CN110066688A

CN110066688A - Use the hydrocarbon material expanded bed method of hydrotreating of reaction product Thermal Synthetic high score device

Info

Publication number: CN110066688A
Application number: CN201910357818.1A
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: 2019-04-25
Filing date: 2019-04-25
Publication date: 2019-07-30

Abstract

Use the hydrocarbon material expanded bed method of hydrotreating of reaction product Thermal Synthetic high score device, suitable for heavy oil expanded bed hydrogenation process, expanded bed hydrogenator working method can for slight expanded-bed, ebullated bed, suspension bed, ebullated bed and suspension bed combination cot etc., the flow at high speed of the liquid phase region setting reaction cycle liquid DSLR of Thermal Synthetic high score device DS, the low speeds flow of the region DV01 and Re Gao liquid separation DSLP of more inefficient degassing, efficient degassing region DV02；DSLR contains a small amount of bubble hydrogen conducive to slagging prevention, and can fill into a small amount of hydrogen in suitable position；DSLP air bubble content is low, conducive to the liquid level operation of the erosion, steady hot high score device that reduce entrainment gas phase hydrogen loss, reduce pressure reducing valve；DV02 upper aqueous phase area forms microbubble supplement reaction zone using carrying hydrogen or filling into hydrogen；Present invention optimizes the process function of Thermal Synthetic high score device liquid phase region and structure simplicity, also create condition to simplify relevant reactor structure.

Description

Use the hydrocarbon material expanded bed method of hydrotreating of reaction product Thermal Synthetic high score device

Technical field

The present invention relates to the hydrocarbon material expanded bed method of hydrotreating for using reaction product Thermal Synthetic high score device, and it is swollen to be suitable for heavy oil Swollen bed hydroprocessing reaction process, expanded bed hydrogenator working method can for slight expanded-bed, ebullated bed, suspension bed, ebullated bed with Suspension bed combination cot etc., the flow at high speed of the liquid phase region setting reaction cycle liquid DSLR of Thermal Synthetic high score device DS, more inefficient degassing The low speeds flow of region DV01 and Re Gao liquid separation DSLP, efficient degassing region DV02；DSLR contains a small amount of bubble hydrogen and is conducive to Slagging prevention, and a small amount of hydrogen can be filled into suitable position；DSLP air bubble content is low, be conducive to reduce entrainment gas phase hydrogen loss, Reduce the erosion of pressure reducing valve, the liquid level operation of steady hot high score device；DV02 upper aqueous phase area using carrying hydrogen or fills into hydrogen Gas forms microbubble and supplements reaction zone；Present invention optimizes the process function of Thermal Synthetic high score device liquid phase region and structure is concise, It is created condition to simplify relevant reactor structure.

Background technique

The present invention relates to heavy oil expanded bed hydrogenation depth method for thermal cracking, the Thermal Synthetic high score device DS refers to hot height Divide liquid product at least 2 tunnels of device, the 1st road liquid product is used as hydrogenation reaction raw material such as circulation fluid TSLR and returns to upstream Reaction zone reactor in, the 2nd road liquid product is used as the high liquid separation TSLP of heat by going separation, fractionating system after decompression； The main problem that the present invention is paid close attention to is how to realize following multiple targets simultaneously:

1. reducing the volume of the liquid phase region of Thermal Synthetic high score device DS, investment is reduced；

2. improving the degassing efficiency of the high liquid separation DSLP overcurrent area DV02 of heat, that is, require the liquid for rationally reducing overcurrent area DV01 Flow velocity ensures the sufficiently long residence time；

3. it is conducive to inhibit the asphalitine coking in heavy oil due to carrying a small amount of hydrogen microbubble secretly, in hydrogen gas bubbles Under the premise of volume content is acceptable, it is desirable to reduce the volume of hydrogenation reaction raw material TSLR overcurrent area DV01, that is, it is reasonable to require The flow rate of liquid of overcurrent area DV01 is improved, shortens the residence time, reduce coking material yield；

4. sky can be used so that the internals of adjacent upstream hydrogenator are simplified using Thermal Synthetic high score device DS Barrel reactor or only in the reactor of lower part setting feed distributor, for heavy oil expanded bed hydrogenation depth thermal cracking process, Improving conversion per pass may cause there are micro free carbon in reaction product liquid phase, and long-term operating is likely to form liquid phase low flow velocity In the case where the equipment internals surface knot carbon accumulation of region contact, using comprehensive separator and reactor be arranged internal liquid collecting cup, The scheme of catheter is compared, and the liquid phases low flow velocity such as the outer surface of internal liquid collecting cup, outer surface of catheter region is eliminated The equipment internals outer surface of contact, to reduce the carbon deposition quantity of reaction system；Meanwhile the liquid phase region section of comprehensive separator is straight Diameter can be less than the liquid phase region diameter of section of built-in liquid collecting cup, and so as to effectively improve liquid phase region flow velocity, it is heavy to reduce coking material Accumulated amount；

5. the inside liquid collecting cup function of reactor is merged with the high pressure hot separator for reacting net product, realize as far as possible The equivalent transformation of the liquid separation function of internal liquid collecting cup；

6. producing the efficient air lift workspace of hydrogenation reaction liquid material DSLR, it is conducive to reduce low in hydrogenation reaction liquid material DSLR Boiling point component content and reduction temperature reduce the gas yield of recycle stock circulation hydrogenation process, improve liquid yield；

7. can alternatively be used low-temperature material, cooling hydrogenation reaction liquid material DSLR or the high liquid separation DSLP of heat；

8. the property of can choose is low to use hydrogen supply hydrocarbon material, inhibit the DSLR coking of hydrogenation reaction liquid material, reduces reactor assembly Coking material yield and cumulant；

9. upstream reactor, Thermal Synthetic high score device DS belong to a hydrogenation reaction grade, can be in the company between 2 equipment The mixing point of other process-streams such as hydrogen, gas-liquid logistics, liquid material is set on adapter tube line, hydrogen can be carried out to reactor product The cooling reactor product of gas air lift low boiling component, cold logistics, addition liquid material realize that liquid material is adding hydrogen in Thermal Synthetic high score device DS Distribution between reaction liquid material DSLR, the high liquid separation DSLP of heat (forms the distribution effect that addition liquid material enters hydrogenation reaction liquid material DSLR It answers)；

10. the inside liquid collecting cup function of reactor is merged with the high pressure hot separator for reacting net product, reduce 1 height Warm high-pressure bottle reduces connecting pipe quantity, conducive to reducing investment outlay, reducing shut-down (breakdown) mainteance workload.

Conception of the invention is: using the hydrocarbon material expanded bed method of hydrotreating of reaction product Thermal Synthetic high score device, being suitable for Heavy oil expanded bed hydrogenation process, expanded bed hydrogenator working method can be slight expanded-bed, ebullated bed, suspension bed, boiling Rise bed and suspension bed combination cot etc., it is the flow at high speed of the liquid phase region setting reaction cycle liquid DSLR of Thermal Synthetic high score device DS, lower Imitate the low speeds flow of the region DV01 and Re Gao liquid separation DSLP of degassing, the region DV02 of efficient degassing；DSLR contains a small amount of hydrogen Pauli can fill into a small amount of hydrogen in suitable position in slagging prevention；DSLP air bubble content is low, is conducive to reduce entrainment vapor phase hydrogen Loss, the erosion for reducing pressure reducing valve, the liquid level operation of steady hot high score device；DV02 upper aqueous phase area, using carry hydrogen or It fills into hydrogen and forms microbubble supplement reaction zone；Present invention optimizes the process function of Thermal Synthetic high score device liquid phase region and structure letters It is bright, also created condition to simplify relevant reactor structure.

Chinese patent ZL200610090484.9 discloses a kind of coal direct liquefaction method, comprising the following steps: (1) pre- place Coal dust after reason is prepared into pumpable coal slurry together with adding hydrogen to recycle solvent and Fe-series catalyst, with fresh hydrogen and/or circulation Hydrogen is successively reacted by concatenated first reactor and second reactor after mixing, being preheated；(2) it is led by second reactor Reaction product out is sent into high-temperature separator 11 and is separated, and material a part of 11 lower part of high-temperature separator discharge passes through decompression Valve discharge, rest part return to first reactor reaction raw materials entrance and are recycled, wherein the weight of recycle stock and fresh feed Measuring the ratio between flow is 2~20, can reduce hydrogen consumption and factor of created gase using method.

In Chinese patent ZL200610090484.9, material a part of 11 lower part of high-temperature separator discharge passes through decompression Valve discharge, rest part return to first reactor reaction raw materials entrance and are recycled, and do not propose similar high temperature of the invention point From 2 liquid phase flow rate differences of device liquid phase region setting, the concept of the sub- liquid phase region of Various Functions, therefore it cannot achieve mesh of the invention , its shortcoming is that:

1. the volume of the liquid phase region of high-temperature separator 11 cannot be effectively reduced；

2. rationally reducing the liquid of overcurrent area DV01 if improving the degassing efficiency of the high liquid separation DSLP overcurrent area DV02 of heat Flow velocity ensures the sufficiently long residence time, then the flow rate of liquid of hydrogenation reaction raw material TSLR overcurrent area DV01 is necessarily caused to reduce, Extended residence time increases volume, increases coking material yield；

3. the bubble hydrogen integration rate reduced in the high liquid separation DSLP of heat is usually required that, in such hydrogenation reaction raw material TSLR Bubble hydrogen integration rate reduce simultaneously, be unfavorable for inhibit hydrogenation reaction raw material TSLR in asphalitine coking；

4. rationally reducing the liquid of overcurrent area DV01 if improving the degassing efficiency of the high liquid separation DSLP overcurrent area DV02 of heat Flow velocity ensures the sufficiently long residence time, then the flow rate of liquid of hydrogenation reaction raw material TSLR overcurrent area DV01 is necessarily caused to reduce, Extended residence time increases volume, and the deposit that may be deposited in high-temperature separator 11 can be hydrogenated reaction raw materials TSLR It is carried along into or is recycled into hydrogenator, can further induce more coking materials to generate as coking center, deteriorate The operating environment of related system；

5. the inside liquid collecting cup function of reactor is merged with the high pressure hot separator for reacting net product, but change phase It is not a kind of equivalent transformation when the working method of the liquid separation function in internal liquid collecting cup；

6. the efficient air lift workspace of hydrogenation reaction liquid material DSLR can not be separately produced, because gas must be consumed simultaneously Hydrogen carrys out the air lift high liquid separation DSLP of heat, will increase air lift hydrogen flowing quantity, increases circulating hydrogen system investments；

7. low-temperature material can not be used alone, selectivity cooling hydrogenation reaction liquid material DSLR or the high liquid separation DSLP of heat, because Low-temperature material must be consumed simultaneously to cool down the high liquid separation DSLP of heat, will increase low-temperature material flow, increased low-temperature material system and throw Money；

8. hydrogen supply hydrocarbon material can not be used alone, selectively inhibit the DSLR coking of hydrogenation reaction liquid material, because must be same When consumption hydrogen supply hydrocarbon material be scattered in the high liquid separation DSLP of heat, will increase hydrogen supply hydrocarbon material flow, increase hydrogen supply hydrocarbon material system Investment.

Chinese patent ZL200810228406.X discloses a kind of hydrogenation method of heavy hydrocarbon multi-segment fluidized bed, and technical process is viscous The gaseous stream that thick heavy hydrocarbon feeds and boiling bed hydrogenation desulfurization and hydrodenitrogeneration reactor are discharged is mixed into hydrodemetallization Reactor, the gaseous stream after reaction can be used as recycle hydrogen through cooling and purified treatment and use, the liquid phase after demetalization reaction Logistics and hydrogen are mixed into boiling bed hydrogenation desulfurization reactor；Liquid phase stream and hydrogen after desulphurization reaction are mixed into plus hydrogen Denitrification reactor；Liquid phase stream after denitrification reaction enters separator 12, the heavy constituent or warp some or all of isolated Pipeline 16 is recycled to boiling bed hydrogenation demetalization reactor, or fills together with the light component isolated through distillation through the discharge of pipeline 14 It sets to obtain petrol and diesel oil product and good catalysis charging.The technique processes high viscosity inferior heavy using new combination of reactors mode Oily raw material can provide flexibly, and efficiently, energy-efficient new operation mode is organic by the performance of raw material and each hydrogenation reaction feature It is combined together, under the premise of guaranteeing device quiet run, makes full use of exothermic heat of reaction, good product quality is provided, and It can be required that operating process is adjusted flexibly according to refinery.

There are basic difference, the main distinction is by Chinese patent ZL200810228406.X and the present invention:

1. Chinese patent ZL200810228406.X method is boiling bed hydrogenation reaction process, can not be applied to suspension bed Hydrogenation process etc.；

2. boiling bed hydrogenation denitrification reactor 9 carries out hydrodenitrogeneration in Chinese patent ZL200810228406.X method Reaction, the gaseous stream after boiling bed hydrogenation denitrification reactor 9 reacts are discharged from reactor through pipeline 10, are recycled to through pipeline 15 Boiling bed hydrogenation demetalization reactor 2；Liquid phase stream after boiling bed hydrogenation denitrification reactor 9 reacts enters separator 12, The heavy constituent isolated all through the discharge of pipeline 14 enter together with the light component isolated atmospheric and vacuum distillation unit obtain gasoline, Diesel oil distillate and catalytic cracking unit charging；

It is obvious that the top of boiling bed hydrogenation denitrification reactor 9 is provided with gas-liquid distribution facilities, with synthesis of the present invention The simple structure of the adjacent upstream hydrogenator of hot high score device DS is different, is the increasingly complex hydrogenator of internal structure；

3. in Chinese patent ZL200810228406.X method, the separator 12 used is and Chinese patent The identical separator of 11 structure of high-temperature separator used in ZL200610090484.9 does not propose similar high temperature of the invention Separator liquid phase region be arranged 2 liquid phase flow rate differences, Various Functions sub- liquid phase region concept, therefore cannot achieve of the invention Purpose exists and is analogous to the identical processing disadvantages of high-temperature separator 11 that Chinese patent ZL200610090484.9 is used.

Chinese patent application 201610884037.4 (107892945 A of application publication number CN) is disclosed with air lift hydrogen With the hydrocarbon material expanded bed hydrogenator system of liquid collection cups, hydrogen, coal tar hydrogenating, coal is added to add suitable for petroleum based heavy fuel oils The processing of middle part product URZE-IP inside the end hydrogenator URZE of liquefaction of hydrogen process, uses air lift hydrogen BH and liquid At least part low boiling hydrocarbon component in the product URZE-IP liquid phase of middle part is vaporizated into gas phase discharge plus hydrogen by body collection cups LD Reactor URZE, while obtaining the collection liquid URZE-TL being mainly made of heavy hydrocarbon, collection liquid URZE-TL of de- low boiling hydrocarbon Unconverted oil from the export of liquid collection cups as setting boiling point boundary, the reactive moieties short-circuit cycle for constituting unconverted oil add hydrogen Mode；The dual formula distributor that air lift hydrogen BH is made up of " nozzle-reflecting plate " of horizontally disposed cartridge type distributing chamber locular wall Enter the de- liquid space in the liquid top collection cups LD with cocurrent after material mixes is risen.Chinese patent application 201610884037.4 with Of the invention different, the efficient air lift workspace of circulation hydrogenation reaction liquid material DSLR can not can not be separately produced in it, because necessary Gas hydrogen is consumed simultaneously and carrys out the air lift high liquid separation DSLP of heat, be will increase air lift hydrogen flowing quantity, is increased circulating hydrogen system investments；In State's patent application 201610884037.4 is not directed to the Thermal Synthetic high score device DS that the present invention uses, cannot achieve mesh of the invention 's.

Since Thermal Synthetic high score device DS of the invention is the commonly used equipment in hydrocarbon material expanded bed hydrogenation process, because This, commercial value is larger.

The method of the present invention has not been reported.

The purpose of invention is the hydrocarbon material expanded bed method of hydrotreating for proposing to use reaction product Thermal Synthetic high score device.

Summary of the invention

The present invention use reaction product Thermal Synthetic high score device hydrocarbon material expanded bed method of hydrotreating, it is characterised in that comprising with Lower step:

(1) in hydrocarbon material expanded bed hydrogenation process UR, there are hydrogen, hydrocarbon liquid phase, there may be solid particles simultaneously Mixed phase material under the conditions of, at least containing the first raw material URF of carbon and protium carry out expanded bed hydrogenation reaction URR obtain Hydrogenation reaction effluent URP-X is discharged in hydrogenation reaction product BASE-URP, and the net product URP of hydrogenation process is discharged；

First raw material URF includes liquid material URFL and solid particulate materials URFS that may be present；

Expanded bed hydrogenation reaction URR, the hydrofining reaction comprising at least part liquid material URFL may be comprising extremely The hydrocracking reaction of few a part of liquid material URFL may include at least part solid material URFS's that may be present Heat from hydrogenation cracking reaction；

Hydrocarbon material expanded bed hydrogenation process UR may use hydrogenation catalyst URC, hydrogenation catalyst URC that may contain gold Belong to molybdenum；

Hydrogenation reaction product BASE-URP, for containing hydrogen, hydrocarbon liquid phase simultaneously may the mixed phase material containing solid particle；

Material based on hydrogenation reaction product BASE-URP is used as hydrogenation reaction effluent URP-X；Hydrogenation reaction effluent URP-X occurs in the form of 1 tunnel or 2 tunnels or multichannel material, and hydrogenation reaction effluent URP-X is that gas phase or liquid phase or gas-liquid are mixed Phase or gas-liquid-solid three-phase logistics；

The liquid stream URP-L for belonging to hydrogenation reaction effluent URP-X, may contain solid particle；

The liquid phase logistics URP-M for belonging to hydrogenation reaction effluent URP-X, may contain solid particle；

Hydrocarbon material expanded bed hydrogenation process UR, using at least 1 hydrogenator, in the hydrogenator used extremely It less include 1 up flow type expanded bed hydrogenator；

One hydrogenation reaction grade, to its hydrogenation products referring to entering a hydrogenation process since hydrocarbon raw material Gas-liquid separation obtains at least one by process section until generating the liquid product that oil forms at least partially, comprising that hydrogen should be added anti- Answer the gas-liquid separation process of the hydrogenation process of grade and at least part hydrogenation reaction product of this grade；

Hydrocarbon material expanded bed hydrogenation process UR includes at least one hydrogenation reaction grade, has liquid phase comprising at least one The product KRP of the hydrogenation reaction grade of product circulation, at least one hydrogenation reaction grade KR for having liquid product to recycle uses Thermal Synthetic High score device KR-DS carries out gas-liquid separation and liquid material distribution；

In hydrogenation reaction grade KR, at least 1 provide to Thermal Synthetic high score device KR-DS may the gas-liquid product containing solid The adjacent hydrocarbon material expanded bed hydrogenator KR9E in upstream is not provided with the expansion of liquid collecting cup, diversion pipe for the top in reactor Bed hydroprocessing reactor；

The product KRP of the hydrogenation reaction grade KR is characterized in that using Thermal Synthetic high score device KR-DS: Thermal Synthetic high score device Liquid short residence time region KR-DV01 and liquid long residence time region KR-DV02 is arranged in the liquid phase region of KR-DS；Region KR- The residence time KR-LT1 of liquid in DV01, less than the residence time KR-LT2 of liquid in the KR-DV02 of region,

At least part liquid material of the liquid short residence time region KR-DV01 discharge of Thermal Synthetic high score device KR-DS is used as Reaction cycle liquid KR-DSLR is returned in the upstream hydrogenator in hydrogenation reaction grade KR and is flowed through hydrocarbon material expansion bed hydroprocessing At least part reaction compartment of reactor KR9E；

At least part part liquid material of the liquid long residence time region KR-DV02 discharge of Thermal Synthetic high score device KR-DS As the high liquid separation KR-DSLP of heat；

Hydrocarbon material expanded bed hydrogenation process UR includes at least one hydrogenation reaction grade, the last one hydrogenation reaction grade That is end hydrogenation reaction grade ENDR may be the hydrogenation reaction grade ENDR for having liquid product to recycle, end hydrogenation reaction grade ENDR's Product ENDR-P may use Thermal Synthetic high score device ENDR-DS to carry out gas-liquid separation and liquid material distribution.

The present invention, in general, in the liquid phase region of Thermal Synthetic high score device KR-DS, liquid in liquid short residence time region KR-DV01 The ratio of the residence time KR-LT2 of liquid in the residence time KR-LT1 and liquid long residence time region KR-DV02 of body 1 kind in following of KT100=(KR-LT1)/(KR-LT2), KT100:

①≤0.17；

2. 0.17~0.25；

3. 0.25~0.33；

4. 0.33~0.50；

5. 0.50~0.67.

