CN110240929A

CN110240929A - The hydrogen supply dissolvent application method of heavy hydrocarbon up flow type hydro-upgrading reaction process inferior

Info

Publication number: CN110240929A
Application number: CN201810211504.6A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Individual
Priority date: 2018-03-10
Filing date: 2018-03-10
Publication date: 2019-09-17

Abstract

The hydrogen supply dissolvent application method of heavy hydrocarbon up flow type hydro-upgrading reaction process inferior, add hydrogen environment using the thermal cracking that a large amount of hydrogen supply dissolvents form sufficiently offer reactive hydrogen in up flow type heat from hydrogenation cracking process RX to handle heavy hydrocarbon HDS inferior and obtain reaction product RX-P, RX-P is separated into the gas S10-V and liquid S10-L of the solvent hydrocarbon ADSC containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor in separation process S10, the logistics DS10 or its stabilized hydrogenation object DSH10 of the ADSC of hydrocarbon containing solvent is obtained based on gas S10-V, at least part logistics DS10 or its stabilized hydrogenation object DSH10 returns to RX and participates in reaction, it is outer for hydrogen supply dissolvent quantity to reduce；The logistics of the ADSC of hydrocarbon containing solvent based on RX-P can contact participation reaction into the up flow type heat from hydrogenation cracking reaction process R10 and R10F of R10F or its hydro-conversion object, and secondary to use solvent hydrocarbon, R10F is heavy oil and/or coal.

Description

The hydrogen supply dissolvent application method of heavy hydrocarbon up flow type hydro-upgrading reaction process inferior

Technical field

The present invention relates to the hydrogen supply dissolvent application method of heavy hydrocarbon up flow type hydro-upgrading reaction process inferior, in up flow type plus Hydrogen thermal cracking process RX adds hydrogen environment to handle inferior heavy using the thermal cracking that a large amount of hydrogen supply dissolvents form sufficiently offer reactive hydrogen Hydrocarbon HDS obtains reaction product RX-P, and RX-P is separated into the solvent containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor in separation process S10 The gas S10-V and liquid S10-L of hydrocarbon ADSC, based on gas S10-V obtain the ADSC of hydrocarbon containing solvent logistics DS10 or its add hydrogen Resistate DSH10, at least part logistics DS10 or its stabilized hydrogenation object DSH10 return to RX and participate in reaction, outer for supplying to reduce Hydrogen amount of solvents；The logistics of the ADSC of hydrocarbon containing solvent based on RX-P can enter the up flow type heat from hydrogenation cracking reaction process of R10F R10 contacts participation reaction with R10F or its hydro-conversion object, and secondary to use solvent hydrocarbon, R10F is heavy oil and/or coal；Based on RX-P The logistics containing heavy hydrocarbon component, participation can be contacted with R10F or its hydro-conversion object by least part reaction process of R10 Heavy hydrocarbon joint processing is realized in reaction；Hydrocarbon HDS inferior, which can be, to be boiled based on what reaction process R10 product R10-P was obtained containing conventional The material that point is higher than 520 DEG C of hydro carbons is such as fractionated tail oil；Material RLK or RLK containing ADSC is obtained based on gas MTHS-VK to add The hydrogen-containing hydrocarbon stream RLKH that hydrogen obtains can return to RX and/or R10A and participate in reaction；R10 can be divided into front conversion zone R10A with after Front conversion zone product R10A-P is separated into containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon predecessor by portion conversion zone R10B in separation process MTHS The gas MTHS-V and liquid MTHS-L of the solvent hydrocarbon ADSC of object, at least part gas MTHS-V do not enter R10B, at least one Partially liq MTHS-L enters R10B and completes reaction, needs R10 using high pressure hot separator between section or across flow reactor；In RX-P At least part of heavy hydrocarbon can enter R10A or R10B, realize the reasonable control of the hot tearing rate of heavy hydrocarbon in RX-P；Solvent hydrocarbon ADSC can be the outer for the conversion product of hydrogen supply hydrocarbon and/or the self-produced hydro carbons of hydrocarbon material HDS, R10F of RX, R10；It is sent out in RX, R10A While waving the inhibition coking function of solvent hydrocarbon ADSC, is reduced in R10B and inhibit the ADSC quantity of thermal cracking function, improve The heat from hydrogenation cracking rate of R10B heavy hydrocarbon, the hot tearing rate for reducing solvent hydrocarbon ADSC, realize the optimization of operating condition；Stabilized hydrogenation is anti- The stabilized hydrogenation for answering process that can also serve as R10 charging (fed upstream or recycle feed or series connection raw material from downstream) reacted Journey.

Background technique

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 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 were reacted Journey, kerosene refine the hydrocarbon component in hydrogenation process with transmitting hydrogen function, such as polycyclic aromatic hydrocarbon altogether.

Solvent hydrocarbon ADSC described herein, refer to be hydrogen supply the hydrocarbon component and/or hydrogen supply hydrocarbon mistake hydrogen after before component or hydrogen supply hydrocarbon Body object serves as hydrogen supply hydrocarbon or hydrogen passes in the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F such as heavy oil and/or coal Pass hydrocarbon.

In the up flow type heat from hydrogenation cracking reaction process R10 of conventional decompression residuum R10F, mentioned in time if can not achieve For the sufficient reactive hydrogen of quantity, there is condensation for compared with before it in the thermal cracking free radical of colloid, asphalitine in decompression residuum R10F The bigger molecule of body object is until condensation is the thermal condensation reaction path of coke.The up flow type heat from hydrogenation of usual decompression residuum R10F is split The property for changing the heat from hydrogenation cracked residue R10-HO that reaction process R10 is generated is more worse than decompression residuum R10F, usual residual oil R10- The hydrogen content of HO is lower and/or carbon residue is higher and/or is easier to coking.In order to carry out effective heavy arene or colloid, asphalitine Add hydrogen saturated reaction, guarantees that its subsequent heat from hydrogenation cracking reaction process stablizes long-term operation, an effective selection is to be formed Inhibit the solution condition of coking and quickly therefore offer reactive hydrogen solution condition adds hydrogen in the up flow type of process residual oils R10-HO Thermal cracking process RX is operated under the conditions of high oil ratio (ratio of solvent hydrocarbon ADSC weight and residue fraction weight) to be used A large amount of hydrogen supply dissolvents, just become inevitable choice.

Compared with decompression residuum R10F, another feature of residual oil R10-HO is that quantity is only decompression residuum R10F quantity 20~35%, and the thermal cracking conversion ratio of the up flow type heat from hydrogenation cracking process RX of process residual oils R10-HO can control in low water Flat, therefore, the product identical with solvent hydrocarbon ADSC boiling point of the up flow type heat from hydrogenation cracking process RX of process residual oils R10-HO is more It is few, it is easy to use gas-liquid separation or air lift gas-liquid separate mode, the solvent hydrocarbon ADSC component in recovery product RX-P, to follow in this way Ring utilization or secondary use or selective hydrogenation stabilization create advantage.

