1PX comprising at least part hydrogenated oil BRA-1PO based on reaction effluent BRA-1P enters plus hydrogen The sub- hydroconversion reaction zone BRA-2 of the second of modified-reaction process BRA, the reaction effluent of last sub- hydroconversion reaction zone, which is used as, to be added Hydrogen modified-reaction effluent BRA-P is used；

The material BRF of the high aromatic hydrocarbons HAC containing higher boiling is divided into the serial operation that at least 2 tunnels enter hydrogenation modification reaction process BRA Different sub- hydroconversion reaction zones.

56. according to claim 1 or 2 or 3 the methods, it is characterised in that:

(2) in removal process SR, thermal high separation process THPS is set；

For the hot high score gas THPS-V isolated in thermal high separation process THPS, the liquid scrubbing that gas phase takes off solid is set Settling section obtains the lower gas of solid content.