The present invention, in general, in the liquid phase region of Thermal Synthetic high score device KR-DS, liquid in liquid short residence time region KR-DV01 The residence time KR-LT1 of body, a kind in following:

1.≤15 seconds；

2. 15~30 seconds；

3. 30~45 seconds；

4. 45~60 seconds；

5. 60~120 seconds.

The present invention, in general, in the liquid phase region of Thermal Synthetic high score device KR-DS, liquid in liquid long residence time region KR-DV02 The residence time KR-LT2 of body, a kind in following:

1. >=480 seconds；

2. 360~480 seconds；

3. 240~360 seconds；

4. 180~240 seconds；

5. 120~180 seconds.

The present invention, in general, in Thermal Synthetic high score device KR-DS, the weight flow KR-DSLR-W of reaction cycle liquid KR-DSLR It is set to recycle ratio K900 with the ratio of the weight flow KR-DSLP-W of the high liquid separation KR-DSLP of heat, K900=(KR-DSLR-W)/ (KR-DSLP-W), a kind in following of K900:

1. 0.001~0.5；

2. 0.5~2.5；

3. 2.5~5.0；

4. > 5.0.

The present invention, the mode of operation of Thermal Synthetic high score device KR-DS can be selected from a kind or several of combinations in following:

1. including air lift hydrogen, the liquid phase that Thermal Synthetic high score device KR-DS is fed in the charging of Thermal Synthetic high score device KR-DS In at least part low boiling component air lift enter in gas phase, and eventually enter into the gaseous products of Thermal Synthetic high score device KR-DS In；

2. including the hydrogen rich gas gas 399S of the component containing high boiling hydrocarbon in the charging of Thermal Synthetic high score device KR-DS as air lift Gas enters at least part low boiling component air lift in the liquid phase of Thermal Synthetic high score device KR-DS charging in gas phase and final Into in the gaseous products of Thermal Synthetic high score device KR-DS, at least one in the hydrogen rich gas gas 399S of the component containing high boiling hydrocarbon Divide higher boiling gas component to enter in liquid phase and carries out secondary plus hydrogen lighting reaction；

Hydrogen rich gas gas 399S, it may be possible to the gas-phase product of the upstream hydrogenation reaction grade QR from hydrogenation reaction grade KR；

3. in the charging of Thermal Synthetic high score device KR-DS include gas-liquid mixed phase material 388S, with Thermal Synthetic high score device KR-DS into The liquid phase hybrid separation of material, the gas component in mixed phase material 388S enter in gas phase and eventually enter into Thermal Synthetic high score device KR- In the gaseous products of DS, the liquid phase component in mixed phase material 388S, which enters in liquid phase, carries out secondary plus hydrogen lighting reaction；

Gas-liquid mixed phase material 388S, it may be possible to which the gas-liquid mixed phase of the upstream hydrogenation reaction grade QR from hydrogenation reaction grade KR produces Object；

4. include hydrocarbon liquid cooling but material 377S in the charging of Thermal Synthetic high score device KR-DS, with Thermal Synthetic high score device KR-DS into The liquid phase of material mixes and reduces its temperature；

Hydrocarbon liquid cooling but material 377S, it may be possible to which separation or fractional distillation process from the net product URP of hydrogenation process obtain Hydrocarbon liquid material；

5. including hydrogen supply hydrocarbon material 366S in the charging of Thermal Synthetic high score device KR-DS, fed with Thermal Synthetic high score device KR-DS Liquid phase mix to inhibit coking；

Hydrogen supply hydrocarbon material 366S, it may be possible to what separation or fractional distillation process from the net product URP of hydrogenation process obtained Hydrocarbon liquid material or its stabilized hydrogenation reaction product or its fractionation fraction.

Liquid short residence time region KR-DV01, operation side is arranged in the liquid phase region of the present invention, Thermal Synthetic high score device KR-DS Formula can be selected from a kind or several of combination in following:

1., will be in the KR-DV01 of region using the material of the hydrogen containing air lift in liquid short residence time region KR-DV01 At least part low boiling component air lift in liquid phase enters in gas phase, and eventually enters into the gas phase of Thermal Synthetic high score device KR-DS In product；

2. using the hydrogen rich gas gas 99S of the component containing high boiling hydrocarbon as gas in liquid short residence time region KR-DV01 Gas is mentioned, at least part low boiling component air lift in the liquid phase in the KR-DV01 of region is entered in gas phase and eventually entered into comprehensive At least part higher boiling in the gaseous products for closing hot high score device KR-DS, in the hydrogen rich gas gas 99S of the component containing high boiling hydrocarbon Gas component, which enters in liquid phase, carries out secondary plus hydrogen lighting reaction；

Hydrogen rich gas gas 99S, it may be possible to the gas-phase product of the upstream hydrogenation reaction grade QR from hydrogenation reaction grade KR；

3. in liquid short residence time region KR-DV01, using gas-liquid mixed phase material 88S, with the liquid in the KR-DV01 of region Separation is mixed, the gas component in mixed phase material 88S enters in gas phase and eventually enters into the gas phase of Thermal Synthetic high score device KR-DS In product, the liquid phase component in mixed phase material 88S, which enters in liquid phase, carries out secondary plus hydrogen lighting reaction；

Gas-liquid mixed phase material 88S, it may be possible to which the gas-liquid mixed phase of the upstream hydrogenation reaction grade QR from hydrogenation reaction grade KR produces Object；

4. using the liquid in hydrocarbon liquid cooling but material 77S, with region KR-DV01 in liquid short residence time region KR-DV01 It mixes and reduces its temperature；

Hydrocarbon liquid cooling but material 77S, it may be possible to what separation or fractional distillation process from the net product URP of hydrogenation process obtained Hydrocarbon liquid material；

5. in liquid short residence time region KR-DV01, using hydrogen supply hydrocarbon material 66S, with the liquid phase in the KR-DV01 of region Mixing is to inhibit coking；

Hydrogen supply hydrocarbon material 66S, it may be possible to the hydrocarbon that separation or fractional distillation process from the net product URP of hydrogenation process obtain Liquid material or its stabilized hydrogenation reaction product or its fractionation fraction.

The present invention, the liquid long residence time region KR-DV02 of Thermal Synthetic high score device KR-DS, mode of operation can be selected from 1 kind or several of combination in following:

1., will be in the KR-DV01 of region using the material of the hydrogen containing air lift in liquid long residence time region KR-DV02 At least part low boiling component air lift in liquid phase enters in gas phase, and eventually enters into the gas phase of Thermal Synthetic high score device KR-DS In product；2. using the hydrogen rich gas gas 199S of the component containing high boiling hydrocarbon as gas in liquid long residence time region KR-DV02 Gas is mentioned, at least part low boiling component air lift in the liquid phase in the KR-DV02 of region is entered in gas phase and eventually entered into comprehensive In the gaseous products for closing hot high score device KR-DS, at least part in the hydrogen rich gas gas 199S of the component containing high boiling hydrocarbon is high boiling Point gas component enters in liquid phase；

Hydrogen rich gas gas 199S, it may be possible to the gas-phase product of the upstream hydrogenation reaction grade QR from hydrogenation reaction grade KR；

3. in liquid long residence time region KR-DV02, using gas-liquid mixed phase material 188S, in the KR-DV02 of region Liquid phase hybrid separation, the gas component in mixed phase material 188S enter in gas phase and eventually enter into Thermal Synthetic high score device KR-DS's In gaseous products, the liquid phase component in mixed phase material 188S enters in liquid phase；

Gas-liquid mixed phase material 188S, it may be possible to which the gas-liquid mixed phase of the upstream hydrogenation reaction grade QR from hydrogenation reaction grade KR produces Object；

4. in liquid long residence time region KR-DV02, using in hydrocarbon liquid cooling but material 177S, with region KR-DV02 Liquid phase mixes and reduces its temperature；

Hydrocarbon liquid cooling but material 177S, it may be possible to which separation or fractional distillation process from the net product URP of hydrogenation process obtain Hydrocarbon liquid material.

The present invention, (1) hydrocarbon material expanded bed hydrogenation process UR can be selected from a kind or 2 of following hydrogenation process Kind or several combinations:

1. the adding using expanded bed of the logistics containing oil product obtained by middle coalite tar or its distillate or its hot procedure Hydrogen process；

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

3. direct hydrogenation liquefaction of coal liquefaction process uses the hydrogenation process of expanded bed, including using the coal of hydrogen supply dissolvent oil to add Hydrogen direct liquefaction liquefaction process, coal refines process to oil altogether, coal faces hydrogen thermosol liquefaction process；

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

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

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

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

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

Above-mentioned hot procedure is selected from coking or catalytic cracking process or catalytic pyrolysis process or hydrogenation process.

The present invention, (1) hydrocarbon material expanded bed hydrogenation process UR, existing solid particle can in following 1 Kind is several:

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

2. catalyst granules；

3. iron rust particle；

4. particles of inorganic material；

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

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

7. the solid particle from shale；

8. the solid particle from oil-sand；

9. other particles being present in hydrogenation reaction product.

The present invention, (1) hydrocarbon material expanded bed hydrogenation process UR, the expanded bed reactor used, mode of operation can be with 1 kind or several of the combination in following:

1. floating bed, that is, slurry bed system hydrogenator；

2. boiling bed hydrogenation reactor；

3. the combination cot hydrogenator of suspension bed and ebullated bed；

4. slight expanded-bed hydrogenator.

The present invention, (1) hydrocarbon material expanded bed hydrogenation process UR, the working method of the hydrogenator URXE used can With a kind or several in following:

Option 1, liquid material and gas material use the counter-current reactor of pure adverse current working method；

Option 2, reactor URXE, forced circulation returns anti-after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump Answer the fluidized bed reactor of device URXE material inlet；

Option 3, reactor URXE, forced circulation returns anti-after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump Answer the suspended-bed reactor of device URXE material inlet；

Option 4, reactor URXE, forced circulation returns anti-after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of device URXE material inlet is answered, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 5, reactor URXE, forced circulation returns anti-after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of device URXE material inlet is answered, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 6, reactor URXE, forced circulation returns anti-after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor for answering device URXE material inlet, be collected simultaneously cup discharge other collection liquids by other dedicated feeding engines to Downstream conveys liquid material product；

Option 7, reactor URXE, forced circulation returns anti-after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor for answering device URXE material inlet, be collected simultaneously cup discharge other collection liquids by other dedicated feeding engines to Downstream conveys liquid material product；

Option 8, reactor URXE, top are arranged liquid collecting cup and liquid material product are discharged by dedicated feeding engine downstream transport liquid Expect product, is not provided with the fluidized bed reactor system of liquid material product forced circulation；

Option 9, reactor URXE, top are arranged liquid collecting cup and liquid material product are discharged by dedicated feeding engine downstream transport liquid Expect product, is not provided with the suspended-bed reactor system of liquid material product forced circulation；

Option 10, reactor URXE, forced circulation returns after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The ebullated bed of reactor URXE material inlet and the combination type reactor of ebullated bed；

Option 11, reactor URXE, forced circulation returns after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The ebullated bed of reactor URXE material inlet and the combination type reactor of ebullated bed, while circulating pump conveys circulation fluid, downwards Trip conveying liquid material product；

Option 12, reactor URXE, forced circulation returns after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The ebullated bed of reactor URXE material inlet and the combination type reactor of ebullated bed are collected simultaneously other collection liquids warp of cup discharge Cross other dedicated feeding engine downstream transport liquid material products；

The suspended-bed reactor system of flow pattern under the center upstream surrounding of internal guide cylinder is arranged in option 13；

The suspended-bed reactor system of flow pattern in the dirty surrounding in center of internal guide cylinder is arranged in option 14；

Option 15, empty cylinder bubbling bed suspended-bed reactor system；

Option 16 is formed reactor top reaction zone liquid phase and is flowed down under Returning reactor using the external circulation pipe of reactor The device outside circulation of portion's reaction zone；

Option 17, in reactor URXE, setting enters stripping step and the top of the end gas-liquid product of top liquid collecting cup Liquid collecting cup gas-liquid separation step, the average molecular weight for the balance liquid phase that hydrogen rich gas gas stripping gas is formed after mixing with end gas-liquid product Greater than the average molecular weight of the balance liquid phase of end gas-liquid product, what hydrogen rich gas gas stripping gas was formed after mixing with end gas-liquid product The concentration for the hydrocarbon component that the normal boiling point for balancing liquid phase is higher than 350 DEG C is greater than the normal boiling point of the balance liquid phase of end gas-liquid product The concentration of the hydrocarbon component higher than 350 DEG C；The possibility that liquid collecting cup in the final reactor of autoreaction section is discharged through diversion pipe is containing solid The liquid material of body may contain the liquid material product or circular response liquid phase of solid as conversion zone.

The present invention, (1) hydrocarbon material expanded bed hydrogenation process UR, hydrogenation reaction grade obtain the mode of product liquid, can With a kind or several in following manner:

1. liquid material of the possibility containing solid that the gas-liquid separation process of autoreaction order reaction product is discharged, as final reaction grade The liquid material product of solid may be contained；

2. the final reactor of order of reaction uses pure counter-current reactor, the bottom liquid phase region of the final reactor of autoreaction grade Liquid material of the possibility of discharge containing solid may contain the liquid material product of solid as order of reaction；

3. top liquid collecting cup is arranged in the final reactor of order of reaction, the liquid collecting cup warp in the final reactor of autoreaction grade Liquid material of the possibility containing solid of diversion pipe discharge, the liquid material product of solid may be contained as order of reaction；

4. top liquid collecting cup is arranged in the final reactor of order of reaction, the liquid collecting cup warp in the final reactor of autoreaction grade Liquid material of the possibility containing solid of diversion pipe discharge, as the liquid material to be de-gassed that may contain solid；

Possibility to be de-gassed contains the liquid of solid, by cyclonic separation step be separated into all the way rich in bubble liquid stream, The liquid stream of lean gas bubble all the way；The liquid stream of lean gas bubble, the possibility as order of reaction contain the product liquid of solid；

5. setting enters stripping step and the top of the end gas-liquid product of top liquid collecting cup in the final reactor of order of reaction Portion's liquid collecting cup gas-liquid separation step, the mean molecule for the balance liquid phase that hydrogen rich gas gas stripping gas is formed after mixing with end gas-liquid product Amount is greater than the average molecular weight of the balance liquid phase of end gas-liquid product, and hydrogen rich gas gas stripping gas is formed after mixing with end gas-liquid product Normal boiling point the conventional of balance liquid phase that is greater than end gas-liquid product higher than the concentration of 350 DEG C of the hydrocarbon component of balance liquid phase boil The concentration of the hydrocarbon component of the point higher than 350 DEG C；The possibility that liquid collecting cup in the final reactor of autoreaction grade is discharged through diversion pipe contains The liquid material of solid may contain the liquid material product or circular response liquid phase of solid as order of reaction.

The present invention, (1) hydrocarbon material expanded bed hydrogenation process UR, the first raw material URF may include in following materials It is one or more of:

1. oil product obtained by coalite tar or its distillate or its hot procedure；

2. oil product obtained by medium temperature coal tar or its distillate or its hot procedure；

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

4. oil product obtained by direct hydrogenation liquefaction of coal liquefaction process, direct hydrogenation liquefaction of coal liquefaction process includes molten using hydrogen supply The direct hydrogenation liquefaction of coal liquefaction process of agent oil, coal refines process to oil altogether, coal faces hydrogen thermosol liquefaction process；

5. oil product obtained by petroleum based heavy fuel oils or its distillate or its hot procedure；

6. oil product obtained by shale oil or its distillate or its hot procedure；

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

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

9. other colloid weight contents are higher than 15% and/or hydrocarbon ils of the asphalitine weight content higher than 5.0%；

The present invention, (1) hydrocarbon material expanded bed hydrogenation process UR, Fu Fang expect that KAS can be mainly 450 by normal boiling point ~510 DEG C of the hydrocarbon component forms and can contain solid particle, and Fu Fang material KAS can enter hydrocarbon material expanded bed hydrogenation reaction mistake Pass through at least part reaction compartment in journey UR.

The present invention, (1) hydrocarbon material expanded bed hydrogenation process UR, Fu Fang expect that KAS can be selected from one in following logistics Kind is several:

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

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

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

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

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

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

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

8. other aromatic hydrocarbons weight contents are higher than 40% hydrocarbon ils.

The present invention, (1) hydrocarbon material expanded bed hydrogenation process UR, Fu Fang expect KAS can in following materials one Kind is several:

1. the middle matter wax oil of petroleum base viscous crude；

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

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

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

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

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

7. kerosene refines the middle matter wax oil that hydrogenation reaction product fractional distillation process obtains altogether.

The present invention, the first raw material URF can mainly be made of 520 DEG C of normal boiling point > of the hydrocarbon component and contain asphalitine Component；

Hydrocarbon material expanded bed hydrogenation process UR includes at least two hydrogenation reaction grade；

The first hydrogenation reaction grade 1R of hydrocarbon material expanded bed hydrogenation process UR, being one has liquid product circulation to add Hydrogen order of reaction；

Hydrocarbon material expanded bed hydrogenation process UR, end hydrogenation reaction grade are ENDR；

End hydrogenation reaction grade is that ENDR is included at least in the hydrogenator used using at least 1 hydrogenator 1 up flow type expanded bed hydrogenator, last 1 hydrogenator ENDR9E are up flow type expanded bed hydrogenator；

The last one hydrogenation reaction grade ENDR is the hydrogenation reaction grade ENDR for having liquid product to recycle, end hydrogenation reaction grade The product ENDR-P of ENDR carries out gas-liquid separation using Thermal Synthetic high score device ENDR-DS and liquid material is distributed；

The reaction cycle liquid ENDR- of the liquid short residence time region ENDR-DV01 discharge of Thermal Synthetic high score device ENDR-DS The composition of DSLR, can a kind or several in following:

1. the weight concentration of the hydrocarbon component of the normal boiling point higher than 350 DEG C is greater than 60%；

2. the weight concentration of the hydrocarbon component of the normal boiling point higher than 450 DEG C is greater than 45%；

3. the weight concentration of the hydrocarbon component of the normal boiling point higher than 480 DEG C is greater than 35%；

4. the ratio of the total weight of twin nuclei aromatic hydrocarbons and multiring structure aromatic hydrocarbons and asphalitine weight is greater than 3.

The present invention, 520 DEG C of normal boiling point > of the hydrocarbon in hydrocarbon material expanded bed hydrogenation process UR, the first raw material URF The one way of component is hydrocracked conversion ratio UR-CON-SX, can a kind in following:

1. being greater than 75%；

2. being greater than 85%；

3. being greater than 90%.

The present invention, 520 DEG C of normal boiling point > of the hydrocarbon in hydrocarbon material expanded bed hydrogenation process UR, the first raw material URF It is UR-CON-SX that the one way of component, which is hydrocracked conversion ratio,；

The normal boiling point in the first hydrogenation reaction grade 1R, the first raw material URF of hydrocarbon material expanded bed hydrogenation process UR The one way for the hydrocarbon component that 520 DEG C of > is hydrocracked conversion ratio 1R-CON-SX, can a kind or several in following:

1. being hydrocracked the 35~60% of conversion ratio UR-CON-SX for one way；

2. being hydrocracked the 60~80% of conversion ratio UR-CON-SX for one way.

The present invention uses hydrogen-containing hydrocarbon stream DS, the confession of hydrogen-containing hydrocarbon stream DS in hydrocarbon material expanded bed hydrogenation process UR Hydrogen hydrocarbon weight concentration, can a kind in following:

1. being 15~20%；

2. being 20~30%；

3. being 30~45%；

4. being 45~65%.

The present invention, in general, (1) is separated into thermal high separation process S100, the net product URP of hydrogenation process comprising normal Rule hydrogen, conventional gas hydrocarbon, conventional liq hydrocarbon gas S100V and liquid mainly may be formed by conventional liq hydrocarbon containing solid The liquid material S100L of phase component；

(2) it in gas recovery section S100V-GU, separates gas S100V and obtains hydrogen-rich gas HPV, at least part hydrogen-rich Gas gas HPV enters hydrogenation process use.

The present invention, in general, the hydrogen volume concentration of hydrogen rich gas gas HPV, a kind in following:

1. being greater than 75%；

2. being greater than 85%.