About the reaction characteristics of hydrogen supply hydrocarbon, hydrogen supply hydrocarbon discharge reactive hydrogen make thermal cracking free radical stabilized hydrogenation while, The concentration of reaction compartment thermal cracking free radical is reduced, to have the function of inhibiting thermal cracking, the thermal cracking of heavy hydrocarbon can be reduced Rate, for example, the front conversion zone R10A of a large amount of heat cracking reactions of generation in heavy-oil hydrogenation heat cracking reaction process R10, uses The sufficient hydrogen supply hydrocarbon of quantity has the function of inhibiting thermal condensation coking have positive influences to production process；And it is anti-in thermal cracking There is the superfluous hydrogen supply hydrocarbon in part, superfluous hydrogen supply hydrocarbon in the hydrogen supply hydrocarbon of equivalent in the rear portion conversion zone R10B for answering quantity to be greatly reduced With the negative effect for inhibiting heavy hydrocarbon thermal cracking, reducing heavy hydrocarbon hot tearing rate.

The first object of the present invention is the up flow type heat from hydrogenation cracking process RX in residual oil R10-HO, is economically formed high agent The condition of oily ratio.

The second object of the present invention is to improve the outer service efficiency for hydrogen supply hydrocarbon, reduces the outer usage amount for hydrogen supply hydrocarbon, i.e., It realizes the recycling of hydrogen supply hydrocarbon or is used in series.

The third object of the present invention is, based on the action character of hydrogen supply hydrocarbon, makes the best use of the advantages and presses down short optimization using effect.

Hydrocarbon material R10F of the present invention, including hydrocarbon liquid material such as heavy oil and/or hydrocarbon powder such as coal.

The up flow type heat from hydrogenation cracking process R10 of hydrocarbon material R10F of the present invention uses up flow type hydrogenator, hair The stabilized hydrogenation reaction of the heat cracking reaction, thermal cracking free radical of the raw hydrocarbon material R10F of at least part, generates at least part The lower hydrocarbon product of boiling point can be inferior heavy oil heat from hydrogenation cracking reaction process, direct hydrogenation liquefaction of coal reaction process, coal Oil refines hydrogenation process altogether.

Basic imagination of the invention is: the hydrogen supply dissolvent application method of heavy hydrocarbon up flow type hydro-upgrading reaction process inferior, Up flow type heat from hydrogenation cracking process RX using a large amount of hydrogen supply dissolvents formed sufficiently provide reactive hydrogen thermal cracking add hydrogen environment with Processing poor quality heavy hydrocarbon HDS obtains reaction product RX-P, before RX-P is separated into containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon by separation process S10 The gas S10-V and liquid S10-L of the solvent hydrocarbon ADSC of body object, obtains the logistics of the ADSC of hydrocarbon containing solvent based on gas S10-V DS10 or its stabilized hydrogenation object DSH10, at least part logistics DS10 or its stabilized hydrogenation object DSH10 return to RX and participate in reaction, It is outer for hydrogen supply dissolvent quantity to reduce；The logistics of the ADSC of hydrocarbon containing solvent based on RX-P can enter the up flow type heat from hydrogenation of R10F Cracking reaction process R10 contacted with R10F or its hydro-conversion object participation reaction, it is secondary use solvent hydrocarbon, R10F be heavy oil and/or Coal；The logistics containing heavy hydrocarbon component based on RX-P can pass through at least part reaction process and R10F or its hydro-conversion of R10 Object contact participates in reaction, realizes heavy hydrocarbon joint processing；Hydrocarbon HDS inferior, which can be, to be obtained based on reaction process R10 product R10-P The material for being higher than 520 DEG C of hydro carbons containing normal boiling point is such as fractionated tail oil；The material containing ADSC is obtained based on gas MTHS-VK The hydrogen-containing hydrocarbon stream RLKH that RLK or RLK adds hydrogen to obtain can return to RX and/or R10A and participate in reaction；It is anti-that R10 can be divided into front Section R10A and rear portion conversion zone R10B are answered, front conversion zone product R10A-P is separated into containing hydrogen supply hydrocarbon in separation process MTHS Or the gas MTHS-V and liquid MTHS-L of the solvent hydrocarbon ADSC of hydrogen supply hydrocarbon precursor, at least part gas MTHS-V do not enter R10B, at least part liquid MTHS-L enter R10B and complete reaction, need R10 anti-using high pressure hot separator between section or across stream Answer device；At least part of heavy hydrocarbon can enter R10A or R10B in RX-P, and the hot tearing rate of heavy hydrocarbon is reasonable in realization RX-P Control；Solvent hydrocarbon ADSC can be the outer for the conversion product of hydrogen supply hydrocarbon and/or the self-produced hydro carbons of hydrocarbon material HDS, R10F of RX, R10； While RX, R10A play the inhibition coking function of solvent hydrocarbon ADSC, the ADSC for inhibiting thermal cracking function is reduced in R10B Quantity, the heat from hydrogenation cracking rate for improving R10B heavy hydrocarbon, the hot tearing rate for reducing solvent hydrocarbon ADSC, realize the optimization of operating condition； Stabilized hydrogenation reaction process can also serve as R10 charging (fed upstream or recycle feed from downstream or series connection raw material) plus hydrogen Stablize reaction process.

Due to the particularity of hydrogen supply dissolvent composition, price is higher, therefore usually reduces outsourcing hydrogen supply dissolvent as far as possible and use Amount tries that hydrogen supply dissolvent is recycled, in this way, the hydro-conversion object of hydrogen supply dissolvent and with the other heavy of boiling point in process Oily isocrackate necessarily mixes, that is to say, that will necessarily reduce purity by ground contamination to a certain degree, therefore, circulation supplies Hydrogen solvent is usually a kind of equilibrium mixture material containing a certain concentration hydrogen supply dissolvent or hydrogen supply dissolvent conversion product, that is to say, that is needed Hydrogen supply dissolvent is isolated in suitable flow points, this is one and is related to the equilibrium composition problem of hydrogen supply dissolvent cyclic process.

About the hydrogenation depth problem of hydrogen supply dissolvent cyclic process, the aromatic carbon rate for being typically due to hydrogen supply dissolvent is preferably 0.45~ 0.55, and it is therefore not desirable to which hydrogen supply dissolvent retains for a long time in adding in hydrogen or heat from hydrogenation cracking environment for shortage hydrogen-abstracting agent, because can make It is decomposed at the excessive hydrogenation saturation even heat from hydrogenation cracking of hydrogen supply dissolvent conversion product, these are that the chemistry of reduction hydrogen supply agent is anti- It answers, therefore, the reaction process of hydrogen supply dissolvent circulation loop is needed in other words there are the reasonable control problem of hydrogenation depth suitable Flow points isolate hydrogen supply dissolvent.

Operation length problem about hydrogen supply dissolvent cyclic process, it is often desirable that the circulation loop is as short as possible, to drop Low investment reduces energy consumption, therefore, it is necessary to isolate hydrogen supply dissolvent in flow points as short as possible, certainly preferably in high pressure system System is internal to form circulation, avoids the pressure reduction of material, boost process, temperature-rise period, temperature-fall period, separation as far as possible and/or divides Step is evaporated, these processes are usually to invest the step of big, energy consumption is high, generation equipment abrasion.

Other hydrocarbon hydrogenation process RX inferior for needing hydrogen supply hydrocarbon of the present invention, can occur hydrofining reaction (including Demetalization adds hydrogen hydrogenolysis, olefins hydrogenation reaction plus hydrogen removing impurities matter (oxygen, sulphur, nitrogen) reaction plus hydrogen aromatic hydrocarbons saturation or portion Divide saturated reaction, removal of ccr by hydrotreating reaction) and/or hydrocracking reaction, but in group technology of the invention, the first of RX Reaction task be usually carry out heavy hydrocarbon inferior removal of ccr by hydrotreating reaction be heavy arene or colloid, asphalitine plus hydrogen saturation it is anti- It answers.

Therefore, the heavy oil RXF of RX processing, heavy hydrocarbon up flow type heat from hydrogenation cracking process R10 processing usually more of the present invention Heavy oil R10FL mass it is worse, the hydrogen content of usual heavy oil RXFL is lower and/or carbon residue is higher and/or is easier to coking.In order to carry out Effective heavy arene or colloid, asphalitine plus hydrogen saturated reaction, guarantee that its subsequent heat from hydrogenation cracking reaction process stablizes length Periodic duty it may first have to form the solution condition for inhibiting coking and reactive hydrogen solution condition, therefore, hydro-upgrading are quickly provided Process RX is operated under the conditions of high oil ratio uses a large amount of hydrogen supply dissolvents, just becomes inevitable choice.

The product heavy oil R10-HO of heavy oil floating bed hydrogenation thermal cracking process R10, is commonly referred to as 470 DEG C of normal boiling point > Hydro carbons, generally referred to as 500 DEG C of hydro carbons of normal boiling point > particularly refer to 530 DEG C of hydro carbons of normal boiling point >, in process flow In usually become vacuum fractionation tower tower bottom residual oil, this residual oil R10-HO usually contains the catalyst conversion product of addition as vulcanized Molybdenum, the R10 product metal sulfide from heavy oil R10FL, these concentration containing metal solid in residual oil R10-HO are much higher than The concentration of the metallic catalyst of heavy oil floating bed hydrogenation thermal cracking process R10, this is a progress residual hydrogenation saturated reaction Advantage.

For heavy oil floating bed hydrogenation thermal cracking process R10, first free-revving engine of the invention is to be used in series hydrogen supply Hydrocarbon reduces the usage amount of hydrogen supply hydrocarbon.

For heavy oil floating bed hydrogenation thermal cracking process R10, second free-revving engine of the invention is, for using hydrogen supply The hydrocarbon material up flow type heat from hydrogenation cracking reaction process of solvent supplies at least part surplus in the reaction process R10A-P of front Hydrogen hydrocarbon is separated, from pass through rear portion reaction process R10B, so as to improve the thermal cracking of rear portion reaction process R10B Rate.

For heavy oil floating bed hydrogenation thermal cracking process R10, third free-revving engine of the invention is to reduce hydrogen supply hydrocarbon Hot tearing rate.

For heavy oil floating bed hydrogenation thermal cracking process R10, the 4th free-revving engine of the invention is the hydrogen supply isolated Hydrocarbon or its stabilized hydrogenation object for restoring hydrogen supply capacity, can return to R10 and/or add hydrogen by other hydrocarbon inferior for needing hydrogen supply hydrocarbon Process RX is recycled or is used in series.

For heavy oil floating bed hydrogenation thermal cracking process R10, the 5th free-revving engine of the invention is to reduce hydrogen supply hydrocarbon to follow The length of loop back path reduces investment and energy consumption.

For heavy oil floating bed hydrogenation thermal cracking process R10, the 6th free-revving engine of the invention is proposed on hydrocarbon material The combined method of streaming heat from hydrogenation cracking process R10 and its product heavy oil R10-HO up flow type hydro-upgrading process RX, the original of R10 Expect that hydrocarbon material can be coal and/or oil, is particularly suitable for processing inferior heavy oil；It is obvious that if can initiatively improve product heavy oil The quality (as improved hydrogen content, reducing gum level, reduction asphalt content) of R10-HO, necessarily can be effectively reduced inferior heavy Hydrocarbon up flow type hydro-upgrading process RX's adds hydrogen severity, effectively improves the overall hydrogenation conversion and economy of technique, this is related to And the either shallow heat from hydrogenation cracking zone R10A of heavy oil R10FL up flow type heat from hydrogenation cracking process R10 plus hydrogen effect, i.e., for initial The thermal cracking free radical of colloid, asphalitine in raw material R10FL provides the quantity and speed of reactive hydrogen；And use hydrogen supply agent or confession Hydrogen agent precursor can accelerate the transmission speed of reactive hydrogen, increase the quantity of reactive hydrogen to be well known technological means, hydrogen supply agent or The dosage of precursor of hydrogen donor is bigger, and the transmission speed of fast reactive hydrogen, the quantity for increasing reactive hydrogen are more, but process Cost is higher.

Present invention is primarily intended to propose that economic efficient combination technique, control and reduction reaction process green coke amount improve The overall heat from hydrogenation cracking rate of group technology, key problem therein are series connection or the circulating series Land use systems of hydrogen supply agent, with And the control of heavy hydrocarbon thermal cracking conversion ratio.

Chinese patent ZL200810228415.9 combined technological method for heavy oil modification, the floating bed hydrocracking of heavy oil feedstock Reaction effluent is separated, and the unconverted tail oil of floating bed hydrocracking is mixed with hydrogen supply dissolvent carries out first supercritical processing, is supplied Hydrogen solvent includes naphthane or decahydronaphthalene, and supercritical processing conditions are in the case where 15~40MPa of pressure and temperature are 300~500 DEG C Processing 0.2~5 hour, heat from hydrogenation cracking conversion rate is usually 40~80%, and processing product is divided after isolating solid impurity Evaporate processing；The invention organically combines floating bed hydrocracking and first supercritical processing, has synergistic effect, can reduce coking and incline To raising removing impurities mass-energy power can be improved the operational stability of slurry-bed hydrocracking process, can handle original more inferior Material.

The advantages of Chinese patent ZL200810228415.9, is:

1. using hydrogen supply dissolvent, the unconverted tail oil of floating bed hydrocracking is effectively modified；

2. reaction mass carries out fractionation processing after isolating solid after floating bed hydrocracking processing, can with it is overcritical anti- Answering treated, material separates in a fractionating system, simple flow；

3. the ends fraction or whole containing hydrogen supply dissolvent or mistake hydrogen hydrogen supply dissolvent that supercritical reaction effluent is isolated It is recycled back to floating bed hydrocracking to be handled, replenishes the hydrogen that supercritical fluid loses, restore hydrogen supply function, be subsequently used for surpassing Critical reaction process, it is not necessary to build individual hydrogen supply dissolvent and bring back to life reaction process；

4. using fractional method that the hydrogen supply including superfluous hydrogen supply dissolvent or mistake hydrogen is molten in the mixture of supercritical reaction Agent is separated, direct reuse after separation, or is recycled after the fresh hydrogen supply dissolvent of supplement, or pass it through suspension bed and add It is recycled after hydrogen cracking process；

5. supercritical reaction device is continuously stirred tank reactor (CSTR) or batch reactor.