The present invention, in general, (3), in liquid material recovery section S100L-GU, separation may be containing solid mainly by conventional liquid Body hydrocarbon forms the liquid material S100L of liquid phase component, obtains that the hydrocarbon mainly by normal boiling point higher than 520 DEG C forms and boils containing conventional The heat from hydrogenation cracked vacuum residue THC-VR that rich in colloid, the possibility of asphalitine contains solid particle of the point higher than 570 DEG C.

The present invention, in general, at least part heat from hydrogenation cracked vacuum residue THC-VR does not enter hydrogenation process UR.

The present invention, in general, at least part heat from hydrogenation cracked vacuum residue THC-VR is as reaction-fractionation circulating path Recycle oil S66 enters hydrogenation process UR, and recycle oil S66 is possibly into any 1 of hydrogenation process UR or 2 or more Among a hydrogenation reaction grade.

In hydrocarbon material expanded bed hydrogenation process UR, the weight chemistry hydrogen consumption of the first raw material URF can be selected from following In a kind:

1. being 0.50~1.0%；

2. being 1.0~2.0%；

3. being 2.0~3.0%；

4. being 3.0~4.0%.

The present invention, in general, the first raw material URF, can mainly be made of 520 DEG C of normal boiling point > of the hydrocarbon component and contain drip Green matter component；

The carbon residue content of first raw material URF, can a kind in following:

1. being 10~18%；

2. being 18~28%；

3. being 28~35%；

4. for greater than 35%.

The present invention, in general, (1) first raw material URF, is mainly made of 520 DEG C of normal boiling point > of the hydrocarbon component and contains drip Green matter component；

Hydrocarbon material expanded bed hydrogenation process UR is heavy oil up flow type floating bed hydrogenation heat cracking reaction process, operation Mode can a kind or several in following:

1. reaction process UR, operating condition are as follows: reaction temperature is 400~485 DEG C, and reactor pressure is 6~30MPa, gas Phase hydrogen volume concentration 50~95%, gas-liquid volume ratio are 300~1500Nm³/m³, hydrogenation catalyst additive amount is heavy oil feedstock 0.001~3 mass % of weight, co-catalyst additive amount are that sulphur in co-catalyst/catalyst activity metal molar ratio is 1.0 ~2.0, volume space velocity is 0.25~5.0hr^-1；

2. reaction process UR, the heat from hydrogenation Cracking catalyst URC used, include at least Mo element, Mo is anti-in first plus hydrogen The body of work form for answering process UR is M₀S₂, powdery that the hydrogenation catalyst URC of working morphology is 0.3 nanometer~100 microns Grain；

3. reaction process UR, the heat from hydrogenation Cracking catalyst URC used, include at least Mo element, Mo is anti-in first plus hydrogen The body of work form for answering process UR is M₀S₂, powdery that the hydrogenation catalyst URC of working morphology is 0.3 nanometer~100 microns Grain；

Hydrogenation catalyst URC, addition state are or mixtures thereof the water soluble salt compound of molybdenum；

4. reaction process UR, the heat from hydrogenation Cracking catalyst URC used, include at least Mo element, Mo is anti-in first plus hydrogen The body of work form for answering process UR is M₀S₂, powdery that the hydrogenation catalyst URC of working morphology is 0.3 nanometer~100 microns Grain；

Hydrogenation catalyst URC, addition state are or mixtures thereof the oil-soluble salt compounds of molybdenum；

5. reaction process UR, the heat from hydrogenation Cracking catalyst URC used are catalyzed comprising nanometer ultra-fine grain hydrated ferric oxide Agent；

It include high activity group 6. reaction process UR, the hydrogenation catalyst URC used are a kind of composite hydrogenation catalysts Divide and low activity component；The weight ratio of the high-activity component metal and low activity component metals is 0.1 to 10；The high activity Component contains or mixtures thereof oil-soluble salt compounds or water soluble salt compound of molybdenum；The low activity group is divided into oxidation Iron ore or iron sulfide ore, wherein iron in ore content is not less than 40wt%, and heat from hydrogenation Cracking catalyst water content is lower than 2wt%；The powdered granule that heat from hydrogenation cracking catalyst particles diameter is 1~100 μm；

7. reaction process UR, the heat from hydrogenation Cracking catalyst URC used include iron oxide and/or pyrite and/or bloodstone And/or molybdenum oxide and/or molybdenum sulfide and/or ammonium molybdate and/or nickel sulfide.

Hydrocarbon material expanded bed hydrogenation process UR is heavy oil up flow type floating bed hydrogenation heat cracking reaction process；

In reaction process UR, the hydrogenation catalyst URC used includes at least Mo element, and Mo adds hydrogen anti-in heavy oil up flow type The body of work form for answering process UR is M₀S₂, powdery that the hydrogenation catalyst URC of working morphology is 0.3 nanometer~100 microns Grain；

The operating condition of reaction process UR is, can a kind in following:

1. the operating condition of reaction process UR are as follows: temperature is 350~480 DEG C, pressure is 6.0~30.0MPa, hydrogen/original Expect oil volume than being the 0.001~8.0% of heavy oil F1 weight, volume for 0.01~2000, hydrogenation catalyst R10C addition weight Air speed is 0.1~10.0hr^-1；

2. weight is added in hydrogenation catalyst URC, the M of working morphology based on conversion₀S₂, with the first raw material URF weight flow Ratio be 400/7/1000000ths ten to million, reactor volume air speed be 0.1~2.0hr^-1；

The operation temperature of reaction process UR is 400~450 DEG C；

The average operating temperature of first hydrogenation reaction grade 1R, lower than the average operating temperature 5~20 of follow-up hydrogenation order of reaction ℃；

3. weight is added in hydrogenation catalyst URC, the M of working morphology based on conversion₀S₂, with the first raw material URF weight flow Ratio be hundred a ten thousandths 300/100000000ths to million, reactor volume air speed is 0.2~1.0hr^-1；

The operation temperature of reaction process UR is 410~445 DEG C；

The average operating temperature of first hydrogenation reaction grade 1R, lower than the average operating temperature 10~15 of follow-up hydrogenation order of reaction ℃。

Detailed description of the invention

The present invention is described below in conjunction with attached drawing uses the hydrocarbon material expansion bed hydroprocessing side of reaction product Thermal Synthetic high score device The reaction process technological principle process and structure of reactor of method, still, it cannot limit the contents of the present invention and application field.

Fig. 1 is 1st kind reaction of the present invention using the hydrocarbon material expanded bed method of hydrotreating of reaction product Thermal Synthetic high score device Process principle process schematic diagram and structure of reactor schematic diagram.

As shown in Figure 1, belonging to the hydrocarbon material level-one hydrogenation process comprising 1 order of reaction 1R, it is suitable for heavy-oil hydrogenation The floating bed hydrogenation reactor A R of bottoms material distribution plate, intermediate material distribution plate is arranged using 1 for heat cracking reaction process, The separation process of reaction product uses Thermal Synthetic high score device DS；Reaction cycle liquid DSLR is arranged in the liquid phase region of Thermal Synthetic high score device DS Flow at high speed, the low speeds flow of region DV01 and Re Gao liquid separation DSLP of more inefficient degassing, efficient degassing region DV02.

As shown in Figure 1, the possibility conveyed through pipeline 101 contains the slurry oil material of hydrogen in reactor A RE system ARF1, the gas material ARH1 containing hydrogen conveyed through pipeline 111, (can with the circulation liquid phase ARRL1 conveyed through pipeline 161 Gas phase can be contained) it is mixed into the feed distributor of the comprehensive charging ARTF usually bottom reacted device ARE feed inlet top installation ARFS (not shown) carries out the entire horizontal feed section that predistribution makes charging be evenly distributed to distribution plate ARBS as far as possible On；ARFS feed distributor can be arbitrary suitable construction, such as aperture or the distribution pipe cracked, aperture or the distribution cracked Cover；Distribution plate ARBS can be arbitrary suitable construction, usually using multiple allocation unit ARBSK, each allocation unit The lower part distribution plate ARBS feed pipe (not shown) and the top distribution plate ARBS bubble-cap (not shown) is arranged in ARBSK, comes Gas, liquid, solid body particle mixed phase material from the lower part distribution plate ARBS passes through distribution plate by distribution plate ARBS lower part feed pipe Enter in the bubble-cap of the top distribution plate ARBS after ARBS, is then fed by distribution plate ARBS top bubble-cap and the lower part distribution plate ARBS Gap the upper section pipeline section across distribution plate ARBS of pipe sprays to distributor upper surface, then disperses, collides, mixing, turning It flows up backward, heavy-oil hydrogenation heat cracking reaction is carried out during the uplink of the AR1 section in reactor A RE main reaction space AR1-R is converted into the main reaction region product AR1-P of reaction process AR1.

As shown in Figure 1, the circulation liquid material ARRL2 that the possibility conveyed through pipeline 162 contains hydrogen enters in reactor A RE Portion is mixed into mixture AR1-PM with the main reaction region the AR1 product AR1-P of uplink after distributor tentatively distributes dispersion, and Forced Mixing is carried out by reallocation disk ARTS and is uniformly distributed, and the mixture homogeneity of top reaction process AR2 charging is improved.

Fig. 2 is the detail drawing for the built-in endless tube distributor 162CP being connected in Fig. 1 with circulation liquid material ARRL2 conveyance conduit 162.

As shown in Fig. 2, being the top view of distributor 162CP, ARE is the shell of reactor A RE, the non-table in liquid collecting cup section Show, 162CP is the endless tube distributor for recycling liquid material ARRL2, and 162CPH is the cloth hole on endless tube distributor 162CP.

As shown in Fig. 2, the circulation liquid material ARRL2 that pipeline 162 conveys enters in endless tube distributor 162CP, pass through cloth hole 162CPH sprays to surrounding space.

As shown in Fig. 2, circulation liquid material ARRL2 enters endless tube distributor 162CP through pipeline 162, pass through distribution hole 162CPH It sprays into reaction compartment and is mixed with intermediate product AR1-P to the lower part, or produced after spraying to reallocation disk ARTS to top with centre Object AR1-P mixing or generally horizontal direction spray into reaction compartment to be mixed with intermediate product AR1-P.

As shown in Figure 1, circulation liquid material ARRL2 enters endless tube distributor 162CP through pipeline 162, pass through distribution hole 162CPH It sprays into reaction compartment after being mixed into mixture AR1-PM with intermediate product AR1-P, is reacted by reallocation disk ARTS to top Space AR2 distribution charging；Reallocation disk ARTS, can be arbitrary suitable construction, usually used multiple allocation unit ARTSK, The each allocation unit ARTSK setting lower part reallocation disk ARTS feed pipe (not shown) and the top reallocation disk ARTS bubble-cap (not shown), the gas, liquid, solid body particle mixed phase material from the lower part reallocation disk ARTS, by under reallocation disk ARTS Portion's feed pipe enters in the bubble-cap of the top reallocation disk ARTS after passing through reallocation disk ARTS, then passes through the top reallocation disk ARTS The gap across the upper section pipeline section of reallocation disk ARTS of bubble-cap and the lower part reallocation disk ARTS feed pipe sprays to reallocation The upper surface disk ARTS, then disperse, collide, mixing, turn to after flow up, in the top reaction compartment AR2 of reactor A RE The main reaction region product AR2-P that heat from hydrogenation cracking reaction is converted into reaction zone AR2 is carried out during uplink, as reactor A R's Product ARTP uplink is discharged by reactor A RE top nozzle 171, and the middle part of Thermal Synthetic high score device DS is entered through pipeline 172, into Row gas-liquid separation, the degassing of liquid subregion and branch discharge.

As shown in Figure 1, Thermal Synthetic high score device DS include upper gas take off liquid zone DS1, middle part gas-liquid flash stage DS2, The degassing of lower liquid subregion and discharge region DS3, DS3 include the region of the flow at high speed of reaction cycle liquid DSLR, more inefficient degassing The region DV02 of the low speeds flow of DV01 and Re Gao liquid separation DSLP, efficient degassing, region DV01, DV02 partition P11 are divided.

As shown in Figure 1, gas-liquid mixed phase material product ARTP enters the middle part gas-liquid flash distillation of Thermal Synthetic high score device DS from middle part Disengagement zone DS2 is separated into the gas phase DSV of entrained drip, the liquid phase DSL of entrained air bubbles herein；Gas phase DSV uplink passes through top gas Body takes off liquid zone DS1, becomes hot high score gas DSVP through the discharge Thermal Synthetic high score device DS of nozzle 191, along pipeline 192 after deviating from drop Conveying.

As shown in Figure 1, liquid phase DSL point is 2 tunnels, downlink is by region DV01, DV02 respectively, purpose according to the invention, Its working method meets following at least one regulation:

1. the flow velocity LV1 of the vertical direction of liquid in the DV01 of region, greater than the stream of the vertical direction of liquid in the DV02 of region Fast LV2, i.e., higher to the frequency of replacement of liquid in space, the ratio K 10=LV1/LV2, K10 of flow velocity LV1 and flow velocity LV2 are usual It is greater than 3.0, even greater than 4.0, particularly greater than 6.0 greater than 1.5, generally higher than 2.0, preferably；

2. the residence time LT1 of liquid in the DV01 of region, less than the residence time LT2 of liquid in the DV02 of region, when stop Between the ratio K 20=LV1/LV2, K10 of LT1 and residence time LT2 be usually less than 0.67, be generally less than 0.50, preferably and be less than 0.33, it is even less than 0.25, particularly less than 0.17.

As shown in Figure 1, in gas-liquid mixed phase material product ARTP Partial Liquid Phase flow path 1000, preferably first pass through region DV01 The space on top, space subsequently into the region top DV02 and under be advanced into region DV02, in this way in Thermal Synthetic high score device DS Liquid level within the scope of, in any case, the flow path region DV01 of reaction cycle liquid DSLR is full of liquid material always, and heat is high The adjacent liquid Space in top of the flow path region DV02 of liquid separation DSLP belongs to the more rich liquid phase region of bubble, is conducive to inhibit coking.

As shown in Figure 1, in reactor A RE system, in the inner space reactor A R, circulation liquid material ARRL2 and centre The specific working mode that product AR1-P mixing, then reallocation enter AR2 reaction compartment is unrestricted, and a kind is illustrated in Fig. 1 Possible working method.

As shown in Figure 1, the circulation liquid phase ARRL2 conveyed through pipeline 162 that may be used, has the effect that

1. the gas-liquid volume ratio and reaction time of AR2 can be adjusted flexibly；

2. under circulating pump DSLR-PUMP flow permanence condition, can be adjusted flexibly AR1, AR2 gas-liquid volume ratio and Reaction time.

Fig. 3 is the flow path region DV01 setting air lift hydrogen point of the reaction cycle liquid DSLR of Thermal Synthetic high score device DS in Fig. 1 The detail drawing of cloth device.

As shown in figure 3, the air lift hydrogen charging 1BH conveyed through piping 194, passes through the flow path area of reaction cycle liquid DSLR The distributor 194CP of domain DV01 is evenly distributed on the horizontal cross-section of flow path region DV01, with descending liquid phase counter current contacting air lift Low boiling component enters in gas phase, and in counter current contacting area, liquid material main body flow direction is downlink, and bubble phase body gas flow direction is upper Row takes off liquid zone DS1 into upper gas after the bubble of uplink is detached from liquid phase region DS23, middle part gas-liquid flash stage DS2.

The flow path region DV02 of the high liquid separation DSLP of heat of Thermal Synthetic high score device DS shown in Fig. 3, also can be set hydrogen Distributor is passed through a small amount of hydrogen, inhibits coking.

Fig. 4 is 2nd kind reaction of the present invention using the hydrocarbon material expanded bed method of hydrotreating of reaction product Thermal Synthetic high score device Process principle process schematic diagram and structure of reactor schematic diagram.

As shown in figure 4, belong to 2 grades of hydrogenation processes of hydrocarbon material comprising 2 order of reactions 1R, AR, suitable for heavy oil plus Hydrogen heat cracking reaction process, the 1st order of reaction 1R use 1 internal Liquid product recycle formula that top liquid collecting cup and catheter is arranged Reactor 1RE, the 2nd order of reaction AR use 1 and the isostructural suspended-bed reactor ARE of ARE phase in Fig. 1.

As shown in figure 4, the partial liquid product 1RLP that liquid collecting cup is discharged at the top of reactor 1RE, is connected in series through reactor ARE；The gas-liquid mixed phase material 1RTMP of liquid collecting cup discharge, first passes through the reaction cycle of Thermal Synthetic high score device DS at the top of reactor 1RE The flow path region DV01 of liquid DSLR is evenly distributed to flow path region DV01's by the distributor 1RTMP-CP of flow path region DV01 On horizontal cross-section, being mixed with descending liquid phase counter current contacting, gas phase and the low boiling point liquid phase component being stripped enter in uplink gas phase, It liquid phase and is absorbed higher boiling gaseous component and enters in the liquid phase of downlink, the bubble of uplink is detached from liquid phase region DS23, middle part gas-liquid After the DS2 of flash stage, liquid zone DS1 is taken off into upper gas；The reaction cycle liquid of the bottom discharge of DV01 in flow path region DSLR is the liquid material that main body flow direction is downlink, and includes the liquid phase components such as the heavy hydrocarbon from gas-liquid mixed phase material 1RTMP, in this way, Liquid phase in gas-liquid mixed phase material 1RTMP, the heavy hydrocarbon component in gas phase have been fully entered and have been carried out in the 2nd order of reaction reactor A RE The deep hydrogenation heat cracking reaction needed, and the gas phase in gas-liquid mixed phase material 1RTMP, the low boiling component in liquid phase, then not It is entered by the 2nd order of reaction reactor A RE in the gaseous products of Thermal Synthetic high score device DS and reaction process has been discharged, avoid gas The deep hydrogenation heat cracking reaction of gas phase in liquid mixed phase material 1RTMP, the low boiling component in liquid phase can reduce hydrogen consumption, drop Low gas yield improves liquid receipts；Hydrogen in certain gas-liquid mixed phase material 1RTMP secondary can not be used in series, and the 2nd order of reaction is anti- Device ARE is answered to need to fill into hydrogen, but these hydrogen can just serve as cooling medium, and can be anti-with the 2nd order of reaction of air lift Answer the low boiling component in the liquid phase feeding of device ARE, make it into gas phase one way by the 2nd order of reaction reactor A RE without It is that circulation is hydrocracked generation gas, hydrogen consumption can be reduced, gas yield is reduced, improve liquid receipts.

As shown in figure 4, the possibility conveyed through pipeline 01 contains the slurry oil material 1RF1 of hydrogen in reactor 1RE system, The gas material 1RH1 containing hydrogen conveyed through pipeline 11 (may contain gas with the circulation liquid phase 1RRL1 conveyed through pipeline 61 Phase) it is mixed into comprehensive charging 1RTF, the feed distributor 1RFS of the usual bottom reacted device 1RE feed inlet top installation is (in figure Be not shown) carry out predistribution make charging be evenly distributed on the entire horizontal feed section of distribution plate 1RBS as far as possible；1RFS into Material distributor can be arbitrary suitable construction, such as aperture or the distribution pipe cracked, aperture or the distribution cap cracked；Distribution plate 1RBS can be arbitrary suitable construction, usually using multiple allocation unit 1RBSK, each allocation unit 1RBSK setting distribution The lower part disk 1RBS feed pipe (not shown) and the top distribution plate 1RBS bubble-cap (not shown), under distribution plate 1RBS The gas, liquid, solid body particle mixed phase material in portion enters distribution plate after distribution plate 1RBS lower part feed pipe passes through distribution plate 1RBS In the bubble-cap of the top 1RBS, then pass through distribution plate 1RBS top bubble-cap with the lower part distribution plate 1RBS feed pipe across distribution plate Gap between the upper section pipeline section of 1RBS sprays to distributor upper surface, then disperses, collides, mixes, flows up after steering, Heavy-oil hydrogenation heat cracking reaction 1R-R is carried out during the uplink of the 1R in reactor 1RE main reaction space is converted into reaction process 1R Main reaction region product 1R-P.

As shown in figure 4, main reaction region product 1R-P uplink passes through outside reactor 1RE upper inside wall and liquid collection cups 1RV Behind annular gap between wall, into the portion being made of reactor head wall and liquid collection cups 1RV on the top reactor 1RE Divide de- liquid formula gas-liquid separation space 1RKD, carries out gas-liquid separation.

As shown in figure 4, the mixing liquid in top product preferentially settles into collection cups 1RV under the effect of gravity, and Gradually deviate from bubble during decline inside collection cups 1RV, the circulation liquid phase 1RRL for deviating from bubble enters the bottom collection cups 1RV It flows downward in the conduit 1RVP in portion and reactor 1RE is discharged, enter in circulation force (forcing) pump 1RPUMP through piping 58, after pressurization Circulation liquid phase 1RRL1 is conveyed through piping 61, total as bottom after mixing with the bottom hydrogen material 1RH1 conveyed through pipeline 11 Body raw material 1RTF enters cyclic process in reactor 1RE through bottom feed inlet.