The shortcomings that Chinese patent ZL200810228415.9, is:

1. hydrogen supply dissolvent dosage is 1: 0.5~1 by the weight ratio of heavy oil feedstock (not being suspension bed tail oil) and hydrogen supply dissolvent: 10, and tail oil yield is usually 20~40%, such hydrogen supply dissolvent dosage is 1 by the weight ratio of suspension bed tail oil and hydrogen supply dissolvent : 1.2~1: 50, the hydrogen supply dissolvent quantity used is too big, uneconomical；

2. reaction mass carries out fractionation processing after isolating solid after floating bed hydrocracking processing, the group of technique is limited Conjunction mode；

3. not utilizing the catalyst being enriched in supercritical reaction product repeatedly；

4. the ends fraction or whole containing hydrogen supply dissolvent or mistake hydrogen hydrogen supply dissolvent that supercritical reaction effluent is isolated It is recycled back to floating bed hydrocracking to be handled, restores hydrogen supply function；Since floating bed hydrogenation splits reaction process, but one is deposited In the reaction process of a large amount of thermal cracking free radical, that is, hydrogen-abstracting agents, therefore, it is not possible to realize the best On Reactivation of hydrogen supply dissolvent, no Conducive to target material heavy oil, heat cracking reaction stage is quickly obtained reactive hydrogen in the early stage；

5. being isolated using fractional method includes the hydrogen supply dissolvent of surplus or the confession for losing hydrogen in the mixture of supercritical reaction Hydrogen solvent composition, is then recycled, but the component is by the same boiling range group in heavy oil floating bed hydrogenation hot cracked product Divide and polluted, a large amount of nonideal the hydrocarbon components are contained in the circulation hydrogen supply dissolvent of equilibrium state；

6. floating bed hydrogenation thermal cracking cannot be used for whole hydrogen supply dissolvent groups in supercritical reaction product in two times Journey is not at least its main target in other words because this is not the target of Chinese patent ZL200810228415.9.

A kind of heavy oil hydrogenation modifying method of Chinese patent ZL200910204290.0, heavy oil feedstock and homogeneous catalyst are mixed It closes, and is mixed with overcritical hydrogen supply dissolvent (including naphthane or decahydronaphthalene), content of the hydrogen supply dissolvent in heavy oil feedstock is 50PPm~5wt%；The mixture of heavy oil feedstock and catalyst and hydrogen supply dissolvent in presence of hydrogen, under certain reaction condition The hydrocracking reaction of heavy oil is carried out, heat from hydrogenation cracking conversion rate is usually 40~80%.The invention heavy oil upgrading process will hang Floating bed is hydrocracked to be organically combined with first supercritical processing, has synergistic effect, can be reduced coking tendency, be improved removing impurities mass-energy power, The operational stability of slurry-bed hydrocracking process can be improved.But this method has the disadvantage in that

1. the hydrogen supply dissolvent quantity used is very little, inhibit the amplitude of coking little；

2. will include the hydrogen supply dissolvent of surplus or the hydrogen supply dissolvent for losing hydrogen in reaction product using extraction or fractional method Hydrogen supply dissolvent is separated, due to hydrogen supply dissolvent additive amount is few and floating bed hydrogenation hot cracked product yield is big, it is described extraction or The efficiency of fractional method is too low, the rate of recovery will not very high or regenerant purity it is lower；

3. the circulating path of hydrogen supply dissolvent is too long；

4. floating bed hydrogenation tail oil directly returns to floating bed hydrogenation thermal cracking process, directly to carry out secondary heat from hydrogenation cracked Journey, rather than first pass through and hydrogen is added to be saturated de- carbon residue process, it is unfavorable for floating bed hydrogenation thermal cracking process and inhibits coking.

A kind of low hydrogen content heavy oil using hydrogen supply hydrocarbon of Chinese patent ZL201210022921.9 adds hydrogen lightening method, The hydrogen-containing hydrocarbon stream that will be enriched in hydrogen supply hydrocarbon adds hydrogen lighting process for heavy oil such as coal tar pitch, has and inhibits condensation coking speed Degree improves coal tar heavy oil hydroconversion process liquid product yield, improves product quality, reduces reaction temperature rising, enhancement device The effect of smooth operation and safety, but the concept of the stabilized hydrogenation process without proposing floating bed hydrogenation residual oil, do not have yet There is the similar group technology of the invention of proposition.

A kind of up flow type heat from hydrogenation cracking of high aromatic carbon rate poor quality hydrocarbon branch charging of Chinese patent ZL201610525311.9 Method is suitable for the high aromatic carbon rate poor quality hydrocarbon such as high normal boiling point of metal, polycyclic aromatic hydrocarbon, colloid, asphalt content higher than 450 DEG C Coal tar heavy oil HDS floating bed hydrogenation heat cracking reaction process R10, R10 include 2 or multiple serial operations first, Second sub- hydroconversion reaction zone R101, R102 etc., hydrocarbon HDS inferior points are two-way or demultiplex raw material HDS1, HDS2, HDS1 entrance The reaction effluent R101P or logistics R101PX containing its hydrogenated oil obtained by R101 enters R102 and contacts with HDS2, can reduce Concentration of the fresh feed HDS2 in R102 liquid phase is remarkably improved SHS and flows through instead when R101 uses hydrogen-containing hydrocarbon stream SHS The ratio for answering in area " hydrogen supply hydrocarbon weight/fresh feed HDSX weight " can reduce thermal condensation coking speed, but outstanding without proposing The concept of the stabilized hydrogenation process of floating bed hydrogenated residue, also without proposing similar group technology of the invention.

A kind of heavy oil hydrogenation modifying method of above-mentioned Chinese patent ZL200910204290.0, Chinese patent ZL200810228415.9 combined technological method for heavy oil modification and similar process, Chinese patent A kind of low hydrogen content heavy oil using hydrogen supply hydrocarbon of ZL201210022921.9 adds hydrogen lightening method, Chinese patent A kind of up flow type heat from hydrogenation cracking method of high aromatic carbon rate poor quality hydrocarbon branch charging of ZL201610525311.9, with master of the invention It wants target different, can not achieve the purpose of the present invention, therefore be the technical solution being different from the present invention.

In fact, heavy oil floating bed hydrogenation thermocracking process substantially has 7 critical issues:

1. prevent heavy-oil heating furnace coking, this relate to how reduce heavy-oil heating heater outlet temperature the problem of, be also related to as What uses the problem of coking inhibitor such as hydrogen supply dissolvent；

2. inhibiting the thermal condensation of the incipient thermal cracking process of heavy oil feedstock, this relates to how quickly to provide asking for reactive hydrogen Topic, the problem of also relating to how using hydrogen supply dissolvent；

3. preventing heat cracking reaction process latter stage solution system from over-saturation pitch mutually i.e. second liquid phase occur, this is related to rationally Conversion per pass problem is controlled, also relates to how that lightweight saturated hydrocarbons is discharged in time prevents it from reducing solution aromaticity problem；

4. reducing tail oil yield, process economics are improved, this is related to the later half of a thermal cracking process of the fresh material of heavy oil The raising problem of journey hot tearing rate, the problem of also relating to how using hydrogen supply dissolvent；

5. reducing tail oil yield, process economics are improved, this is related to tail oil modification and circulation heat from hydrogenation cracking issues, also relates to And the problem of how using hydrogen supply dissolvent；

6. reducing tail oil heat from hydrogenation cracking cyclic process cost, process economics are improved, this is related to tail oil modification and circulation Heat from hydrogenation cracking reaction process, the combined method with fresh heavy oil floating bed hydrogenation heat cracking reaction process, also relates to how height The problem of effect is using hydrogen supply dissolvent；

7. if which kind of method shortening its circulating path using hydrogen supply dissolvent using, reducing contaminated degree, raising use Efficiency.

And the present invention is to be related to a kind of comprehensive solution of above-mentioned multiple problems.

Compared with other conventional schemes, the present invention may be constructed following group technologies:

1. the floating bed hydrogenation process of fresh heavy oil, anti-by initial stage heat from hydrogenation cracking using Liquid product recycle reactor It answers heat to be transferred to raw material heavy oil, so that its preheating temperature is reduced to 360~380 DEG C, prevents heavy oil heater tube coking, A small amount of (such as the 5~10% of heavy oil amount) hydrogen supply dissolvent further pre- anti-coking can be used；

2. using high dispersive high activated catalyst such as molybdenum series catalyst, while hydrogen supply dissolvent is used, reactive hydrogen is quickly provided, Inhibit the thermal condensation of the incipient thermal cracking process of heavy oil feedstock, this is a kind of active approach substantially, can significantly improve one Secondary heat from hydrogenation cracking tail oil property；

3. preventing heat cracking reaction process latter stage solution system from over-saturation pitch occur, mutually i.e. second liquid phase, this requirement are reasonable It controls conversion per pass and improves reactor exit hydrocarbon liquid phase using Liquid product recycle reactor in 65~80% ranges Aromaticity, while lightweight saturated hydrocarbons is discharged in time using reactor outlet penetrating air lift hydrogen prevents its reduction solution aromaticity from asking Topic, being also prevented from its excessively circulation thermal cracking reduces liquid yield；And reduce the presence of excessively more hydrogen supply dissolvents, it can improve Hot tearing rate, the hot tearing rate that hydrogen supply dissolvent can be reduced again；

4. reducing tail oil yield, process economics are improved, tail oil hydro-upgrading reaction process RX is set, in high agent oil Than, under conditions of high catalyst concn, low reaction temperature, react using aromatic hydrogenation saturated reaction as main target Hydro-upgrading process, then by product RX-P import floating bed hydrogenation heat cracking reaction process R10 in rear portion reaction zone R12 into The heat from hydrogenation cracking reaction of row appropriateness prevents the too high excessive thermal condensation of initiation of modification tail oil R20-HO one way hot tearing rate anti- It answers, controls the ratio of reaction type in the whole circulation hydrogenation process of a tail oil R10-HO, properly increase plus hydrogen is saturated ratio, Heat from hydrogenation cracking ratio is reduced, by way of increasing internal circulating load, realization repeatedly converts in batches, controls the stability of solution, drops Low outlet tail oil quantity improves outlet tail oil quality；It is optimal the result is that outlet tail oil amount seldom (for example be lower than 3~5%), Being only used for discharge solid particle (including catalyst granules, raw material heavy oil metal sulfide, minimal amount of coking particle) prevents it It is built up in reaction system；

Meanwhile batch feed technology can be used, further increase the coke forming property for inhibiting tail oil circulation hydrogenation process；

5. tail oil circulation hydro-upgrading reaction process of the invention and fresh heavy oil floating bed hydrogenation heat cracking reaction process Combined method, can reduce tail oil circulation hydro-upgrading reaction process cost, improve process economics, it is molten due to foring hydrogen supply The secondary use of agent, therefore the overall hydrogen supply capacity of the circulating path of hydrogen supply dissolvent is significantly improved, it improves and recycles efficiency；

6. providing the efficient circulation path of hydrogen supply dissolvent, its circulating path length can be shortened, reduce circulation loop investment And energy consumption, it reduces hydrogen supply dissolvent and is contaminated degree, can effectively reduce cycle cost；

7. can combine the dedicated resurrection step of hydrogen supply dissolvent with distillate hydrogenation upgrading step, process collection is further increased Cheng Du reduces the investment and energy consumption of overall craft；

7. heavy-oil hydrogenation process uses floating bed hydrogenation reactor, it is preferred to use Liquid product recycle formula floating bed hydrogenation is anti- Answer device.

The technological advantage or feature that the present invention is shown during heavy oil floating bed hydrogenation heat cracking reaction, it is very aobvious It writes, these advantages also exist in other similar hydrocarbon material, and (such as direct hydrogenation liquefaction of coal reaction process, kerosene refine hydrogenation reaction altogether Process) hydrogenation process in.

If heavy oil floating bed hydrogenation thermal cracking recycles in tail oil RKL inherently heavy oil from the point of view of component characteristic The residue or conversion product of macromolecular, or be more precisely the residue or conversion product of the non-lighting of macromolecular in heavy oil Concentrate is convenient for shape because its quantity is seldom such as usually the 0.15~0.40 of heavy oil weight compared with heavy oil feedstock Such as reach 0.5~1.00 progress floating bed hydrogenation at high solvent-oil ratio solvent condition to obtain adding hydrogen saturated products RX-P, then may be used It realizes that the secondary of hydrogen supply dissolvent is used in series to enter reaction process R10A, or enters after isolating hydrogen supply dissolvent into MTH Bis- series connection of reaction process R10B processing carries out appropriate heat from hydrogenation cracking, recycles the catalyst action that has being enriched in tail oil RKL Particle is used to generate reactive hydrogen, other solid particles of enrichment are used to carry possible green coke, and the collaboration between above-mentioned element is made With being objective reality, therefore, problem andsolution proposed by the present invention is that hydrocarbon material heat from hydrogenation cracking reaction process exists A common problem and the technical solution that generally uses, since influential effect of the invention is huge, appearance of the invention is must Right.

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

For specific application, as needed, the present invention can be reasonably selected to having hydrocarbon material hydrogen addition technology Using or be used cooperatively.

The method of the invention has not been reported.

Therefore, the first object of the present invention is to propose the hydrogen supply dissolvent circulation of heavy hydrocarbon up flow type hydro-upgrading process RX inferior Application method, heavy hydrocarbon inferior can be the heavy hydrocarbon containing solid matter.