As shown in figure 4, the top gas-liquid product 1RTMP of reactor 1RE, through the diversion pipe 91 inside insertion collection cups 1RV Reactor 1RE is discharged, is conveyed through pipeline 92, into the flow path region DV01 of the reaction cycle liquid DSLR of Thermal Synthetic high score device DS, It is mixed with downlink liquid material, carries out gas-liquid separation；As previously mentioned, in liquid phase, gas phase in gas-liquid mixed phase material 1RTMP Heavy hydrocarbon component, having fully entered in the 2nd order of reaction reactor A RE with the liquid-phase product DSLR of Thermal Synthetic high score device DS is needed The deep hydrogenation heat cracking reaction wanted；Gas phase from gas-liquid product 1RTMP enters the gaseous products of Thermal Synthetic high score device DS Reaction process has been discharged in DSVP without the 2nd order of reaction reactor A RE, has avoided the gas in gas-liquid mixed phase material 1RTMP The deep hydrogenation heat cracking reaction of low boiling component in phase, liquid phase can reduce hydrogen consumption, reduce gas yield, improve liquid receipts.

As shown in figure 4, the partial liquid product 1RLP that liquid collecting cup is discharged at the top of reactor 1RE, after pump 1RPUMP pressurization, Enter second reactor ARE, the deep hydrogenation heat cracking reaction needed through pipeline 95, pipeline 135.

As shown in figure 4, it is defeated through pipeline 366 that circulation liquid material AR-T01R-RL can be used in reactor 1RE, ARE system Send, by the liquid-phase product DSLR of part Thermal Synthetic high score device DS input first reactor 1RE with reaction feed or intermediate product It is mixed, specific working mode is unrestricted, is the working method being mixed with reaction feed shown in Fig. 4.

As shown in Figure 1, the circulation liquid phase AR-T01R-RL conveyed through pipeline 366 that may be used, has the effect that

1. the gas-liquid volume ratio and reaction time of AR can be adjusted flexibly；

2. the gas-liquid volume ratio of 1R, AR and anti-can be adjusted flexibly under circulating pump DSLR-PUMP flow permanence condition Answer the residence time；

3. the AR high-temp liquid product being discharged is brought into 1R, AR reaction heat is had input to the charging cold material for bringing 1R into In, its preheating temperature can be reduced, fuel consumption is saved；

4. the AR product liquid containing diesel oil, gasoline being discharged is brought into 1R, can reduce 1R it is comprehensive feed cold viscosity, Improve mobility；

5. the AR suitable product liquid containing decompression residuum, wax slop being discharged is brought into 1R, these components are realized High pressure-temperature short-circuit cycle heat from hydrogenation cracking, with by fractionating system recycle compared with, fractionating system scale, energy consumption can be reduced, The ratio 1 for reducing flux oil such as straight run wax slop in raw material 1RF1, improves the selectivity of the reaction process of vacuum residuum feed.

Fig. 5 is 3rd kind reaction of the present invention using the hydrocarbon material expanded bed method of hydrotreating of reaction product Thermal Synthetic high score device Process principle process schematic diagram and structure of reactor schematic diagram.

As shown in figure 5, belong to 2 grades of hydrogenation processes of hydrocarbon material comprising 2 order of reactions 1R, AR, suitable for heavy oil plus Hydrogen heat cracking reaction process, the 1st order of reaction 1R use 1 sky cylinder floating bed hydrogenation reactor 1RE and a Thermal Synthetic high score device It is essentially identical shown in the composition and Fig. 4 of 1R-DS, the 2nd order of reaction AR.

As shown in figure 5, the possibility conveyed through pipeline 01 contains the slurry oil material 1RF1 of hydrogen in reactor 1RE system, The gas material 1RH1 containing hydrogen conveyed through pipeline 11 (may contain gas with the circulation liquid phase 1RRL1 conveyed through pipeline 61 Phase) it is mixed into comprehensive charging 1RTF, the feed distributor 1RFS of the usual bottom reacted device 1RE feed inlet top installation is (in figure Be not shown) carry out predistribution make charging be evenly distributed on the entire horizontal feed section of distribution plate 1RBS as far as possible；1RFS into Material distributor can be arbitrary suitable construction, such as aperture or the distribution pipe cracked, aperture or the distribution cap cracked；Distribution plate 1RBS can be arbitrary suitable construction, usually using multiple allocation unit 1RBSK, each allocation unit 1RBSK setting distribution The lower part disk 1RBS feed pipe (not shown) and the top distribution plate 1RBS bubble-cap (not shown), under distribution plate 1RBS The gas, liquid, solid body particle mixed phase material in portion enters distribution plate after distribution plate 1RBS lower part feed pipe passes through distribution plate 1RBS In the bubble-cap of the top 1RBS, then pass through distribution plate 1RBS top bubble-cap with the lower part distribution plate 1RBS feed pipe across distribution plate Gap between the upper section pipeline section of 1RBS sprays to distributor upper surface, then disperses, collides, mixes, flows up after steering, Heavy-oil hydrogenation heat cracking reaction 1R-R is carried out during the uplink of the 1R in reactor 1RE main reaction space is converted into reaction process 1R Main reaction region product 1RTP, the nozzle 71 at the top of reacted device 1RE is discharged, and enters Thermal Synthetic high score device 1R-DS through pipeline 72 Middle part, carry out gas-liquid separation, liquid subregion degassing and branch discharge.

As shown in figure 5, Thermal Synthetic high score device 1R-DS includes that upper gas takes off liquid zone 1R-DS1, middle part gas-liquid flash separation Area 1R-DS2, the degassing of lower liquid subregion and discharge region 1R-DS3,1R-DS3 include the high velocity stream of reaction cycle liquid 1R-DSLR It moves, the region 1R-DV02 of the low speeds flow of the region 1R-DV01 and Re Gao liquid separation 1R-DSLP of more inefficient degassing, efficient degassing, Region 1R-DV01,1R-DV02 partition 1R-P11 are divided.

As shown in figure 5, gas-liquid mixed phase material product 1RTP is dodged from the middle part gas-liquid that middle part enters Thermal Synthetic high score device 1R-DS Disengagement zone 1R-DS2 is steamed, is separated into the gas phase 1R-DSV of entrained drip, the liquid phase 1R-DSL of entrained air bubbles herein；Gas phase 1R-DSV Uplink takes off liquid zone 1R-DS1 by upper gas, integrates as hot high score gas 1R-DSVP through the discharge of nozzle 91 after deviating from drop Hot high score device 1R-DS is conveyed along pipeline 92.

As shown in figure 5, hot high score gas 1R-DSVP it is comprehensive can to enter Thermal Synthetic high score device DS from middle part through pipeline 921 The flow path region DV01 of the reaction cycle liquid DSLR of hot high score device DS, is mixed with downlink liquid material, carries out gas-liquid separation； As previously mentioned, the heavy hydrocarbon component in gas 1R-DSVP, enters the 2nd reaction with the liquid-phase product DSLR of Thermal Synthetic high score device DS The deep hydrogenation heat cracking reaction needed in stage reactor ARE；Gas phase from gas 1R-DSVP, the liquid of air lift downlink Low boiling component in phase, make it into the gaseous products DSVP of Thermal Synthetic high score device DS reaction process has been discharged and without 2nd order of reaction reactor A RE avoids the deep hydrogenation heat cracking reaction of these low boiling components, can reduce hydrogen consumption, reduce gas Body yield improves liquid receipts.

As shown in figure 5, at least partly liquid phase in Thermal Synthetic high score device 1R-DS, in gas-liquid mixed phase material product 1RTP Flow path 1R-1000, preferably first pass through the space on the region top 1R-DV01, subsequently into the region top 1R-DV02 space simultaneously Under be advanced into region 1R-DV02, in this way within the scope of the Liquid level of Thermal Synthetic high score device 1R-DS, in any case, reaction is followed The flow path region 1R-DV01 of ring liquid 1R-DSLR is full of liquid material, and the flow path region 1R-DV02 of the high liquid separation 1R-DSLP of heat always The adjacent liquid Space in top belong to the more rich liquid phase region of bubble, be conducive to inhibit coking.

As shown in figure 5, liquid phase 1R-DSL points are 2 tunnels, downlink is by region 1R-DV01,1R-DV02 respectively, according to this hair Bright purpose, working method meet following at least one regulation:

1. the flow velocity 1R-LV1 of the vertical direction of liquid in the 1R-DV01 of region, greater than in the 1R-DV02 of region liquid it is vertical The flow velocity 1R-LV2 in direction, i.e., higher to the frequency of replacement of liquid in space, the ratio K 10 of flow velocity 1R-LV1 and flow velocity 1R-LV2 =(1R-LV1)/(1R-LV2), K10 be typically larger than 1.5, generally higher than 2.0, preferably be greater than 3.0, even greater than 4.0, especially Ground is greater than 6.0；

2. the residence time 1R-LT1 of liquid in the 1R-DV01 of region, less than the residence time of liquid in the 1R-DV02 of region Ratio K 20=(1R-LV1)/(1R-LV2) of 1R-LT2, residence time 1R-LT1 and residence time 1R-LT2, K10 is usually less than 0.67, it is generally less than 0.50, preferably less than 0.33, even less than 0.25, particularly less than 0.17.

As shown in figure 5, what the flow region 1R-DV01 of the reaction cycle liquid 1R-DSLR of Thermal Synthetic high score device 1R-DS was discharged Reaction cycle liquid 1R-DSLR, into circulating pump 1RPUMP pressurization after through pipeline 61, tank bottom 35 as reaction cycle liquid 1RRL1 into Enter reactor 1R circular response.

As shown in figure 5, the heat of the flow region 1R-DV02 discharge of the high liquid separation 1R-DSLP of heat of Thermal Synthetic high score device 1R-DS High liquid separation 1R-DSLP is fed through pipeline 95,135 as second reactor AR.

As shown in figure 5, it is defeated through pipeline 366 that circulation liquid material AR-T01R-RL can be used in reactor 1RE, ARE system Send, by the liquid-phase product DSLR of part Thermal Synthetic high score device DS input first reactor 1RE with reaction feed or intermediate product It is mixed, specific working mode is unrestricted；As shown in figure 4, part circulation liquid material AR-T01R-RL is as the 1st road circulation fluid Expect that AR-T01R-RL1 enters the bottom reactor 1RE through pipeline 35, part circulation liquid material AR-T01R-RL can be used as the 2nd tunnel and follow Ring liquid material AR-T01R-RL2 through pipeline 72 enter Thermal Synthetic high score device 1R-DS, then part with reaction cycle liquid 1R-DSLR into Enter in reactor 1RE, partially enters in reactor A RE with the high liquid separation 1R-DSLP of net product heat.

Fig. 6 is 4th kind reaction of the present invention using the hydrocarbon material expanded bed method of hydrotreating of reaction product Thermal Synthetic high score device Process principle process schematic diagram and structure of reactor schematic diagram.

As shown in fig. 6, belong to 2 grades of hydrogenation processes of hydrocarbon material comprising 2 order of reactions 1R, AR, suitable for heavy oil plus Hydrogen heat cracking reaction process is the hydrocarbon material expanded bed method of hydrotreating that the present invention uses reaction product Thermal Synthetic high score device with Fig. 4 The 2nd kind of reaction process technological principle process and structure of reactor the difference is that: the top gas-liquid product of reactor 1RE 1RTMP, after the conveying of pipeline 92 is mixed with the top gas-liquid product ARTP of reactor A RE, as mixed feeding DSMF through pipeline 181 enter Thermal Synthetic high score device DS, rather than as the flow path of the reaction cycle liquid DSLR into Thermal Synthetic high score device DS in Fig. 4 The working method of region DV01；Working method shown in Fig. 6, mixing step is more simple, is conducive to simplify Thermal Synthetic high score device DS Internal structure, but the liquid phase in gas-liquid product 1RTMP cannot fully enter reactor A RE, but be directly entered net production In the high liquid separation DSLP of object heat.

Fig. 7 is 5th kind reaction of the present invention using the hydrocarbon material expanded bed method of hydrotreating of reaction product Thermal Synthetic high score device Process principle process schematic diagram and structure of reactor schematic diagram.

As shown in fig. 7, belong to 2 grades of hydrogenation processes of hydrocarbon material comprising 2 order of reactions 1R, AR, suitable for heavy oil plus Hydrogen heat cracking reaction process is the hydrocarbon material expanded bed method of hydrotreating that the present invention uses reaction product Thermal Synthetic high score device with Fig. 5 The 3rd kind of reaction process technological principle process and structure of reactor the difference is that: the top gas phase of Thermal Synthetic high score device 1R-DS Product 1R-DSVP, after the conveying of pipeline 92 is mixed with the top gas-liquid product ARTP of reactor A RE, as mixed feeding DSMF Enter Thermal Synthetic high score device DS through pipeline 181, rather than as the reaction cycle liquid DSLR into Thermal Synthetic high score device DS in Fig. 5 Flow path region DV01 working method；Working method shown in Fig. 7, mixing step is more simple, is conducive to simplify Thermal Synthetic height Divide the internal structure of device DS, but the dissolvable high boiling component in gas-phase product 1R-DSVP cannot fully enter reactor ARE, but be directly entered in the high liquid separation DSLP of net product heat.

In Fig. 1, Fig. 4, Fig. 5, Fig. 6, Fig. 7, each hydrogenation reaction grade only includes 1 reactor and at least one gas-liquid separation Process.

The present invention, according to different material, different editing objectives, each hydrogenation reaction grade can be used concatenated 2 or Multiple reactors, at this point, on duct coupling between reactor as needed, hydrogen can be added and (be used as cooling material and benefit Be flushed with hydrogen gas), circular response liquid material, quench oil, hydrogen supply dissolvent oil, rich aromatic hydrocarbons material etc..

In Fig. 1, Fig. 4, Fig. 5, Fig. 6, Fig. 7, the different process position of 2 operating pressures is sent to after the pressurization of same source liquid material When setting, when the pressurization amplitude difference that such as 2 tunnel liquid materials need is larger, can respectively it be pressurizeed using 1 booster pump；Such as in Fig. 4 ARPUMP conveys 1 tunnel liquid material ARRL1 through 161 dereaction device ARE of pipeline, 1 tunnel liquid material AR-T01R-RL through 366 dereaction device of pipeline 1RE could alternatively be and be pumped using 2, aspirate liquid material DSLR from pipeline 195 respectively, then defeated respectively after respective pump is pressurizeed It send.

In Fig. 1, Fig. 4, Fig. 5, Fig. 6, Fig. 7, the circular response liquid material DSLR from Thermal Synthetic high score device DS can be by certainly Circular response in Returning reactor ARE is pressed, but requires the height of the outlet of the circular response liquid material of Thermal Synthetic high score device DS Sufficiently high with the elevation difference of the feed inlet for the reactor A RE for receiving circular response liquid material, usually this requires reactor A RE to have foot Thermal Synthetic high score device DS is simultaneously arranged in the sufficiently high position of height by enough absolute altitudes, forms gas-liquid in reactor to provide potential difference Difference " H100- between the static pressure difference fluid column H100X and circular response liquid material DSLR fluid column H100 of mixed phase height of materials H100 H100X " carries out liquid material circulation as motive force.

Specific embodiment

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 350~575 DEG C, generally 370~ 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.

Present invention is primarily based on heavy oil floating bed and/or boiling bed hydrogenation cracking reaction process, oily coals to refine hydrogenation reaction mistake altogether Journey describes.

Hydrocarbon material F1 of the present invention, refers to carbon containing, protium liquid and/or solid, such as oil and/or coal.

Rich virtue material KAS of the present invention, refers to the material of the aromatic hydrocarbons rich in 2 ring structures and multiring structure, mainly by normal It advises the hydrocarbon component that boiling range is 230~530 DEG C to form, wherein the weight content of 350 DEG C of normal boiling point > of the hydrocarbon component is greater than 50%.

The aromatic hydrocarbons of 2 ring structure and multiring structure of the present invention, refers to containing 2 cyclic structures and at least one Cyclic structure belongs to the aromatic hydrocarbons of phenyl ring.

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

Hydrocarbon material hydrogenation process UR of the present invention, typical example are the coal tar pitch floating bed hydrogenations of high temperature coal-tar Deep refining reaction process, the coal tar pitch floating bed hydrogenation heat cracking reaction process of middle coalite tar, direct hydrogenation liquefaction of coal Reaction process, oily coal refine hydrogenation process, petroleum based heavy fuel oils (decompression residuum) suspension bed or boiling bed hydrogenation cracking reaction altogether Process.

Hydrocarbon material hydrogenation process UR of the present invention, in order to which self-produced is rich in twin nuclei aromatic hydrocarbons, multiring structure The wax oil component URPP-VGOC cracking of aromatic hydrocarbons is low boiling hydrocarbon component, can be followed in reaction process UR to wax oil URP-VGOC-RL At this moment ring crack recycles the liquid phase of reaction compartment that wax oil URP-VGOC-RL flows through it, have improve twin nuclei aromatic hydrocarbons, The effect of the concentration of multiring structure aromatic hydrocarbons increases the solubility of asphalitine, is guaranteeing UR terminal liquid stable without generating drip Under conditions of green matter aggregation phase, allow to improve the initial of the hydrocarbon material hydrogenation process UR of asphaltenes in reaction product URP The conversion per pass of raw material or intermediate product asphalitine, this is conducive to coal tar suspension bed heat from hydrogenation cracking reaction process, petroleum base Heavy oil floating bed or boiling bed hydrogenation cracking reaction process, direct hydrogenation liquefaction of coal reaction process, oily coal refine hydrogenation reaction mistake altogether Journey etc. improves liquid product yield, increases economic efficiency.

Hydrogenation of the present invention, refers to hydroconversion process.

Hydrogenation grade of the present invention, refers to hydrogenation reaction grade.

Expanded bed reactor of the present invention refers to up flow type expanded bed reactor.

Expanded bed hydrogenator of the present invention refers to up flow type expanded bed hydrogenator

Expanded bed hydrogenation process of the present invention at least uses 1 expanded bed hydrogenator.

The macroscopic view flowing of processing medium in up-flow reactor of the present invention, reaction compartment or catalyst bed 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 co-flow with uplink from bottom to top； Expanded bed refers to that working condition catalyst bed is in swelling state, and catalyst bed expansion ratio, which is defined as catalyst bed, to be had The height CUH of the empty bed static condition of the maximum height CWH and catalyst bed of working condition when reaction raw materials pass through it Ratio K BED, in general, referred to as slight expanded-bed when KBED is lower than 1.10, referred to as ebullated bed when KBED is between 1.25~1.55, and hang Floating bed is considered as the expanded bed of most extreme form.

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 intermediate production at flow points K Upstream reaction of at least part liquid phase XK-L as circulating fluid XK-LR Returning process point K in object XK or final product XK Area, the reaction product of circulating fluid XK-LR flow through K point and are present among XK.The mode for forming back-mixing stream can be any conjunction Built-in inner ring flow cartridge, built-in outer ring flow cartridge, built-in liquid collecting cup+built-in diversion pipe+built-in circulation is such as arranged in suitable mode Pump, built-in liquid collecting cup+built-in diversion pipe+external circulating pump, external 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 reactor of the present invention 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-LR Reaction product flow through K point and be present among XK.The mode for forming Liquid product recycle can be any appropriate mode, but It is that gas-liquid separation zone must be set in the headspace in reactor, obtains circulation fluid and other products, that is, built-in collection is set Liquid cup+diversion pipe+circularly-supercharged device, circularly-supercharged device are generally circulated pump, can be arranged in inside reactor or outside.

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

Hydrogenation products high pressure hot separator of the present invention is referred to for separating hydrogenation reaction intermediate product or final production The gas-liquid separation equipment of object.

Hydrocarbon material second level of the present invention or multistage method of hydrotreating refer to including two order of reactions or multiple order of reactions Hydrocarbon material method of hydrotreating.

A hydrocarbon material hydrogenation reaction grade of the present invention is referred to since hydrocarbon material enters a hydrogenation process At least one process section until generating the liquid product that oil forms by least part is obtained to its hydrogenation products gas-liquid separation, The gas-liquid separation process of at least part hydrogenation reaction product of hydrogenation process comprising the hydrogenation reaction grade and this grade.Cause This, level-one method of hydrotreating refers to that the process of initial hydrocarbon feedstock only includes a hydrogenation reaction step and the hydrogenation reaction The flow model of step products gas-liquid separation process；One hydrogenation reaction step, can be used 1 or 2 as needed The hydrogenator of platform or more serial operations, thus number of reactors and form be not determine order of reaction foundation, one or The reaction step and its product separator common combination of some tandem reactor compositions could form one and complete adding in meaning Hydrogen order of reaction.

Hydrocarbon material secondary hydrogenation method of the present invention refers to that the process of initial hydrocarbon material adds comprising liquid material Work process is serial operation " by the gas-liquid separation of two different hydrogenation reaction steps and corresponding hydrogenation reaction step products The logistics of the flow model of journey " composition, wherein at least a part of level-one hydrogenated oil composition enters secondary hydrogenation reaction process.

Hydrocarbon material three-level method of hydrotreating of the present invention refers to that the process of initial hydrocarbon material adds comprising liquid material Work process is serial operation " by the gas-liquid separation of three different hydrogenation reaction steps and corresponding hydrogenation reaction step products The logistics of the flow model of journey " composition, wherein at least a part of level-one hydrogenated oil composition enters secondary hydrogenation reaction process, The logistics that at least part secondary hydrogenation generates oil composition enters three-level hydrogenation process.The hydrocarbon material of more series adds hydrogen side The flowage structure of method, analogizes according to mentioned above principle.Multistage method of hydrotreating refers to that the process of initial hydrocarbon material includes liquids Expect that processing flow is " by three or more different hydrogenation processes and hydrogenation products gas-liquid separation process " of serial operation The flow model of composition.

Hydrocarbon material three-level method of hydrotreating, it is string that the process for referring to initial hydrocarbon material, which includes liquid material processing flow, Connection operation forms " by the gas-liquid separation process of three different hydrogenation reaction steps and corresponding hydrogenation reaction step products " Flow model, 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 With the progress of part or all of joint, for illustrating gas-liquid separation process, there may be part combinations for this.

Seemingly hydrocarbon material secondary hydrogenation method, the method for referring to being similar to secondary hydrogenation method of the present invention work as rear class When liquid phase flow ratio tends to infinity in the back-mixing liquid phase flow and upper feeding of upper feeding back-mixing stream expanded bed reactor, effect Fruit is essentially identical to secondary hydrogenation method, but residence time of the gaseous product at initial stage in second reactor is extreme.

Up flow type heat from hydrogenation cracking reaction process UR, the reaction product BASE-URP of hydrocarbon material of the present invention, at least For gas-liquid two-phase logistics, most cases belong to gas, liquid, solid three-phase logistics.Hydrogenation reaction effluent URP of the present invention is for arranging Hydrogenation reaction product BASE-URP out occurs in the form of 1 tunnel or 2 tunnels or multichannel material, is gas phase or liquid phase or gas-liquid mixed phase Or gas-liquid-solid three-phase logistics.

Definition according to the present invention, the present invention expand bed hydroprocessing side using the hydrocarbon material of reaction product Thermal Synthetic high score device Method may include 1 or 2 or multiple hydrogenation reaction grades (or hydrogenation grade).

As needed, the present invention " Liquid product recycle hydrogenates Jia Fufang material among grade " this method, can be applied to this hair Bright hydrocarbon material expanded bed hydrogenation process any one need it is to be used have Liquid product recycle hydrogenation reaction grade (or hydrogenation Grade).

The present invention is applied to heavy oil floating bed and/or boiling bed hydrogenation cracking reaction process, coal tar suspension bed heat from hydrogenation When cracking reaction process, oily coal refine hydrogenation process altogether, usual 1st order of reaction (and have a Liquid product recycle plus hydrogen it is anti- Answer grade) particularly suitable for using the present invention.

The present invention is described below in conjunction with heavy oil floating bed hydrocracking reaction process.

Heavy hydrocarbon of the present invention refers to the logistics containing heavy oil, usually contains asphalitine.

Heavy oil F1 of the present invention, 350 DEG C of the usual > of the normal boiling point of hydro carbons, 450 DEG C of general >, particularly 530 > DEG C, more particularly 570 DEG C of >.

Decompression residuum of the present invention, 450 DEG C of the usual > of the normal boiling point of hydro carbons, 530 DEG C of general >, particularly > 570℃。

The up flow type floating bed hydrogenation heat cracking reaction process of heavy oil F1 of the present invention is referred to comprising floating bed hydrogenation The reaction process of heat cracking reaction process can be individual floating bed hydrogenation heat cracking reaction process, suspension bed and ebullated bed Combined type heat from hydrogenation cracking reaction process etc..

At least part heavy oil occurs for the up flow type floating bed hydrogenation heat cracking reaction process UR of heavy oil F1 of the present invention The heat cracking reaction of F1, the reaction of thermal cracking free radical stabilized hydrogenation, generate the lower hydrocarbon product of at least part boiling point；Heavy oil Up flow type floating bed hydrogenation heat cracking reaction process UR usually cannot achieve one way and react whole lightings, and usually it is rationally high Conversion per pass be usually 70~85%, in such heat from hydrogenation cracked reaction product URP there are certain amount such as 15~ 30% tail oil (heat from hydrogenation crackate residual oil) URP-VR.

If from the point of view of component structure, in heat from hydrogenation crackate residual oil URP-VR inherently heavy oil, macromolecular is not The residue or conversion product of lighting or the concentrate of thermal condensation object macromolecular, with its heat from hydrogenation cracking precursor raw material heavy oil F1 Compared with boiling fraction, in general, gum level therein, asphalt content, carbon residue content significantly increase such as increase 30~ 100%.

In order to improve the processing efficiency of device, preferably increase the conversion per pass of heavy oil F1；And the conversion per pass of heavy oil F1 The raising of rate, necessarily reduces the quantity of the wax oil fraction of rich polycyclic aromatic hydrocarbon in reaction product, while increasing thermal condensation object colloid, drip Green matter, liquid phase coke quantity, this " increase of colloid, asphalitine, the quantity of liquid phase coke " and " colloid, asphalitine, liquid phase coke The reduction of the solvent naphtha quantity of charcoal " develops to over-saturation degree or critical degree of saturation, and it is burnt to will lead to colloid, asphalitine, liquid phase It is mutually second liquid phase that charcoal, which is precipitated as over-saturation pitch from stable colloidal solution system, is caused in the containers such as reactor quickly Coking forces device to be stopped work.

The conversion per pass of heavy oil F1 " improve necessarily increase thermal condensation object colloid, asphalitine, liquid phase coke quantity " this The method under the premise of one fact, avoiding " colloid, asphalitine, liquid phase coke are precipitated ", necessarily reduces heavy oil F1 conversion per pass Rate and/or the fragrant oil KAS of the richness for introducing rich 2 rings and polycyclic aromatic hydrocarbon, since reduction heavy oil F1 conversion per pass is passively method, meeting Device processing efficiency is reduced, therefore " introduces suitable colloid, asphalitine, the solvent naphtha of liquid phase coke and its application method ", just At an important initiative technical problem, it is related to the up flow type floating bed hydrogenation heat cracking reaction process UR of heavy oil F1 Economy, and core of the invention target is, under the premise of total refining richness virtue oil KAS, changes to the proposition of existing reaction method Into, to simplify reaction feed heating system, reduce feed furnace load, diminution reaction zone operating temperature range, reduction reaction system, Fractionating system process scale reduces investment outlay, reduces fuel consumption, reduces device operating severity, improves the economy of overall craft Property.

Rich virtue material KAS of the present invention, refers to the material rich in aromatic hydrocarbons, is generally rich in 2 rings and polycyclic aromatic hydrocarbons, can be with It is coal tar or its distillation distillate oil, can be Rfcc Products diesel oil, wax oil, can be coking heavy oil product wax Oil.

Rich virtue material KAS of the present invention, main hydro carbons is preferably wax oil component, and the conventional boiling range of main hydro carbons can Think 250~530 DEG C, be usually 350~530 DEG C, generally 380~500 DEG C, in particular 400~480 DEG C.

Particularly, it invents the rich virtue and expects that can be heavy oil floating bed hydrogenation hot cracked product circulation wax oil (especially follows Matter wax oil in ring) when, that is, constitute heavy oil floating bed wax oil circulation cracking process.

In heavy oil F1 heat from hydrogenation cracking reaction process UR, the hydrogen supply oil or rich virtue material that normal boiling point is 330~500 DEG C are constituted Solvent naphtha property and quantity, strong will influence asphalitine, the association thermal condensation reaction of colloid or heat scission reaction, solvent naphtha Property is most important.For decompression residuum heat from hydrogenation cracking process inferior, in order to pursue high thermal cracking conversion ratio, it is often desirable that The weight flow 15~30% of fresh decompression residuum is usually about using the weight flow of suitable rich virtue material KAS, Fu Fang material KAS It is even more.

Heavy oil F1 heat from hydrogenation cracking reaction process UR of the present invention, usually in the raw material or product of the hydrogenation process Contain asphalitine.

Heavy oil floating bed hydrogenation reaction process UR of the present invention, the thermal cracking including heavy oil generate free radicals the anti-of fragment It answers and/or the reaction of the stabilized hydrogenation of thermal cracking free radical fragment, and usually hydrofining reaction occurs and/or catalytic hydrogenation is split simultaneously Change the reaction process such as reaction and/or heat from hydrogenation cracking reaction；Therefore, heavy oil floating bed hydrogenation reaction process UR can be to add hydrogen Hydrogenation process based on thermal cracking can be the hydrogenation process based on hydrofinishing effect.

Heavy oil F1 heat from hydrogenation cracking reaction process UR of the present invention, the thermal cracking that heavy oil occurs generate free radicals fragment The reaction of the stabilized hydrogenation of reaction and/or thermal cracking free radical fragment, and hydrofining reaction and/or catalytic hydrogenation usually occur simultaneously The reaction process such as cracking reaction and/or heat from hydrogenation cracking reaction.

The hydrofining reaction of the heavy oil F1, can be plus hydrogen removing impurities qualitative response such as hydrodemetallization reaction plus hydrogen is de- Organic oxygen is reacted plus hydrogen removal of organic sulfur reacts, adding hydrogen to take off, organic oxygen is reacted plus the de- organochlorine of hydrogen reacts plus the de- Organic fluoride of hydrogen is anti- It answers, can be unsaturated carbon-carbon bond adds hydrogen saturated reaction such as olefins hydrogenation reaction, alkynes that hydrogen saturated reaction, aromatic hydrocarbons is added to add Hydrogen saturated reaction can be one or more of above-mentioned reaction.The heat from hydrogenation cracking reaction and thermal cracking of the heavy oil F1 is certainly It is reacted, is usually always occurred together, it is generally present in the high-temperature hydrogenation thermal cracking of heavy oil by the stabilized hydrogenation of base fragment In reaction process.

Heavy oil F1 heat from hydrogenation cracking reaction process UR of the present invention also includes the low high temperature coal-tar of thermal cracking conversion ratio Partial function of the invention may be implemented to produce needle-shape coke raw material pitch in the hydro-upgrading reaction process of pitch.

Heavy oil of the present invention refers to mainly being higher than by normal boiling point 350 DEG C of hydro carbons, preferably mainly by routine The weight that the heavy hydrocarbon oil that hydro carbons of the boiling point higher than 450 DEG C forms, the preferably mainly hydro carbons by normal boiling point higher than 530 DEG C form Matter hydrocarbon ils (decompression residuum), be particularly preferably mainly by normal boiling point it is low higher than 530 DEG C of hydrogen content be rich in aromatic structure The inferior heavy oil of the heavy hydrocarbon composition of unit；Hydrogenation process especially heat from hydrogenation cracking reaction for inferior heavy oil Journey, in order to accelerate hydrogen supply speed, inhibit thermal condensation reaction, reduction heat of reaction, improvement reaction operability, efficient inferior heavy Oily hydrogenation process needs to add the virtue in liquid phase of the rich virtue material of the present invention to increase reaction process more than 2 rings and 2 rings The quantity and concentration of hydrocarbon increase the dispersion degree to liquid phase studies on asphaltene, increase the efficiency of solution transmitting hydrogen, reduce the heat of asphalitine It is condensed coking reaction；Particularly, when rich virtue expects while being rich in hydrogen supply hydrocarbon, also have and the ability of reactive hydrogen is provided in time, can press down The thermal condensation coking reaction of asphalitine processed.

For decompression residuum floating bed hydrogenation thermal cracking process, since reaction initial phase is that reaction liquid phase studies on asphaltene is dense The highest stage of reaction is spent, that is, to the asphalitine diluent demand amount highest stage, therefore, usually rich virtue material or hydrogen supply are molten Agent starts the response procedures of the first floating bed hydrogenation reactor after mixing with fresh decompression residuum, in this way, there is liquid product to follow The first reactor AR1 entrance of first hydrogenation reaction grade AR of ring, logistics to be heated up include fresh heavy oil F1, hydrogen, Fu Fang material KAS, for oily for the hydrothermal solution phase product circulation of certain pressure, certain flow, certain component, certain temperature, the two was mixed The temperature drop of journey is a definite value, this is also the apparent temperature rise value of the main reaction region of the first hydrogenation reaction grade AR.

For heavy-oil hydrogenation heat cracking reaction process, under conditions of average reaction temperature is certain, main reaction region Apparent temperature rise value is about big, indicates that the reaction zone volume ratio for the non-ideal reaction zone that temperature is too low, temperature is excessively high is bigger；Temperature Too low non-ideal reaction zone, will lead to low-temp reaction space reaction speed it is too low, reduce space efficiency；The excessively high unreasonably of temperature Think reaction zone, will lead to the excessive thermal cracking of reaction compartment, thermal condensation and coking reaction it is too fast, will increase pyroreaction space Gas yield, pyrocondensation compound production and green coke amount, therefore, for heavy oil heat from hydrogenation cracking reaction process, it is desirable to reaction zone temperature Liter is low as far as possible, to reduce deviation of the operation temperature to ideal temperature, improves reaction compartment efficiency, reduces nonideal side reaction production Object (gas and coke) yield improves liquid phase stability.

For the first hydrogenation reaction grade AR comprising 2 or the heavy-oil hydrogenation heat cracking reaction process UR of multiple order of reactions Speech, it is usually a reaction time longest order of reaction, and is easy to the concentration stage of reaction of the hydrocarbon component of heat from hydrogenation cracking, It is a reaction heat ratio higher stage, task is to avoid too fast generation under reaction temperature as rationally low as possible Under conditions of thermal condensation object, it is later period heat from hydrogenation cracking reaction process that carry out asphalitine, which adds hydrogen saturation and either shallow thermal cracking, BR prepares the methylene bridged bond for being easy to thermal cracking.That is, the operating effect of the first hydrogenation reaction grade AR, adds whole heavy oil Hydrogen heat cracking reaction process UR has significant impact, and the task of the present invention is propose that the first hydrogenation reaction grade AR of reduction is apparently warm The economically effectively method of non-ideal reaction zone ratio is risen, reduces, " Fu Fang material or hydrogen supply dissolvent and complete for this reason, it may be necessary to abandon Start the response procedures of the first floating bed hydrogenation reactor after portion's fresh feed mixing " conventional method.

In fact, the reasons for the above problems are, first for heavy-oil hydrogenation heat cracking reaction process UR plus hydrogen Order of reaction AR, the richness virtue material or hydrogen supply dissolvent of addition have been configured to material to be heated, outstanding in the leading portion for having liquid product to recycle Floating bed hydrogenation process AR will be needed based on leading portion product gas-liquid separator, the leading portion product liquid material circulating pump that must be used Richness virtue material or hydrogen supply dissolvent be changed into first order reaction process high-temperature liquid-phase product go to heat it is other wait the charging that heats up (heavy oil and Or hydrogen) be it is entirely possible, the process recycle the first hydrogenation reaction grade AR reaction heat while, not only reduce dedicated Chilling inventory reduces AR product ARP temperature to reduce AR product amount, that is, time of incrementss AR reaction heat Yield；In this way, reducing the heat that ARP brings downstream into, downstream reactor can be reduced and feed the chilling inventory used；Therefore, Final product URP quantity can be substantially reduced, the heat for bringing high pressure hot separator into can be substantially reduced, thermal high separation can be reduced Device feeds the chilling inventory used；Meanwhile reducing hot high score destiny amount, hot high score oil quantity, reduce hydrogen gas system rule Mould, investment, energy consumption reduce fractionating system scale, investment, energy consumption, in general, can reduce reaction process, hydrogen gas system, The scale of fractionating system is conducive to significantly reduce investment, reduces energy consumption；Particularly, reaction zone operation can be effectively reduced in this way Temperature range effectively reduces deviation of the operation temperature to ideal temperature, improves reaction compartment efficiency, reduces nonideal side reaction Product (gas and coke) yield improves liquid phase stability, is conducive to stable operation, extends the continuous operation period, improves asphalitine Conversion ratio, this point for the decompression residuum floating bed hydrogenation thermal cracking process inferior high for carbon residue content, have great shadow It rings, directly determines reliability, the economy of technical process.

And rich virtue material KAS is used as supplies, conversion per pass is a secondary problem, and influence compared with It is small, especially under the conditions of the recycle ratio of the first hydrogenation reaction grade AR recycle oil is biggish, influence smaller.

For the decompression residuum floating bed hydrogenation thermal cracking process inferior high for carbon residue content, the first hydrogenation reaction grade AR The second half reaction temperature it is higher, therefore, it is necessary to more hydrogen supply dissolvents, when Fu Fang expects that KAS is rich in hydrogen supply the hydrocarbon component, using this The flowing of invention, circulating path mode, more conducively play its effect.

Liquid product recycle hydrogenates the mode of Jia Fufang material among grade, can be 2 times or is repeatedly added portionwise, then can be formed 3 times or more small size temperature drops more greatly reduce apparent temperature rise, reduce the deviation to ideal response temperature by a larger margin Degree.

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

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

In current decompression residuum floating bed hydrogenation thermal cracking technology, disperse type catalyzer is used, catalyst has iron-based Catalyst, catalyst with base of molybdenum and compound bimetallic or multimetal reforming catalyst, wherein catalyst with base of molybdenum has activation hydrogen Ability is strong, reaction temperature is low, has stronger plus hydrogen saturability to polycyclic aromatic hydrocarbon, catalyst surface noncoking, can be repeated several times It the use of, additive amount is only that about 1 the percent of ferrum-based catalyst additive amount, decompression residuum overall conversion is higher by the crowds such as 5~8% More advantages are most competitive hydrogenation of residual oil suspended bed hot cracking catalysts.But molybdenum base hydrogenation of residual oil suspended bed thermal cracking The suitable range of reaction temperature of catalyst is relatively narrow, for example reaction temperature at especially less than 415 DEG C, is reacted lower than 420 DEG C Speed declines quickly, and reaction speed is very low, this will lead to, and the residence time is too long, reactor volume is excessive；On the other hand, it reacts When temperature is higher than 430 DEG C especially greater than 435 DEG C, reaction speed rises quickly, and thermal condensation reaction meeting rapid increase, this It will lead to the disadvantages of tetrahydrofuran insoluble yield is excessive, gas yield is excessive, hydrogen consumption is excessive.Therefore, catalyst with base of molybdenum Range of reaction temperature be it is narrow, usually 410~440 DEG C of preferablies are 420~435 DEG C, it is evident that use molybdenum base When hydrogenation of residual oil suspended bed hot cracking catalyst, need to control reaction temperature in range as narrow as possible.

As needed, of the invention, any one that can be applied to heavy oil floating bed hydrogenation thermal cracking process has liquid production The hydrogenation reaction grade of object circulation, usual last 1 hydrogenation reaction grade are suitable for using the present invention.

For simple flow, in the upper space setting of the end hydrogenator of either shallow heat from hydrogenation cracking reaction process 1R Formula liquid collecting cup is set, so that hot circulating solution is returned to 1R's with the system that liquid header, drain pipeline, circulating pump, liquor charging pipeline form In hydrogenation reaction space.

In order to provide more hot logistics to the first hydrogenation reaction grade 1R and form the high pressure of end reaction product liquid High temperature short-circuit cycle, can on the Thermal Synthetic high score device that the hydrogenation reaction product of deep hydrogenation heat cracking reaction process AR uses, The hot high score oil in part is recycled back into the hydrogenation reaction space of 1R.

Rich virtue material KAS described herein, refers to the material rich in bicyclic and more polycyclic aromatic hydrocarbons, can be hydrogen supply hydrocarbon predecessor Object or hydrogen supply hydrocarbon serve as hydrogen in the up flow type hydrogenation process (hydrogenation modification reaction process, heat from hydrogenation cracking reaction process) of heavy oil Transmit hydrocarbon or hydrogen supply hydrocarbon.