The second object of the present invention is to propose poor quality heavy hydrocarbon up flow type hydro-upgrading process RX, hydrocarbon material up flow type heat from hydrogenation The series connection of the hydrogen supply dissolvent of cracking process R10, recycling method, hydrocarbon material can be coal and/or oil, and heavy hydrocarbon inferior can be The material containing residual oil of heat from hydrogenation cracking conversion product of coal and/or oil, to constitute group technology；According to outer for solvent hydrocarbon The need of the number of ADSC amount and/or hydrocarbon material up flow type heat from hydrogenation cracking process R10 differential responses stage to solvent hydrocarbon ADSC amount It asks, high pressure hot separator or across the flow reactor process simplification process flow of use between section can be used in R10；Stabilized hydrogenation reaction process Multichannel solvent hydrocarbon material even whole solvent hydrocarbon material (fed upstream or recycle feeds or series connection original from downstream can be also served as Material) stabilized hydrogenation reaction process, formed integrated flow.

The third object of the present invention is to propose poor quality heavy hydrocarbon up flow type hydro-upgrading process RX, hydrocarbon material up flow type heat from hydrogenation Cracking process R10, the combined method containing solid residuum coking process is got rid of outside, getting rid of oil containing solid slag outside can be with devulcanization as coking raw material Coking processing can go delayed coking as blending Raw material processing, coal coking process can be gone as blending raw material Processing, and the coal gas that coal coking process generates can be used as hydrogen feedstock hydrogen making, and tar that coal coking process generates or The distillate of tar can be used as good hydrogen supply dissolvent precursor and enter joint processing in group technology of the invention, thus structure At the big combination of a kind of process of coking and processing of heavy oil process.Oil containing solid slag is got rid of as coal coking process ingredient outside in use, making After individually crushing for room temperature solid oil containing solid slag with coking coal blending it is used as coking raw material or room temperature be that solid contains solid slag Oil crushes together after blending with coking coal is used as coking raw material, since oil containing solid slag is rich in colloid, asphalitine, in high-temperature coking mistake Journey is equivalent to the use of the coal rich in gel, and compared with the gel inside coal particle, the ratio of the gel from residual oil is more Greatly, mobility is more preferable, and energy filled solid particulate interspaces have good cementation；Compared with the gel inside coal particle, First, the molecular weight of the gel from residual oil is smaller, thus its to be heated the critical transition temperature with mobility lower i.e. Flow regime can be entered in advance in heating process, the hydrogen content of the second gel from residual oil is higher, so its is dehydrogenation curing Time it is longer i.e. colloidal state it is longer there are the time, therefore have better bond effect；Containing solid coking of residues product, A part of product, that is, coked solid becomes the component part of coke, and the high temperature thermal cracking reaction of second part product, that is, process of coking produces Raw raw gas, raw gas are the gas comprising components such as hydrogen, conventional gas hydrocarbon, tar, separate the available tar of coal gas, burnt Oil or tarry distillate enter heavy hydrocarbon up flow type hydro-upgrading process inferior and/or hydrocarbon material up flow type heat from hydrogenation cracking process joint Processing.

The fourth object of the present invention is to propose heavy oil catalytic cracking process, heavy hydrocarbon up flow type hydro-upgrading process inferior, carbon The combined method of hydrogen material up flow type heat from hydrogenation cracking process produces heavy oil catalytic cracking process (or heavy-oil catalytic thermal cracking process) (catalytic cracking diesel oil and/or catalytic cracking wax oil and/or hydrocarbon material up flow type add hydrogen to the raw hydrocarbon ils rich in 2~4 ring structure aromatic hydrocarbons The wax slop of thermal cracking process) concentrate be modified as hydrogen supply dissolvent use, getting rid of oil containing solid slag outside as coking raw material can go to fluidize Coking can go delayed coking as blending Raw material processing, coal coking process can be gone to be used as blending Raw material processing, And the gas that coking generates can be used as hydrogen feedstock hydrogen making, the distillate that coking generates can enter this hair Joint processing such as possibly serves for good hydrogen supply dissolvent precursor in bright group technology, thus constitute a kind of heavy-oil catalytic, Hydrogenation of residual oil suspended bed thermal cracking, the big combination of coking.

Summary of the invention

The hydrogen supply dissolvent application method of poor quality heavy hydrocarbon up flow type hydro-upgrading reaction process of the invention, it is characterised in that include Following steps:

In up flow type hydro-upgrading reaction process RX, there are hydrogen, hydrogen supply hydrocarbon, other conventional liq hydrocarbon may deposit simultaneously Under the conditions of the mixed phase material of solid particle, at least partially containing normal boiling point higher than 500 DEG C of the hydrocarbon component hydrocarbon HDS inferior into At least part aromatic hydrogenation saturated reaction, at least part heat cracking reaction, at least one occur for row hydro-upgrading reaction RX-R The stabilized hydrogenation reaction of part free radical is converted into hydrogenation reaction product RX-P；Reaction process RX is received and is contained hydrogen supply hydrocarbon or confession The material of the solvent hydrocarbon ADSC of hydrogen hydrocarbon precursor；

The gas of the solvent hydrocarbon ADSC containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor is separated into separation process S10, RX-P S10-V and liquid S10-L obtains the logistics DS10 or logistics DS10 of the ADSC of hydrocarbon containing solvent based at least part gas S10-V Stabilized hydrogenation object DSH10, at least part logistics DS10 or logistics DS10 stabilized hydrogenation object DSH10 return RX participate in it is anti- It answers, is contacted with hydrocarbon HDS inferior or hydrocarbon HDS hydro-conversion object inferior；

The solvent hydrocarbon ADSC component, be hydrogen supply the hydrocarbon component and/or hydrogen supply hydrocarbon mistake hydrogen after component；

The solvent hydrocarbon ADSC component of hydrogenation process is the outer for hydrogen supply hydrocarbon or outside for hydrogen supply hydrocarbon of hydrogenation process Lose the self-produced hydro carbons of hydrogen conversion product and/or other raw materials；

The stabilized hydrogenation object DSH10 of the logistics DS10 refers to making the confession in logistics DS10 in stabilized hydrogenation process MR The hydrogen supply hydrocarbon that hydrogenation reaction is converted into hydrogen supply capacity enhancing occurs for the mistake hydrogen conversion product of hydrogen hydrocarbon.

The present invention, in general, the weight flow of the stabilized hydrogenation object DSH10 of logistics DS10 or logistics DS10, is that up flow type adds Hydrogen modifies 0.05~50 times of the outer weight flow for hydrogen supply hydrocarbon DSF of reaction process RX.

The present invention, generally, the weight flow of the stabilized hydrogenation object DSH10 of logistics DS10 or logistics DS10, are that up flow type adds Hydrogen modifies 0.10~10 times of the outer weight flow for hydrogen supply hydrocarbon DSF of reaction process RX.

The present invention, in general, the weight flow of the stabilized hydrogenation object DSH10 of logistics DS10 or logistics DS10, is that up flow type adds Hydrogen modifies 0.50~5 times of the outer weight flow for hydrogen supply hydrocarbon DSF of reaction process RX.

The present invention, in general, hydrocarbon HDS inferior, mainly the hydrocarbon component by normal boiling point higher than 500 DEG C is formed.

The present invention, in general, hydrocarbon HDS inferior, may contain solid.

The present invention, in general, hydrocarbon HDS inferior, mainly the hydrocarbon component by normal boiling point higher than 530 DEG C is formed, and contains solid.

The present invention, in general, hydrocarbon HDS inferior, mainly the hydrocarbon component by normal boiling point higher than 500 DEG C forms and contains solid, It is the logistics obtained from the separation process of the reaction product of residual oil up flow type heat from hydrogenation cracking reaction process.

The present invention, in general, hydrocarbon HDS inferior, mainly the hydrocarbon component by normal boiling point higher than 500 DEG C forms and contains solid, It is the logistics obtained from the fractional distillation process of the generation oil of residual oil up flow type heat from hydrogenation cracking reaction process.

The present invention, in general, hydrocarbon HDS inferior, mainly the hydrocarbon component by normal boiling point higher than 500 DEG C forms and contains solid sulfur It changes molybdenum, is obtained from the fractional distillation process of the generation oil of the residual oil up flow type heat from hydrogenation cracking reaction process using dispersed molybdenum catalyst The logistics arrived.

The present invention, in order to be used in series hydrogen supply dissolvent, common operation mode is:

The stabilized hydrogenation object DSH10 of the logistics DS10 refers to making the confession in logistics DS10 in stabilized hydrogenation process MR The hydrogen supply hydrocarbon that hydrogenation reaction is converted into hydrogen supply capacity enhancing occurs for the mistake hydrogen conversion product of hydrogen hydrocarbon；

In the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F, simultaneously can there are hydrogen, conventional liq hydrocarbon Under the conditions of the mixed phase material that can have solid particle, the hydrocarbon material R10F of at least part carries out hydrogenation reaction R10-R generation at least A part of heat from hydrogenation cracking reaction is converted into hydrogenation reaction product R10-P；Reaction process R10 may be received other containing hydrogen supply The material of hydrocarbon or the solvent hydrocarbon ADSC of hydrogen supply hydrocarbon precursor；

In the following process process RX-P-P100 of hydrogenation reaction product RX-P, obtain at least part based on gas S10-V To stabilized hydrogenation the object DSH2O, at least part logistics DS20 or logistics of the logistics DS20 or logistics DS20 of the ADSC of hydrocarbon containing solvent The stabilized hydrogenation object DSH2O of DS20 passes through at least partly reaction process of reaction process R10, adds hydrogen to turn with hydrocarbon material R10F or its Compound contact.

In group technology of the invention, in general, making in the following process process RX-P-P100 of hydrogenation reaction product RX-P At least part obtains the stabilized hydrogenation object DSH2O of the logistics DS20 or logistics DS20 of the ADSC of hydrocarbon containing solvent based on gas S10-V, The stabilized hydrogenation object DSH2O of at least part logistics DS20 or logistics DS20 was at least partly reacted by reaction process R10's Journey contacts, working method with hydrocarbon material R10F or its hydro-conversion object, can a kind or several in following:

1. gas or its stabilized hydrogenation of at least part based on the obtained ADSC component of hydrocarbon containing solvent of gas S10-V produce Object passes through at least partly reaction process of reaction process R10；

2. at least part the possibility based on the obtained ADSC component of hydrocarbon containing solvent of gas S10-V containing the liquid of solid or its Stabilized hydrogenation product passes through at least partly reaction process of reaction process R10；

3. possibility gas-liquid mixed phase containing solid of at least part based on the obtained ADSC component of hydrocarbon containing solvent of gas S10-V Material or its stabilized hydrogenation product, pass through at least partly reaction process of reaction process R10.

Group technology of the invention, in general, in the following process process RX-P-P100 of hydrogenation reaction product RX-P, make to Few a part obtains the stabilized hydrogenation object DSH2O of the logistics DS20 or logistics DS20 of the ADSC of hydrocarbon containing solvent based on gas S10-V, until The stabilized hydrogenation object DSH2O of few a part of logistics DS20 or logistics DS20 passes through at least partly reaction process of reaction process R10, It is contacted with hydrocarbon material R10F or its hydro-conversion object, working method, it can a kind or several in following:

1. at least part gas S10-V or its stabilized hydrogenation product, pass through at least partly reacting for reaction process R10 Journey；

2. the possibility for the ADSC component of hydrocarbon containing solvent that separation gas S10-V is obtained is produced containing the liquid of solid or its stabilized hydrogenation Object passes through at least partly reaction process of reaction process R10；

3. gas-liquid mixed phase material of the possibility of the ADSC component of hydrocarbon containing solvent that separation gas S10-V is obtained containing solid or its add Stabilized hydrogen product passes through at least partly reaction process of reaction process R10.

Group technology of the invention, in general, making liquid in the following process process RX-P-P100 of hydrogenation reaction product RX-P At least part normal boiling point in body S10-L is anti-by the cracking of up flow type heat from hydrogenation higher than 500 DEG C of the hydrocarbon component S10-L-VRC At least partly reaction process for answering process R10 is contacted with hydrocarbon material R10F or its hydro-conversion object.

Group technology of the invention, in general, making liquid in the following process process RX-P-P100 of hydrogenation reaction product RX-P At least part normal boiling point in body S10-L is anti-by the cracking of up flow type heat from hydrogenation higher than 500 DEG C of the hydrocarbon component S10-L-VRC At least partly reaction process for answering process R10 contacts, working method, Ke Yixuan with hydrocarbon material R10F or its hydro-conversion object 1 kind or several in following:

1. at least part liquid S10-LS10-L passes through at least partly reaction process of reaction process R10；

2. at least part is based on the obtained the hydrocarbon component S10-L-VRC's containing normal boiling point higher than 500 DEG C of liquid S10-L The liquid that solid may be contained passes through at least partly reaction process of reaction process R10；

3. at least part is based on the obtained the hydrocarbon component S10-L-VRC's containing normal boiling point higher than 500 DEG C of liquid S10-L The gas-liquid mixed phase material that solid may be contained passes through at least partly reaction process of reaction process R10.

1. at least part liquid S10-L passes through at least partly reaction process of reaction process R10；

2. the possibility for the hydrocarbon component S10-L-VRC containing normal boiling point higher than 500 DEG C that separation liquid S10-L is obtained is containing solid Liquid, pass through at least partly reaction process of reaction process R10；

3. the possibility for the hydrocarbon component S10-L-VRC containing normal boiling point higher than 500 DEG C that separation liquid S10-L is obtained is containing solid Gas-liquid mixed phase material, pass through at least partly reaction process of reaction process R10.