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

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

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

The gas-liquid volume ratio or hydrogen to oil volume ratio of hydrogenation process of the present invention, refer to the standard state of hydrogen The ratio of volume flow and the normal pressure of specified oily logistics, 20 DEG C of volume flow.

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

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

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

Back-mixing stream expanded bed 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 intermediate production at flow points K Upstream reaction of at least part liquid phase XK-L as circulating fluid XK-LR Returning process point K in object XK or final product XK Area, the reaction product of circulating fluid XK-LR flow through K point and are present among XK.The mode for forming back-mixing stream can be any conjunction Built-in inner ring flow cartridge, built-in outer ring flow cartridge, built-in liquid collecting cup+diversion pipe+circulating pump, external is such as arranged in suitable mode 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 intermediate product XK or final product at flow points K At least part liquid phase XK-L in XK as the upstream reaction zone circulating fluid XK-LR return logistics XK, circulating fluid XK-LR's Reaction product flows through K point and is present among XK.The mode for forming Liquid product recycle can be any appropriate mode, still Gas-liquid separation zone must be set in the headspace in reactor, obtain circulation fluid and other products, that is, built-in liquid collecting is set Cup+diversion pipe+circularly-supercharged device, circularly-supercharged device are generally circulated pump, can be arranged in inside reactor or outside.

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

Each section of the invention described in detail below.

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 and the stabilized hydrogenation for lose hydrogen hydrogen supply dissolvent MFS resurrection process Reaction process MR.

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 contain hydrogen supply the hydrocarbon component DS and/or 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 hydrocarbon mixtures rich in hydrogen supply the hydrocarbon component DS and/or hydrogen supply hydrocarbon precursor the hydrocarbon component DS-BF.

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

Since hydrogen supply dissolvent can face in heavy oil, hydrogen hot-working aromatic hydrogenation saturated reaction process, that heavy oil faces hydrogen thermal cracking is anti- It answers process quickly to provide reactive hydrogen, quickly transmit reactive hydrogen and (for example pass out the reactive hydrogen of catalyst surface quickly to improve The utilization rate that catalyst generates active hydrogen efficiency, improves reactive hydrogen), therefore, in the cyclic process of a hydrogen supply dissolvent, if energy It is enough to keep hydrogen supply the hydrocarbon component DS transmitting more living with reasonable flow model (for example passing through more hydrocarbons hydrogenation reaction process) Property hydrogen, then can be improved the service efficiency of reactive hydrogen, to form the effective use method of reactive hydrogen, the present invention also utilizes this Kind 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 dissociation 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 SH of recycling is from rich in double ring arene and/or polycyclic The hydrogen supply hydrocarbon precursor logistics SHSBF of aromatic hydrocarbons hydrogenation reaction obtained by the hydroconversion reaction zone MR conversion for being prepared as target with hydrogen supply hydrocarbon The logistics of effluent MRP；It is prepared as the hydroconversion reaction zone MR of target with hydrogen supply hydrocarbon, can work under conditions of any be 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 300~3000 reaction condition under operate.

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

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

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

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

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

The hydroconversion reaction zone MR that target is prepared as with hydrogen supply hydrocarbon, the hydrogenation catalyst MR-CAT used are included at least Hydrocatalyst for saturating arylhydrocarbon, usually also comprising Hydrodemetalation catalyst, (workflow position is likely located at aromatic hydrogenation saturation and urges Before agent bed).

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

Hydrogen supply dissolvent is used in the up flow type hydrogenation process of heavy oil, free radical can be quickly eliminated, can be improved hot tearing Change product hydrogen content, but also therefore heat cracking reaction can be inhibited to reduce thermal cracking conversion ratio；And the up flow type of heavy oil adds hydrogen The raising of the residual oil quality of reaction process allows its further heat from hydrogenation cracking (such as circulation heat from hydrogenation cracking) total to improve Body heat cracking conversion rate.With regard to the thermal cracking again of thermal cracking tail oil of thermal cracking of heavy oil and heavy oil general effect and Speech, can effectively improve overall heat from hydrogenation cracking conversion rate using hydrogen supply dissolvent, is effectively reduced and gets rid of the yield containing solid tail oil outside, from And improve the economy of process.

Reaction of the richness aromatic hydrocarbons wax oil KVGO described in detail below during heat from hydrogenation cracking reaction tends to.

From the point of view of component characteristic, richness aromatic hydrocarbons wax oil KVGO of the present invention, is that heat from hydrogenation cracking reaction difficulty is inferior to Decompression residuum, the hydrocarbon component for depressurizing heavy wax oil；Residual oil, heavy-oil hydrogenation hot cracked product for heavy-oil hydrogenation hot cracked product Wax slop for, although the middle matter wax oil of heavy-oil hydrogenation hot cracked product is the fraction of arene rich, but its colloid, pitch Matter content is much lower, have lower carbon residue, thermal condensation sensibility, during heat from hydrogenation cracking reaction, hydrogenation reaction with Thermal condensation reaction exists parallel, but is leading with hydrogenation reaction.

From the point of view of component characteristic, the wax slop of heavy-oil hydrogenation hot cracked product, be heat from hydrogenation cracking reaction difficulty only The hydrocarbon-fraction of enrichment polycyclic aromatic hydrocarbon inferior to heat from hydrogenation crackate decompression residuum URP-VR, carbon residue with higher, pyrocondensation More thermal condensation objects can be generated in heavy-oil hydrogenation heat cracking reaction process iterative cycles by closing sensibility；It is anti-in heat from hydrogenation cracking During answering, hydrogenation reaction reacts presence parallel with thermal condensation, i.e., there is parallel to add hydrogen lighting reaction and dehydrogenative condensation Heaviness reaction, both the Direction of Reaction are:

1. plus hydrogen lighting reaction i.e. inhibit coking reaction, direction be " condensed-nuclei aromatics → polycyclic aromatic hydrocarbon → fractional saturation Multiring structure aromatic hydrocarbons → higher hydro carbons of hydrogen content "；

2. dehydrogenation reaction, that is, coking reaction, direction are " coke ← Carbonaceous mesophase ← asphalitine component ← colloid ← condensed ring Aromatic hydrocarbons ← polycyclic aromatic hydrocarbon ".

Heavy-oil hydrogenation hot cracked product decompression residuum URP-VR of the invention described in detail below.

Heavy-oil hydrogenation hot cracked product decompression residuum URP-VR of the present invention, under the conditions of not using hydrogen supply dissolvent, Other operating condition (reaction pressure, reaction temperature, catalyst composition and additive amount and amount, residence time, hydrogen oil volumes Than, way of operation) under the same conditions, coking tendency of URP-VR during heat from hydrogenation cracking reaction compares heavy oil Coking tendency of the identical fraction of boiling range during heat from hydrogenation cracking reaction is more serious in URF, i.e., coking yield is higher and/or adds hydrogen Thermal cracking conversion ratio is lower；In general, the normal boiling point in URP-VR is higher than the carbon residue of 530 DEG C of hydro carbons than the routine in heavy oil F1 The carbon residue that boiling point is higher than 530 DEG C of hydro carbons is higher.

In group technology of the invention, the first reaction task of URP-VR circulation heat from hydrogenation cracking process of the present invention It is that the removal of ccr by hydrotreating reaction i.e. heavy arene for carrying out heavy hydrocarbon inferior or colloid, asphalitine add hydrogen saturated reaction, certainly, simultaneously Can occur hydrofining reaction (including demetalization plus hydrogen hydrogenolysis, olefins hydrogenation reaction plus hydrogen removing impurities matter (oxygen, Sulphur, nitrogen) react, add hydrogen aromatic hydrocarbons saturation or fractional saturation reaction, removal of ccr by hydrotreating reaction) and/or hydrocracking reaction.URP-VR, In the tower bottom residual oil that it is enriched in vacuum fractionation tower in product fractionation process, this residual oil URP-VR usually contains the catalysis of addition Agent conversion product such as molybdenum sulfide etc., the UR product metal sulfide from heavy oil F1, the coke that may be accumulated.

Normal boiling point in up flow type floating bed hydrogenation heat cracking reaction process UR product URP from heavy oil F1 is higher than 530 DEG C of hydro carbons URP-VR, carbon residue content is usually above the carbon residue content of the identical fraction of boiling range in raw material F1, hydrocarbon in other words Liquid phase in material up flow type floating bed hydrogenation heat cracking reaction process UR is adapted as the heat from hydrogenation cracking of hydrocarbon URP-VR inferior The colloid of reaction process, asphalitine, liquid phase coke dispersion solution, therefore, URP-VR is introduced the upstream of heavy oil F1 by the present invention The reaction process (front reaction process AR or rear portion reaction process BR) of formula floating bed hydrogenation heat cracking reaction process UR is fitted Spend heat from hydrogenation cracking reaction.

In the up flow type hydrogenation process of URP-VR, when reactive hydrogen is supplied not in time, colloid, the heat of asphalitine Condensation reaction will occur for cracking free radical, and production molecular weight bigger molecule or structure group, repeatedly dehydrogenation and condensation are anti- The final result answered is to generate coke, and certainly, this is the negative reaction for needing inhibition or reduction.

The reactor types of the up flow type hydrogenation process of URP-VR of the present invention, can be any appropriate shape Formula can be the combination of one or more of combination cot reactor of suspended-bed reactor, ebullated bed and suspension bed.

The up flow type hydrogenation process of URP-VR of the present invention, the reactor used can be 1 or 2 or more Platform, reactor working method can be any suitable form, usually up flow type expanded bed reactor or carrying liqs product circulation Up flow type expanded bed reactor, the W-response area of separate unit up flow type expanded bed reactor, may be considered that be divided into 2 or Multiple reaction zones.The control mode of the inlet temperature of any reaction zone of up flow type expanded bed reactor of the present invention, can be tune The temperature and/or flow for saving hydrogen can be the temperature and/or flow for adjusting oil product.

The up flow type hydrogenation process of URP-VR, the reactor used, liquid phase, gas phase (or vapour phase) in reaction compartment Volume ratio, 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, is even greater than 0.80, actual reinforcing liquid-phase hydrogenatin mode is formed, in order to keep reaction compartment hydrogen partial pressure sufficiently high, it may be necessary to anti- It answers the position 2 times of the different height of device or repeatedly adds hydrogen.

It, can be with liquid material F1 in batches in order to adjust reaction feed property, or in order to control reaction process property of liquid phase The different spaces of hydrogenation process UR, the batch charging mode that the formation residence time is not waited is added.Such as Chinese patent ZL201610525311.9 discloses a kind of up flow type heat from hydrogenation cracking method of high aromatic carbon rate poor quality hydrocarbon branch charging, is suitable for The floating bed hydrogenation heat of coal tar heavy oil of the high normal boiling point of metal, polycyclic aromatic hydrocarbon, colloid, asphalt content higher than 450 DEG C Cracking reaction process UR, UR include 2 or first, second sub- hydroconversion reaction zone UR1, UR2 of multiple serial operations etc., hydrocarbon inferior F1 point is two-way or demultiplex raw material F11, F12, and F11 enters reaction effluent UR1P obtained by UR1 or containing its hydrogenated oil Logistics UR1PX enter UR2 and contacted with F12, concentration of the fresh feed F12 in UR2 liquid phase can be reduced, use hydrogen supply in UR1 When hydrocarbon stream SHS, it is remarkably improved the ratio that SHS flows through in reaction zone " hydrogen supply hydrocarbon weight/fresh feed F1X weight ", can be dropped Low-heat is condensed coking speed.

The up flow type floating bed hydrogenation heat cracking reaction process UR of heavy oil F1 of the invention described in detail below.

The heavy oil that the up flow type floating bed hydrogenation heat cracking reaction process UR of heavy oil F1 of the present invention can be carried out is described below Heat from hydrogenation cracking reaction process.

The hydro carbons of the raw material heavy oil F1 of the up flow type floating bed hydrogenation heat cracking reaction process UR of heavy oil F1 of the present invention 470 DEG C of the usual > of normal boiling point, 500 DEG C of general >, particularly 530 DEG C of >；The up flow type of heavy oil F1 of the present invention suspends Heat cracking reaction, the thermal cracking free radical stabilized hydrogenation of at least part heavy oil F1 occur for bed hydroprocessing heat cracking reaction process UR Reaction generates the lower hydrocarbon product of at least part boiling point；Heavy oil up flow type floating bed hydrogenation heat cracking reaction process UR leads to The normal one way that cannot achieve reacts whole lightings, i.e., its usual rationally high thermal cracking depth is usually 70~85% one way turn Rate, there are the tail oils of certain amount such as 15~30% in such heat from hydrogenation cracked reaction product URP, and in order to reduce outlet Tail oil quantity, it is often necessary to the heat from hydrogenation cracking reaction process of tail oil is set, and in order to simplify overall procedure, reduce investment and energy Consumption, usually by the up flow type floating bed hydrogenation heat cracking reaction process UR shape of the heat from hydrogenation cracking reaction process of tail oil and heavy oil F1 At group technology.

Although the up flow type floating bed hydrogenation heat cracking reaction process UR of heavy oil F1 with the heat cracking reaction of macromolecule hydrocarbon, The reaction of thermal cracking free radical stabilized hydrogenation is goal response, but due to the up flow type floating bed hydrogenation heat cracking reaction of heavy oil F1 Process UR usually used hydrogenation catalyst itself has the function of that hydrofinishing and existing reactive hydrogen also can induce hydrocarbon molecule Hydrofining reaction occurs therefore in the up flow type floating bed hydrogenation heat cracking reaction process UR of heavy oil F1, also necessarily to occur Some hydrofining reactions.

In the up flow type floating bed hydrogenation heat cracking reaction process UR of heavy oil F1, when reactive hydrogen is supplied not in time, Colloid, asphalitine thermal cracking free radical will occur condensation reaction, production molecular weight bigger molecule or structure group, repeatedly The final result of ground dehydrogenation and condensation reaction is to generate coke, and certainly, this is the negative reaction for needing inhibition or reduction.

Main application of the invention is the up flow type floating bed hydrogenation heat cracking reaction process UR of heavy oil F1, is used Reactor can be 1 or 2 or more, and usually used reactor is 2~4；The up flow type floating bed hydrogenation of heavy oil F1 The reactor working method of heat cracking reaction process UR can be any suitable form, usually up flow type expanded bed reactor or The up flow type expanded bed reactor of carrying liqs product circulation, the W-response area of separate unit up flow type expanded bed reactor can be by Think to be divided into 2 or multiple reaction zones.The control of the inlet temperature of any reaction zone of up flow type expanded bed reactor of the present invention Mode processed can be the temperature and/or flow for adjusting hydrogen, can be the temperature and/or flow for adjusting oil product.

The up flow type floating bed hydrogenation heat cracking reaction process UR of heavy oil F1, the reactor used, liquid in reaction compartment The volume ratio of phase, gas phase (or vapour phase), can be with liquid phase be it is main the case where, define reaction compartment in " the practical body of liquid phase Product/(liquid phase actual volume+gas phase actual volume) " is reaction compartment liquid phase fraction KL, and a point rate KL is typically larger than 0.45, is general big In 0.55, even greater than 0.70, 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.

When the second half reaction process URB of the up flow type floating bed hydrogenation heat cracking reaction process UR of heavy oil F1 combines processing When heavy oil component CRPVR in the reaction product CRP of the up flow type hydrogenation modification reaction process CR of hydrocarbon CRF inferior, the second half is anti- It answers the residence time of process URB usually to meet the requirement of the heat from hydrogenation cracking rate of control heavy oil component CRPVR first, is usually arranged The heat from hydrogenation cracking rate upper limit of heavy oil component CRPVR is to prevent conversion per pass excessively high.

The reactor types of heavy oil up flow type floating bed hydrogenation heat cracking reaction process UR of the present invention can be any Suitable form, there are many known form, such as suspended-bed reactor, ebullated bed and suspension bed combination cot reactor and its The combination of particular form, and it is most of have industrial application case, form relatively fixed technical characterstic.

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

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

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

Up flow type boiling bed hydrogenation technology, be characterized in that makes to urge with the uplink flowing of reaction mass (mainly liquid phase) Agent bed generates violent expansion, and expansion rate is typically in the range of 25~45%, to lose part fixed bed hydrogenation catalyst The advantages of " high activity, high interception rate, material hydro-conversion depth are uniform " is cost, forms " ability for destroying catalyst agglomeration " " the wide area channel of little particle impurity being freely discharged ", so as to process, tenor is higher, residual carbon content is higher heavy Oil, product quality have declined too much compared with bed technology, but its quality is preferably far beyond suspension bed；It is swollen due to ebullated bed Swollen power is mainly derived from the carrying of liquid phase material, and process should not usually prevent the liquid phase of reactor using a large amount of hydrogen Volume efficiency is too low, and therefore, the exothermic effect for also limiting reaction process cannot be excessively high, and usual boiling bed hydrogenation technology is more suitable The thermal discharge of hydrogen is added to support together in processing paraffinic base or paraffin intermediate crude base weight oil, caloric receptivity and the free radical of heat scission reaction Macroscopical fuel factor after disappearing is smaller, and reactor overall temperature rise is lower, and the Unit Weight hydrogen consumption of feedstock oil is usually 1.4~2.3%. But even so, the deactivation rate of catalyst is still too high, for this purpose, the old catalyst low by regular discharge part activity Then amount of activated high raw catelyst is filled into maintain the average activity of catalyst, therefore is formed expensive high activity and added The consuming cost of hydrogen catalyst, in fact, less economic when processing petroleum base poor residuum.Meanwhile the feature of thermal response Hydrogenation tail oil poor quality when leading to high conversion, vaporizes raw material after can only making fuel oil, therefore, the raw material of boiling bed hydrogenation is light Matter conversion ratio is usually 60~75%, i.e. conversion ratio is low.Since the pellet type catalyst that boiling bed hydrogenation technology uses is basic It is same as conventional fixed bed graininess (preferably spherical) Hydrobon catalyst, is still fallen within rich in a large amount of inner ducts, high inner surface Long-pending high activity, pellet type catalyst, are unable to satisfy diffusion and the hydro-conversion of poor residuum macromolecular, normal boiling point is higher than The heavy end or forming aperture blocking to catalyst duct loses the duct that 530 DEG C of molecular dimension is huge, polarity is strong Activity or Long-Term Sorption are in inner wall activated centre generation shadowing effect, under conditions of lacking reactive hydrogen, because being difficult to add hydrogen solid It is difficult to solve adsorption desorption, thermal condensation leading reaction occurs, formed in the road of duct and blocked.Too fast catalyst inactivation speed forms nothing The hydrogenation catalyst consuming cost that method is born, and more importantly the aromatic hydrocarbons saturation hydrogen of flood tide consumes released flood tide reaction Heat makes boiling bed hydrogenation technology not have safety, the quick coking of the gum asphalt of high-temperature induction, also in reactor Bottom distribution plate, center liquid circulation pipe form a large amount of cokings, and device is forced quickly to be stopped work.If selection up flow type ebullated bed adds Hydrogen technology processes the poor residuum that tenor is high, carbon residue content is high, result necessarily a large amount of green cokes, operation in reactor device Period is too short, reaction temperature is unable to control that i.e. dangerous, catalyst inactivation cost is odd high, these effects have been the poor quality of test manufacture The Industrial Operation of heavy oil boiling bed hydrogenation device is confirmed.

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

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

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

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

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

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

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

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

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

1. slight expanded-bed hydrogenator；

2. boiling bed hydrogenation reactor, boiling bed hydrogenation reactor usually draw off work from bed bottom in an intermittent fashion Property decreased catalyst, fill into fresh catalyst from bed top in an intermittent fashion and maintain bed catalyst reserve；

3. floating bed hydrogenation reactor；

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

Hydrocarbon catalytic heat cracking reaction process of the present invention, refers to the raw material hydrocarbon under hot cracking catalyst existence condition What is occurred is broken heat cracking reaction process as the main purpose with carbon-carbon bond, including the usually catalytic cracking reaction process or urges Change cracking reaction process, the body material oil usually processed is wax oil, reduced crude, records a document T001 of this kind of technology It is: 1. publication title: " catalytic cracking process and engineering "；2. retrieval is encoded with books: ISBN coding: 7-80043-537-7； Chinese depository library CIP data core word: (2004) No. 131193；3. chief editor: Chen Junwu；4. publishing house: Sinopec goes out Version society.It is (light to describe typical catalytic cracking light diesel fuel for pages 459 to page 488 of document T001 " catalytic cracking process and engineering " Recycle oil), catalytic cracking recycle oil (heavy-cycle oil), catalytic cracking clarified oil physical data.According to the operation of specific device The difference of condition and product separation scheme, catalytic cracking light diesel fuel (light cycle oil), are urged at catalytic cracking recycle oil (heavy-cycle oil) The boiling point range for changing cracking clarified oil fluctuates in a certain range, and based on the present invention, it is raw that catalytic thermal cracking reaction can be improved It is reduced in the processing ratio of catalytic thermal cracking reaction process at the yield of the wax oil of oil, then goes up flow type hydrogenation modification mistake Cheng Jinhang hydrogenation reaction.

Coking heavy oil reaction process of the present invention is referred to the mink cell focus of poor hydrogen (such as decompression residuum, cracked residue Deng) it is raw material, under the conditions of high temperature and long reaction time, carry out the hot procedure of depth thermal cracking and condensation reaction, raw material It is converted into gas, naphtha, gasoline, diesel oil, heavy distillate (coking light wax oil, coking wax slop) and coke.Coking Technology type include autoclave coking, open hearth coking, delayed coking, contact coking, fluid coking, flexicoking.Modern heavy The techniques such as oily coking, including delayed coking, contact coking, fluid coking, flexicoking.Record a text of this kind of technology Offering 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. publishing Society: Sinopec publishing house.Pages 188 to page 254 of document T002 " delay coking process and engineering ", describe typical delay The physical data of wax tailings.According to the difference of the operating condition of specific device and product separation scheme, the boiling range of wax tailings Range fluctuates in a certain range, and based on the present invention, coking can be improved and generate the yield of oily heavy wax oil and reduce it In the processing ratio of pyrogenetic reaction process, up flow type hydrogenation modification process is then gone to carry out hydrogenation reaction.

Due to catalytic cracking recycle oil (heavy-cycle oil), catalytic cracking clarified oil, wax tailings, heavy oil floating bed hydrogenation heat Cracking heavy wax oil, middle matter wax oil etc. belong to the wax oil rich in polycyclic aromatic hydrocarbon, it is difficult to direct catalytic cracking, it is also difficult to use Fixed-bed catalytic catalyst hydrocracking, and using the present invention to carry out heat from hydrogenation cracking then realizes suitable processing, and improves simultaneously The concentration of polycyclic aromatic hydrocarbon in reaction liquid phase, it is suppressed that the thermal condensation of asphalitine is reacted.

DCL/Direct coal liquefaction process is described below.

DCL/Direct coal liquefaction process of the present invention, refers to the side under solvent naphtha existence condition by adding hydrogen to make coal liquefaction Method according to the difference of solvent naphtha and catalyst, pyrolysis way and adds the difference of hydrogen mode and the difference of process conditions, Ke Yifen For following several techniques:

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

2. solvent adds hydrogen to extract liquefaction process: if any solvent refined coal process I and II (SRC-I and SRC-II), Exxon donor solvent process EDS, Japanese New Energy Development Organization liquefaction process (NEDOL) etc., using hydrogen, but pressure is less high, and solvent naphtha has apparent work With；

3. Hydrogenation method: such as the H coal process (H- of the old and new's liquefaction process (IG and the New1G) and the U.S. of Germany ) etc. Coal this kind is belonged to；

4. coal and residual oil joint processing method (C0processing): once passing through together with coal using residual oil as solvent naphtha anti- Device is answered, recycle oil is not had to；Hydrocracking occurs is converted into light oil to residual oil simultaneously；The U.S., Canada, Germany and former Soviet Union etc. are each There is different technique；

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

6. underground liquefaction process: solvent being injected subterranean coal, makes coal depolymerization and dissolution, in addition the impact force of fluid collapses coal It dissipates, the coal not being completely dissolved is then suspended in solvent, is extracted solution out with pump and is separated processing.

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

What patent CN100547055C stated clearly a kind of is pressed in lignite with the thermally dissolving and catalytic of lignite preparing liquid fuel is owned by France Add hydrogen direct liquefaction process, including Coal liquefaction process and liquefied coal coil hydrogenation modification process totally two processes.In order to improve The conversion ratio and realization coal feedstock of coal direct liquefaction enter reactor, and coal enters before reactor usually Coal dust is made, is made into coal with the solvent naphtha for having good hydrogen supply capacity, coal is pressurized, it is anti-to enter coal liquefaction after heating Answer device.

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

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

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

The final goal of Coal liquefaction process is the outer oil product supplied of production, and usual liquefied coal coil hydrogenation modification process generates Hydrogenation modification oil be two parts: a part be used as Coal liquefaction process hydrogen supply dissolvent oil, a part be used as coal liquefaction The outer oil extraction of liquefaction process.In general, at least part coal liquefaction light oil that Coal liquefaction process generates is used as outside coal oil process Oil extraction A, it is molten that remaining liquefied coal coil is used as liquefied coal coil hydrogenation modification process feedstock oil production Coal liquefaction process hydrogen supply There is the outer oil extraction of A and B two-way in agent oil and outer oil extraction B, the final whereabouts of the outer oil extraction of A and B two-way is usually by depth at this time Hydrogen grading process is added to produce high-quality oil product such as diesel oil distillate, naphtha cut.

DCL/Direct coal liquefaction process of the present invention usually using expanded bed hydrogenator, including uses hydrogen supply dissolvent oily Direct hydrogenation liquefaction of coal liquefaction process, oil coal refines process altogether, coal faces hydrogen thermosol liquefaction process etc..

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

1. reactor shell；

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

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

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

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

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

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

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

Up-flow reactor of the present invention, accessory are external insulation material, supporting element (skirt or trunnion), base Plinth, ladder, operating platform and fire-fighting accessory that may be present such as steam smothering ring.According to the conditions such as construction ground geology, meteorology, knot The conditions such as weight of equipment, height are closed, up-flow reactor of the present invention needs to drive piles to control under its basis as needed The sinking speed on its basis.

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 combination cot hydrogenator of suspension bed and ebullated bed；

4. slight expanded-bed.

Characteristic of the invention described in detail below.

①≤0.17；

2. 0.17~0.25；

3. 0.25~0.33；

4. 0.33~0.50；

5. 0.50~0.67.

1.≤15 seconds；

2. 15~30 seconds；

3. 30~45 seconds；

4. 45~60 seconds；

5. 60~120 seconds.

1. >=480 seconds；

2. 360~480 seconds；

3. 240~360 seconds；

4. 180~240 seconds；

5. 120~180 seconds.

1. 0.001~0.5；

2. 0.5~2.5；

3. 2.5~5.0；

4. > 5.0.

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

2. catalyst granules；

3. iron rust particle；

4. particles of inorganic material；

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

7. the solid particle from shale；

8. the solid particle from oil-sand；

9. other particles being present in hydrogenation reaction product.

1. floating bed, that is, slurry bed system hydrogenator；

2. boiling bed hydrogenation reactor；

3. the combination cot hydrogenator of suspension bed and ebullated bed；

4. slight expanded-bed hydrogenator.

Option 15, empty cylinder bubbling bed suspended-bed reactor system；

6. oil product obtained by shale oil or its distillate or its hot procedure；

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

1. the middle matter wax oil of petroleum base viscous crude；

1. being greater than 75%；

2. being greater than 85%；

3. being greater than 90%.

1. being hydrocracked the 35~60% of conversion ratio UR-CON-SX for one way；

2. being hydrocracked the 60~80% of conversion ratio UR-CON-SX for one way.

1. being 15~20%；

2. being 20~30%；

3. being 30~45%；

4. being 45~65%.

1. being greater than 75%；

2. being greater than 85%.

1. being 0.50~1.0%；

2. being 1.0~2.0%；

3. being 2.0~3.0%；

4. being 3.0~4.0%.

The carbon residue content of first raw material URF, can a kind in following:

1. being 10~18%；

2. being 18~28%；

3. being 28~35%；

4. for greater than 35%.

The operating condition of reaction process UR is, can a kind in following:

The operation temperature of reaction process UR is 400~450 DEG C；

The operation temperature of reaction process UR is 410~445 DEG C；

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, with Guarantee the necessary vulcanization kenel of catalyst.The supplement sulphur can be sulfide hydrogen or can be converted into hydrogen sulfide to adding hydrogen Material of the conversion process without ill-effect, such as hydrogen sulfide containing gas or oil product, or vulcanization is generated after contacting with high-temperature hydrogen The molten sulfur or carbon disulfide of hydrogen 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 set The high pressure hot separator that operation temperature is usually 150~450 DEG C is set, hydrogenation reaction effluent enters high pressure hot separator point at this time It by conventional liq hydrocarbon and may mainly be deposited from the hot high score gas gas being mainly made of hydrogen in volume for one and one Solid composition hot high score oil liquid body, hot high score gas enters the cold high pressure separator point that operation temperature is usually 20~80 DEG C Following target is realized: cold since a large amount of high boiling components enter in hot high score oil liquid body from for cold high score oil and cold high score gas High score oil density becomes smaller or viscosity becomes smaller or is easily isolated with water.Thermal high is arranged in the high pressure separation process of hydrogenation reaction effluent Separator is also equipped with the advantages of reducing thermal loss, because hot high score oil liquid body can be to avoid hot high score gas experience using empty The process that cools of cooler or water cooler.Meanwhile the hot high score oil liquid body in part can be returned to the hydrogenation process of upstream Be recycled, with improve receive the recycle oil hydrogenation process overall raw material property, or to the cycling hot high score oil into Row circulation plus hydrogen.

Between thermal high separate section and cold anticyclone separate section, as needed, warm high pressure separate section can be set, Become gas-liquid two-phase material after hot high score air cooling at this time, one is separated into warm high-pressure separator in volume mainly by hydrogen The warm high score gas gas and the warm high score oil liquid being mainly made of conventional liq hydrocarbon and solid that may be present of gas composition Body, 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 in the hydrogenation reaction effluent gas phase degree (usually with reactive moieties feed exchange heat) to about 220~100 DEG C Crystallization temperature, the crystallization temperature of sal-ammoniac of sulphur hydrogenation ammonia), then usually injection washing water formation water filling back end hydrogenation is anti-thereto Answer effluent, it may be necessary to which 2 or multiple injection points are set, and washing water is used for absorbing ammonia and issuable other impurity such as chlorine Change hydrogen etc., and the aqueous solution after absorbing ammonia necessarily absorbs hydrogen sulfide.In cold anticyclone separate section, the water filling back end hydrogenation reaction stream Object separates out are as follows: the cold high score gas being mainly made of hydrogen in volume, one mainly by conventional liq hydrocarbon and dissolved hydrogen The cold high score oil of composition, a cold high score water be mainly made of water and dissolved with ammonia, hydrogen sulfide.The cold high score water, The content of middle ammonia is generally 0.5~15% (w), preferably 1~8% (w).One purpose of note washing water is to absorb hydrogenation reaction Ammonia and hydrogen sulfide in effluent prevent from forming sulphur hydrogenation ammonia or more sulphur ammonia Crystallization Plugging heat exchanger channels, increase system pressure Drop.The injection rate of the washing water should be determined according to following principles: on the one hand, washing water divides after injecting hydrogenation reaction effluent For vapour phase water and liquid phase water, liquid phase water has to be larger than zero, preferably washs 30% or more of water inventory；In another aspect, washing Water is washed for absorbing the ammonia in hydrogenation reaction effluent, prevents the ammonia density of high score gas too high, reduces catalyst activity, usually height Divide the ammonia volumetric concentration of gas more lower better, generally no greater than 200PPm (v), desirably no more than 50PPm (v).The cold anticyclone Separator operation pressure be hydrogenation reaction partial pressure subtract actual pressure drop, cold anticyclone separate section operating pressure with add hydrogen it is anti- The difference of pressure is answered, it is unsuitable too low or excessively high, it is usually generally 0.35~3.2MPa, 0.5~1.5MPa.The cold high score The hydrogen volume concentration value of gas, should not too low (cause device operating pressure rise), generally should not less than 70% (v), it is preferably not low In 80% (v), preferably not below 85% (v).As previously described at least part, be usually 85~100% cold high score gas return It is recycled in hydrogenation reaction part, to provide the necessary amounts of hydrogen in hydrogenation reaction part and hydrogen concentration；It is thrown to improve device Provide efficiency, it is necessary to assure circulation hydrogen concentration be not less than lower limit value above-mentioned, for this purpose, according to specific feedstock property, reaction condition, Product distribution can exclude a part of cold high score gas to exclude methane, the ethane that reaction generates.For the cold high score of discharge Gas can realize hydrogen and non-hydrogen gas component point using conventional membrane separation process or pressure swing adsorption technique or oil wash technique From, and the hydrogen of recycling is used as new hydrogen.It, can be using conventional membrane separation process or change for the cold high score gas of recycling It presses absorbing process or oil wash technique to realize hydrogen and the separation of non-hydrogen gas component, and the hydrogen of recycling is used as new hydrogen reuse.

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 the One 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 direct hydrogenation liquefaction of coal reaction process, because of conventional gas hydrocarbon, CO, CO₂Yield is huge, usually most of cold Cold high score gas of the high score gas than such as from about 70~100%, after being purified as membrane separation process obtained by permeated hydrogen pressurization after return plus Hydrogen reaction process, do not permeate gas by PSA mention hydrogen or after " steam reforming hydrogen manufacturing+PSA mentions hydrogen " pressurization return plus hydrogen it is anti- Process is answered to be recycled.

Claims

1. using the hydrocarbon material expanded bed method of hydrotreating of reaction product Thermal Synthetic high score device, it is characterised in that comprise the steps of:

(1) in hydrocarbon material expanded bed hydrogenation process UR, there are hydrogen, hydrocarbon liquid phase, there may be the mixed of solid particle simultaneously Under the conditions of phase materials, expanded bed hydrogenation reaction URR at least is carried out containing the first raw material URF of carbon and protium and obtains adding hydrogen Hydrogenation reaction effluent URP-X is discharged in reaction product BASE-URP, and the net product URP of hydrogenation process is discharged；

Expanded bed hydrogenation reaction URR, the hydrofining reaction comprising at least part liquid material URFL may include at least one The hydrocracking reaction of operative liquid raw material URFL may add hydrogen comprising at least part solid material URFS that may be present Heat cracking reaction；

Hydrocarbon material expanded bed hydrogenation process UR may use hydrogenation catalyst URC, hydrogenation catalyst URC that may contain metal molybdenum；

Material based on hydrogenation reaction product BASE-URP is used as hydrogenation reaction effluent URP-X；Hydrogenation reaction effluent URP- X occurs in the form of 1 tunnel or 2 tunnels or multichannel material, hydrogenation reaction effluent URP-X be gas phase or liquid phase or gas-liquid mixed phase or Gas-liquid-solid three-phase logistics；

Hydrocarbon material expanded bed hydrogenation process UR is at least wrapped in the hydrogenator used using at least 1 hydrogenator Containing 1 up flow type expanded bed hydrogenator；

One hydrogenation reaction grade, to its hydrogenation products gas-liquid referring to entering a hydrogenation process since hydrocarbon raw material At least one isolated process section until generating the liquid product that forms of oil by least part, includes the hydrogenation reaction grade Hydrogenation process and this grade at least part hydrogenation reaction product gas-liquid separation process；

Hydrocarbon material expanded bed hydrogenation process UR includes at least one hydrogenation reaction grade, has liquid product comprising at least one The product KRP of the hydrogenation reaction grade of circulation, at least one hydrogenation reaction grade KR for having liquid product to recycle uses Thermal Synthetic high score Device KR-DS carries out gas-liquid separation and liquid material distribution；

In hydrogenation reaction grade KR, at least 1 to Thermal Synthetic high score device KR-DS provide may the gas-liquid product containing solid upstream Adjacent hydrocarbon material expanded bed hydrogenator KR9E is that the top in reactor is not provided with liquid collecting cup, the expanded bed of diversion pipe adds Hydrogen reactor；

The product KRP of the hydrogenation reaction grade KR is characterized in that using Thermal Synthetic high score device KR-DS: Thermal Synthetic high score device KR- Liquid short residence time region KR-DV01 and liquid long residence time region KR-DV02 is arranged in the liquid phase region of DS；Region KR- The residence time KR-LT1 of liquid in DV01, less than the residence time KR-LT2 of liquid in the KR-DV02 of region,

At least part liquid material of the liquid short residence time region KR-DV01 discharge of Thermal Synthetic high score device KR-DS is used as reaction Circulation fluid KR-DSLR is returned in the upstream hydrogenator in hydrogenation reaction grade KR and is flowed through hydrocarbon material expanded bed hydrogenation reaction At least part reaction compartment of device KR9E；

At least part part liquid material of the liquid long residence time region KR-DV02 discharge of Thermal Synthetic high score device KR-DS is used as The high liquid separation KR-DSLP of heat；

Hydrocarbon material expanded bed hydrogenation process UR, includes at least one hydrogenation reaction grade, the last one hydrogenation reaction grade is end End hydrogenation reaction grade ENDR may be the hydrogenation reaction grade ENDR for having liquid product to recycle, the product of end hydrogenation reaction grade ENDR ENDR-P may use Thermal Synthetic high score device ENDR-DS to carry out gas-liquid separation and liquid material distribution.

2. according to the method described in claim 1, it is characterized by:

The residence time KR- of liquid in the liquid phase region of Thermal Synthetic high score device KR-DS, liquid short residence time region KR-DV01 The ratio K T100=(KR-LT1) of the residence time KR-LT2 of liquid in LT1 and liquid long residence time region KR-DV02/ (KR-LT2), a kind in following of KT100:

①≤0.17；

2. 0.17~0.25；

3. 0.25~0.33；

4. 0.33~0.50；

5. 0.50~0.67.

3. according to the method described in claim 1, it is characterized by:

The residence time KR- of liquid in the liquid phase region of Thermal Synthetic high score device KR-DS, liquid short residence time region KR-DV01 LT1, a kind in following:

1.≤15 seconds；

2. 15~30 seconds；

3. 30~45 seconds；

4. 45~60 seconds；

5. 60~120 seconds.

4. according to the method described in claim 1, it is characterized by:

The residence time KR- of liquid in the liquid phase region of Thermal Synthetic high score device KR-DS, liquid long residence time region KR-DV02 LT2, a kind in following:

1. >=480 seconds；

2. 360~480 seconds；

3. 240~360 seconds；

4. 180~240 seconds；

5. 120~180 seconds.

5. according to the method described in claim 1, it is characterized by:

In Thermal Synthetic high score device KR-DS, the weight flow KR-DSLR-W and the high liquid separation KR-DSLP of heat of reaction cycle liquid KR-DSLR The ratio of weight flow KR-DSLP-W be set to recycle ratio K900, K900=(KR-DSLR-W)/(KR-DSLP-W), K900 choosing 1 kind in following:

1. 0.001~0.5；

2. 0.5~2.5；

3. 2.5~5.0；

4. > 5.0.

6. according to the method described in claim 1, it is characterized by:

1 kind or several of combination of the mode of operation of Thermal Synthetic high score device KR-DS in following:

1. it include air lift hydrogen in the charging of Thermal Synthetic high score device KR-DS, it will be in the liquid phase of Thermal Synthetic high score device KR-DS charging At least part low boiling component air lift enters in gas phase, and eventually enters into the gaseous products of Thermal Synthetic high score device KR-DS；

2. include in the charging of Thermal Synthetic high score device KR-DS the component containing high boiling hydrocarbon hydrogen rich gas gas 399S as gas stripping gas, At least part low boiling component air lift in the liquid phase of Thermal Synthetic high score device KR-DS charging is entered in gas phase and eventually entered into In the gaseous products of Thermal Synthetic high score device KR-DS, at least part in the hydrogen rich gas gas 399S of the component containing high boiling hydrocarbon is high Boiling point gases component, which enters in liquid phase, carries out secondary plus hydrogen lighting reaction；

3. including gas-liquid mixed phase material 388S in the charging of Thermal Synthetic high score device KR-DS, with Thermal Synthetic high score device KR-DS charging Liquid phase hybrid separation, the gas component in mixed phase material 388S enter in gas phase and eventually enter into Thermal Synthetic high score device KR-DS's In gaseous products, the liquid phase component in mixed phase material 388S, which enters in liquid phase, carries out secondary plus hydrogen lighting reaction；

Gas-liquid mixed phase material 388S, it may be possible to the gas-liquid mixed phase product of the upstream hydrogenation reaction grade QR from hydrogenation reaction grade KR；

4. including hydrocarbon liquid cooling but material 377S in the charging of Thermal Synthetic high score device KR-DS, with Thermal Synthetic high score device KR-DS charging Liquid phase mixes and reduces its temperature；

Hydrocarbon liquid cooling but material 377S, it may be possible to the hydrocarbon that separation or fractional distillation process from the net product URP of hydrogenation process obtain Liquid material；

5. it include hydrogen supply hydrocarbon material 366S in the charging of Thermal Synthetic high score device KR-DS, the liquid with Thermal Synthetic high score device KR-DS charging It mixes to inhibit coking；

Hydrogen supply hydrocarbon material 366S, it may be possible to the hydrocarbon liquid that separation or fractional distillation process from the net product URP of hydrogenation process obtain Material or its stabilized hydrogenation reaction product or its fractionation fraction.

7. according to the method described in claim 1, it is characterized by:

The liquid phase region of Thermal Synthetic high score device KR-DS is arranged liquid short residence time region KR-DV01, and mode of operation is in following 1 kind or several of combination:

1. in liquid short residence time region KR-DV01, using the material of the hydrogen containing air lift, by the liquid phase in the KR-DV01 of region In at least part low boiling component air lift enter in gas phase, and eventually enter into the gaseous products of Thermal Synthetic high score device KR-DS In；

2. using the hydrogen rich gas gas 99S of the component containing high boiling hydrocarbon as air lift in liquid short residence time region KR-DV01 At least part low boiling component air lift in liquid phase in the KR-DV01 of region is entered in gas phase and eventually enters into synthesis by gas At least part higher boiling gas in the gaseous products of hot high score device KR-DS, in the hydrogen rich gas gas 99S of the component containing high boiling hydrocarbon Body component, which enters in liquid phase, carries out secondary plus hydrogen lighting reaction；

3. mixed with the liquid phase in the KR-DV01 of region using gas-liquid mixed phase material 88S in liquid short residence time region KR-DV01 Separation is closed, the gas component in mixed phase material 88S enters in gas phase and eventually enters into the gaseous products of Thermal Synthetic high score device KR-DS In, the liquid phase component in mixed phase material 88S, which enters in liquid phase, carries out secondary plus hydrogen lighting reaction；

Gas-liquid mixed phase material 88S, it may be possible to the gas-liquid mixed phase product of the upstream hydrogenation reaction grade QR from hydrogenation reaction grade KR；

4. mixed using the liquid phase in hydrocarbon liquid cooling but material 77S, with region KR-DV01 in liquid short residence time region KR-DV01 Merging reduces its temperature；

Hydrocarbon liquid cooling but material 77S, it may be possible to the hydrocarbon liquid that separation or fractional distillation process from the net product URP of hydrogenation process obtain Material；

5., using hydrogen supply hydrocarbon material 66S, being mixed with the liquid phase in the KR-DV01 of region in liquid short residence time region KR-DV01 To inhibit coking；

Hydrogen supply hydrocarbon material 66S, it may be possible to the hydrocarbon liquid object that separation or fractional distillation process from the net product URP of hydrogenation process obtain Material or its stabilized hydrogenation reaction product or its fractionation fraction.

8. according to the method described in claim 1, it is characterized by:

The liquid long residence time region KR-DV02 of Thermal Synthetic high score device KR-DS, a kind or several in following of mode of operation The combination of kind:

1. in liquid long residence time region KR-DV02, using the material of the hydrogen containing air lift, by the liquid phase in the KR-DV01 of region In at least part low boiling component air lift enter in gas phase, and eventually enter into the gaseous products of Thermal Synthetic high score device KR-DS In；2. using the hydrogen rich gas gas 199S of the component containing high boiling hydrocarbon as air lift in liquid long residence time region KR-DV02 At least part low boiling component air lift in liquid phase in the KR-DV02 of region is entered in gas phase and eventually enters into synthesis by gas At least part higher boiling in the gaseous products of hot high score device KR-DS, in the hydrogen rich gas gas 199S of the component containing high boiling hydrocarbon Gas component enters in liquid phase；

3. in liquid long residence time region KR-DV02, using gas-liquid mixed phase material 188S, with the liquid phase in the KR-DV02 of region Hybrid separation, the gas component in mixed phase material 188S enter in gas phase and eventually enter into the gas phase of Thermal Synthetic high score device KR-DS In product, the liquid phase component in mixed phase material 188S enters in liquid phase；

Gas-liquid mixed phase material 188S, it may be possible to the gas-liquid mixed phase product of the upstream hydrogenation reaction grade QR from hydrogenation reaction grade KR；

4. using the liquid phase in hydrocarbon liquid cooling but material 177S, with region KR-DV02 in liquid long residence time region KR-DV02 It mixes and reduces its temperature；

Hydrocarbon liquid cooling but material 177S, it may be possible to the hydrocarbon that separation or fractional distillation process from the net product URP of hydrogenation process obtain Liquid material.

9. according to the method described in claim 1, it is characterized by:

(1) hydrocarbon material expanded bed hydrogenation process UR, a kind or 2 kinds or several of the combination selected from following hydrogenation process:

1. the logistics containing oil product obtained by middle coalite tar or its distillate or its hot procedure adds hydrogen mistake using expanded bed Journey；

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

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

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

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

10. according to the method described in claim 1, it is characterized by:

(1) hydrocarbon material expanded bed hydrogenation process UR, a kind or several in following of existing solid particle:

2. catalyst granules；

3. iron rust particle；

4. particles of inorganic material；

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

7. the solid particle from shale；

8. the solid particle from oil-sand；

9. other particles being present in hydrogenation reaction product.

11. according to the method described in claim 1, it is characterized by:

(1) hydrocarbon material expanded bed hydrogenation process UR, the expanded bed reactor used, a kind in following of mode of operation Or several combination:

1. floating bed, that is, slurry bed system hydrogenator；

2. boiling bed hydrogenation reactor；

3. the combination cot hydrogenator of suspension bed and ebullated bed；

4. slight expanded-bed hydrogenator.

12. according to the method described in claim 1, it is characterized by:

(1) working method of hydrocarbon material expanded bed hydrogenation process UR, the hydrogenator URXE used in following 1 Kind is several:

Option 2, reactor URXE, forced circulation Returning reactor after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of URXE material inlet；

Option 3, reactor URXE, forced circulation Returning reactor after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of URXE material inlet；

Option 4, reactor URXE, forced circulation Returning reactor after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of URXE material inlet, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 5, reactor URXE, forced circulation Returning reactor after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of URXE material inlet, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 6, reactor URXE, forced circulation Returning reactor after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of URXE material inlet, the other collection liquids for being collected simultaneously cup discharge pass through other dedicated feeding engines downstream Convey liquid material product；

Option 7, reactor URXE, forced circulation Returning reactor after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of URXE material inlet, the other collection liquids for being collected simultaneously cup discharge pass through other dedicated feeding engines downstream Convey liquid material product；

Option 8, reactor URXE, top are arranged liquid collecting cup and liquid material product are discharged by the production of dedicated feeding engine downstream transport liquid material Object is not provided with the fluidized bed reactor system of liquid material product forced circulation；

Option 9, reactor URXE, top are arranged liquid collecting cup and liquid material product are discharged by the production of dedicated feeding engine downstream transport liquid material Object is not provided with the suspended-bed reactor system of liquid material product forced circulation；

Option 10, reactor URXE, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The ebullated bed of device URXE material inlet and the combination type reactor of ebullated bed；

Option 11, reactor URXE, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The ebullated bed of device URXE material inlet and the combination type reactor of ebullated bed, it is downstream defeated while circulating pump conveys circulation fluid Liquor charging material product；

Option 12, reactor URXE, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The ebullated bed of device URXE material inlet and the combination type reactor of ebullated bed are collected simultaneously other collection liquids of cup discharge by it Its dedicated feeding engine downstream transport liquid material product；

Option 15, empty cylinder bubbling bed suspended-bed reactor system；

It is anti-to form the dirty Returning reactor lower part of reactor top reaction zone liquid phase using the external circulation pipe of reactor for option 16 Answer the device outside circulation in area；

Option 17, in reactor URXE, setting enters stripping step and the top liquid collecting of the end gas-liquid product of top liquid collecting cup Cup gas-liquid separation step, the average molecular weight for the balance liquid phase that hydrogen rich gas gas stripping gas is formed after mixing with end gas-liquid product are greater than The average molecular weight of the balance liquid phase of end gas-liquid product, the balance that hydrogen rich gas gas stripping gas is formed after mixing with end gas-liquid product The normal boiling point for the balance liquid phase that the concentration of the hydrocarbon component of the normal boiling point of liquid phase higher than 350 DEG C is greater than end gas-liquid product is higher than The concentration of 350 DEG C of the hydrocarbon component；The possibility that liquid collecting cup in the final reactor of autoreaction section is discharged through diversion pipe is containing solid Liquid material may contain the liquid material product or circular response liquid phase of solid as conversion zone.

13. according to the method described in claim 1, it is characterized by:

(1) hydrocarbon material expanded bed hydrogenation process UR, hydrogenation reaction grade obtains the mode of product liquid, in following manner 1 kind or several:

1. liquid material of the possibility containing solid that the gas-liquid separation process of autoreaction order reaction product is discharged, may as final reaction grade Liquid material product containing solid；

2. the final reactor of order of reaction uses pure counter-current reactor, the bottom liquid phase region of the final reactor of autoreaction grade is discharged Liquid material of the possibility containing solid, the liquid material product of solid may be contained as order of reaction；

3. top liquid collecting cup is arranged in the final reactor of order of reaction, the liquid collecting cup in the final reactor of autoreaction grade is through water conservancy diversion Liquid material of the possibility containing solid of pipe discharge, the liquid material product of solid may be contained as order of reaction；

4. top liquid collecting cup is arranged in the final reactor of order of reaction, the liquid collecting cup in the final reactor of autoreaction grade is through water conservancy diversion Liquid material of the possibility containing solid of pipe discharge, as the liquid material to be de-gassed that may contain solid；

Possibility to be de-gassed contains the liquid of solid, is separated into liquid stream, all the way all the way rich in bubble by cyclonic separation step The liquid stream of lean gas bubble；The liquid stream of lean gas bubble, the possibility as order of reaction contain the product liquid of solid；

5. setting enters the stripping step and top collection of the end gas-liquid product of top liquid collecting cup in the final reactor of order of reaction Liquid cup gas-liquid separation step, the average molecular weight for the balance liquid phase that hydrogen rich gas gas stripping gas is formed after mixing with end gas-liquid product are big In the average molecular weight of the balance liquid phase of end gas-liquid product, hydrogen rich gas gas stripping gas is formed flat after mixing with end gas-liquid product The normal boiling point that the concentration of the hydrocarbon component of the normal boiling point for the liquid phase that weighs higher than 350 DEG C is greater than the balance liquid phase of end gas-liquid product is high In the concentration of 350 DEG C of the hydrocarbon component；The possibility that liquid collecting cup in the final reactor of autoreaction grade is discharged through diversion pipe contains solid Liquid material, the liquid material product or circular response liquid phase of solid may be contained as order of reaction.

14. according to the method described in claim 1, it is characterized by:

(1) hydrocarbon material expanded bed hydrogenation process UR, the first raw material URF include one or more of following materials:

4. oil product obtained by direct hydrogenation liquefaction of coal liquefaction process, direct hydrogenation liquefaction of coal liquefaction process includes using hydrogen supply dissolvent oil Direct hydrogenation liquefaction of coal liquefaction process, oil coal refines process altogether, coal faces hydrogen thermosol liquefaction process；

6. oil product obtained by shale oil or its distillate or its hot procedure；

15. according to the method described in claim 1, it is characterized by:

(1) hydrocarbon material expanded bed hydrogenation process UR, Fu Fang expect the hydrocarbon component that KAS is mainly 450~510 DEG C by normal boiling point Solid particle is formed and can contain, Fu Fang expects that KAS enters and passes through at least one in hydrocarbon material expanded bed hydrogenation process UR Divide reaction compartment.

16. according to the method for claim 15, it is characterised in that:

(1) hydrocarbon material expanded bed hydrogenation process UR, Fu Fang expect that KAS is selected from one or more of following logistics:

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

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

17. according to the method for claim 15, it is characterised in that:

(1) hydrocarbon material expanded bed hydrogenation process UR, Fu Fang expect that KAS is selected from one or more of following materials:

1. the middle matter wax oil of petroleum base viscous crude；

18. according to the method described in claim 1, it is characterized by:

First raw material URF is mainly made of 520 DEG C of normal boiling point > of the hydrocarbon component and contains asphalitine component；

The first hydrogenation reaction grade 1R of hydrocarbon material expanded bed hydrogenation process UR, being one has liquid product circulation plus hydrogen anti- Answer grade；

End hydrogenation reaction grade is ENDR, and using at least 1 hydrogenator, 1 is included at least in the hydrogenator used Up flow type expanded bed hydrogenator, last 1 hydrogenator ENDR9E are up flow type expanded bed hydrogenator；

The last one hydrogenation reaction grade ENDR is the hydrogenation reaction grade ENDR, end hydrogenation reaction grade ENDR for having liquid product to recycle Product ENDR-P carry out gas-liquid separation and liquid material using Thermal Synthetic high score device ENDR-DS and distribute；

The reaction cycle liquid ENDR-DSLR of the liquid short residence time region ENDR-DV01 discharge of Thermal Synthetic high score device ENDR-DS Composition, a kind or several in following:

19. according to the method for claim 18, it is characterised in that:

The one way of 520 DEG C of normal boiling point > of the hydrocarbon component adds in hydrocarbon material expanded bed hydrogenation process UR, the first raw material URF Hydrogen cracking conversion rate UR-CON-SX, a kind in following:

1. being greater than 75%；

2. being greater than 85%；

3. being greater than 90%.

20. according to the method for claim 18, it is characterised in that:

The one way of 520 DEG C of normal boiling point > of the hydrocarbon component adds in hydrocarbon material expanded bed hydrogenation process UR, the first raw material URF Hydrogen cracking conversion rate is UR-CON-SX；

The normal boiling point > 520 in the first hydrogenation reaction grade 1R, the first raw material URF of hydrocarbon material expanded bed hydrogenation process UR DEG C the one way of the hydrocarbon component be hydrocracked conversion ratio 1R-CON-SX, a kind or several in following:

1. being hydrocracked the 35~60% of conversion ratio UR-CON-SX for one way；

2. being hydrocracked the 60~80% of conversion ratio UR-CON-SX for one way.

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

In hydrocarbon material expanded bed hydrogenation process UR, using hydrogen-containing hydrocarbon stream DS, the hydrogen supply hydrocarbon weight of hydrogen-containing hydrocarbon stream DS is dense Degree, a kind in following:

1. being 15~20%；

2. being 20~30%；

3. being 30~45%；

4. being 45~65%.

22. according to the method described in claim 1, it is characterized by:

(1) it is separated into thermal high separation process S100, the net product URP of hydrogenation process comprising conventional hydrogen, conventional gas Hydrocarbon, conventional liq hydrocarbon gas S100V and the liquid material that liquid phase component is mainly made of conventional liq hydrocarbon of solid may be contained S100L；

(2) it in gas recovery section S100V-GU, separates gas S100V and obtains hydrogen-rich gas HPV, at least part hydrogen rich gas gas Body HPV enters hydrogenation process use.

23. according to the method for claim 22, it is characterised in that:

The hydrogen volume concentration of hydrogen rich gas gas HPV, a kind in following:

1. being greater than 75%；

2. being greater than 85%.

24. according to the method for claim 22, it is characterised in that:

(3) in liquid material recovery section S100L-GU, separation mainly may form liquid phase component by conventional liq hydrocarbon containing solid Liquid material S100L, richness that is obtaining mainly being made of normal boiling point higher than 520 DEG C of hydrocarbon and being higher than 570 DEG C containing normal boiling point Contain the heat from hydrogenation cracked vacuum residue THC-VR of solid particle containing colloid, the possibility of asphalitine.

25. according to the method for claim 24, it is characterised in that:

At least part heat from hydrogenation cracked vacuum residue THC-VR does not enter hydrogenation process UR.

26. according to the method for claim 24, it is characterised in that:

At least part heat from hydrogenation cracked vacuum residue THC-VR enters as reaction-fractionation circulating path recycle oil S66 and adds Hydrogen reaction process UR, recycle oil S66 possibly into any 1 of hydrogenation process UR or 2 or multiple hydrogenation reaction grades it In.

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

In hydrocarbon material expanded bed hydrogenation process UR, the weight chemistry hydrogen consumption of the first raw material URF, a kind in following:

1. being 0.50~1.0%；

2. being 1.0~2.0%；

3. being 2.0~3.0%；

4. being 3.0~4.0%.

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

The carbon residue content of first raw material URF, a kind in following:

1. being 10~18%；

2. being 18~28%；

3. being 28~35%；

4. for greater than 35%.

29. according to the method described in claim 1, it is characterized by:

(1) first raw material URF is mainly made of 520 DEG C of normal boiling point > of the hydrocarbon component and contains asphalitine component；

Hydrocarbon material expanded bed hydrogenation process UR is heavy oil up flow type floating bed hydrogenation heat cracking reaction process, mode of operation 1 kind or several in following:

1. reaction process UR, operating condition are as follows: reaction temperature is 400~485 DEG C, and reactor pressure is 6~30MPa, gas phase hydrogen Air volume concentration 50~95%, gas-liquid volume ratio are 300~1500Nm³/m³, hydrogenation catalyst additive amount is heavy oil raw material weight 0.001~3 mass %, co-catalyst additive amount be sulphur in co-catalyst/catalyst activity metal molar ratio be 1.0~ 2.0, volume space velocity is 0.25~5.0hr^-1；

2. reaction process UR, the heat from hydrogenation Cracking catalyst URC used include at least Mo element, Mo is in the first hydrogenation reaction mistake The body of work form of journey UR is M₀S₂, powdered granule that the hydrogenation catalyst URC of working morphology is 0.3 nanometer~100 microns；

3. reaction process UR, the heat from hydrogenation Cracking catalyst URC used include at least Mo element, Mo is in the first hydrogenation reaction mistake The body of work form of journey UR is M₀S₂, powdered granule that the hydrogenation catalyst URC of working morphology is 0.3 nanometer~100 microns；

4. reaction process UR, the heat from hydrogenation Cracking catalyst URC used include at least Mo element, Mo is in the first hydrogenation reaction mistake The body of work form of journey UR is M₀S₂, powdered granule that the hydrogenation catalyst URC of working morphology is 0.3 nanometer~100 microns；

5. reaction process UR, the heat from hydrogenation Cracking catalyst URC used include nanometer ultra-fine grain aqua oxidation iron catalyst；

6. reaction process UR, the hydrogenation catalyst URC used are a kind of composite hydrogenation catalysts, comprising high-activity component with Low activity component；The weight ratio of the high-activity component metal and low activity component metals is 0.1 to 10；The high-activity component Or mixtures thereof oil-soluble salt compounds or water soluble salt compound containing molybdenum；The low activity group is divided into iron oxide ore Stone or iron sulfide ore, wherein iron in ore content is not less than 40wt%, and heat from hydrogenation Cracking catalyst water content is lower than 2wt%； The powdered granule that heat from hydrogenation cracking catalyst particles diameter is 1~100 μm；

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

In reaction process UR, the hydrogenation catalyst URC used includes at least Mo element, and Mo is in heavy oil up flow type hydrogenation reaction mistake The body of work form of journey UR is M₀S₂, powdered granule that the hydrogenation catalyst URC of working morphology is 0.3 nanometer~100 microns；

The operating condition of reaction process UR is, a kind in following:

1. the operating condition of reaction process UR are as follows: temperature is 350~480 DEG C, pressure is 6.0~30.0MPa, hydrogen/feedstock oil Volume ratio is 0.01~2000, hydrogenation catalyst R10C addition weight is the 0.001~8.0% of heavy oil F1 weight, volume space velocity For 0.1~10.0hr^-1；

2. weight is added in hydrogenation catalyst URC, the M of working morphology based on conversion₀S₂, and the ratio of the first raw material URF weight flow It is 0.1~2.0hr that value, which is 400/7/1000000ths ten to million, reactor volume air speed,^-1；

The operation temperature of reaction process UR is 400~450 DEG C；

The average operating temperature of first hydrogenation reaction grade 1R, lower than 5~20 DEG C of average operating temperature of follow-up hydrogenation order of reaction；

3. weight is added in hydrogenation catalyst URC, the M of working morphology based on conversion₀S₂, and the ratio of the first raw material URF weight flow Value is hundred a ten thousandths 300/100000000ths to million, reactor volume air speed is 0.2~1.0hr^-1；

The operation temperature of reaction process UR is 410~445 DEG C；

The average operating temperature of first hydrogenation reaction grade 1R, lower than 10~15 DEG C of average operating temperature of follow-up hydrogenation order of reaction.