Group technology of the invention, in general, the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F points are front Conversion zone R10A and rear portion conversion zone R10B；

In front conversion zone R10A, there are hydrogen, conventional liq hydrocarbon, there may be the mixed phase materials of solid particle simultaneously Under the conditions of, the hydrocarbon material R10F of at least part carries out hydrogenation reaction R10B-R and at least part heat from hydrogenation cracking reaction conversion occurs For hydrogenation reaction product R10A-P；Front conversion zone R10A may be received other molten containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor The material of agent hydrocarbon ADSC；

It is separated into separation process MTHS, front conversion zone product R10A-P molten containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor The gas MTHS-V and liquid MTHS-L of agent hydrocarbon ADSC, at least part gas MTHS-V are used as MTHS-VK, and not enter rear portion anti- Answer a section R10B；

In rear portion hydrogenation reaction section R10B, there are hydrogen, conventional liq hydrocarbon, there may be the mixed phases of solid particle simultaneously Under the conditions of material, at least part liquid MTHS-L carries out hydrogenation reaction R10B-R and at least part heat from hydrogenation cracking reaction occurs It is converted into hydrogenation reaction product R10B-P；Rear portion hydrogenation reaction section R10B, may the other hydrocarbon materials of joint processing.

Group technology of the invention obtains the material RLK or base of the ADSC of hydrocarbon containing solvent generally, based on gas MTHS-VK In the hydrogen-containing hydrocarbon stream RLKH that RLK hydrogenation process 2MR product 2MRP is obtained, returns to up flow type hydro-upgrading reaction process RX and participate in Reaction, contacts with hydrocarbon HDS inferior or its hydro-conversion object；Up flow type hydro-upgrading reaction process RX, may receive it is other containing The material of hydrogen supply hydrocarbon or the solvent hydrocarbon ADSC of hydrogen supply hydrocarbon precursor；

Hydrogenation process 2MR may receive the object of other solvent hydrocarbon ADSC containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor simultaneously Material；

Hydrogenation process 2MR may combine with stabilized hydrogenation process MR, partly or entirely share.

Group technology of the invention obtains the material RLK or base of the ADSC of hydrocarbon containing solvent generally, based on gas MTHS-VK In the hydrogen-containing hydrocarbon stream RLKH that RLK hydrogenation process 2MR product 2MRP is obtained, returns to front conversion zone R10A and participate in reaction, with carbon Hydrogen material R10F or the contact of its hydro-conversion object；Front conversion zone R10A may be received other containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon predecessor The material of the solvent hydrocarbon ADSC of object；

Group technology of the invention, in general, in the following process process RX-P-P100 of hydrogenation reaction product RX-P, work Mode, can a kind or several in following:

1. the material containing normal boiling point higher than 500 DEG C of the hydrocarbon component RX-P-VRC based on liquid S10-L, into reacting Journey R10A contacts participation reaction with hydrocarbon material R10F or its hydro-conversion object；

2. the material containing normal boiling point higher than 500 DEG C of the hydrocarbon component RX-P-VRC based on liquid S10-L, into separating Journey MTHS combines with front conversion zone product R10A-P carries out gas-liquid separation；

3. the material of the hydrocarbon component RX-P-VRC containing normal boiling point higher than 500 DEG C based on liquid S10-L, anti-into rear portion Section R10B is answered to participate in reaction；

4. the material of the hydrocarbon component RX-P-VRC containing normal boiling point higher than 500 DEG C based on liquid S10-L, with rear portion plus hydrogen The reaction product R10B-P of conversion zone R10B is mixed.

Group technology of the invention, hydrocarbon HDS inferior, can be final based on hydrocarbon HDS inferior and/or hydrocarbon material R10F plus The material for being higher than 520 DEG C of hydro carbons containing normal boiling point that hydrogen product obtains, may contain solid.

Group technology of the invention, hydrocarbon HDS inferior, can be final based on hydrocarbon HDS inferior and/or hydrocarbon material R10F plus What the separation process of hydrogen product obtained is mainly higher than the material that 520 DEG C of hydro carbons form by normal boiling point, may contain solid.

Group technology of the invention, hydrocarbon HDS inferior, can be final based on hydrocarbon HDS inferior and/or hydrocarbon material R10F plus What the separation process of hydrogen product obtained is mainly higher than the material that 500 DEG C of hydro carbons form by normal boiling point, may contain solid.

Group technology of the invention, hydrocarbon HDS inferior, can be final based on hydrocarbon HDS inferior and/or hydrocarbon material R10F plus What the separation process of hydrogen product obtained is mainly higher than the material that 480 DEG C of hydro carbons form by normal boiling point, may contain solid.

Hydrocarbon HDS inferior of the invention can be mainly made of the hydrocarbon component that normal boiling point is higher than 530 DEG C.

Hydrocarbon material R10F of the invention can be heavy oil and/or coal, and the heavy oil is mainly higher than 530 DEG C by normal boiling point The hydrocarbon component.

The present invention, in general, up flow type hydro-upgrading reaction process RX and may by up flow type heat from hydrogenation cracking it is anti- It answers in process R10, the overall hot tearing rate of the hydrocarbon component of the normal boiling point higher than 530 DEG C is 15~65 weight % in hydrocarbon HDS inferior.

The present invention, in general, up flow type hydro-upgrading reaction process RX and may by up flow type heat from hydrogenation cracking it is anti- It answers in process R10, the overall hot tearing rate of the hydrocarbon component of the normal boiling point higher than 530 DEG C is 20~75 weight % in hydrocarbon HDS inferior；

In up flow type heat from hydrogenation cracking reaction process R10, normal boiling point is higher than 530 DEG C of the hydrocarbon component in hydrocarbon material R10F Hot tearing rate be 50~85 weight %；

In the up flow type hydro-upgrading reaction process RX of up flow type heat from hydrogenation cracking reaction process R10 and possible combined application In, the overall hot tearing rate of the hydrocarbon component of the normal boiling point higher than 530 DEG C is 80~97 weight % in hydrocarbon HDS inferior.

The present invention, in general, up flow type hydro-upgrading reaction process RX and may by up flow type heat from hydrogenation cracking it is anti- It answers in process R10, the overall hot tearing rate of the hydrocarbon component of the normal boiling point higher than 530 DEG C is 40~60 weight % in hydrocarbon HDS inferior；

In up flow type heat from hydrogenation cracking reaction process R10, normal boiling point is higher than 530 DEG C of the hydrocarbon component in hydrocarbon material R10F Hot tearing rate be 60~78 weight %；

In the up flow type hydro-upgrading reaction process RX of up flow type heat from hydrogenation cracking reaction process R10 and possible combined application In, the overall hot tearing rate of the hydrocarbon component of the normal boiling point higher than 530 DEG C is 88~95 weight % in hydrocarbon HDS inferior.

The present invention, in general, the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F points are front conversion zone R10A With rear portion conversion zone R10B；

Normal boiling point is higher than 530 DEG C of the hydrocarbon component in hydrocarbon material R10F, up flow type heat from hydrogenation cracking reaction process R10's Hot tearing rate is 50~85 weight %；

Normal boiling point is higher than 530 DEG C of the hydrocarbon component in hydrocarbon material R10F, and in front, the hot tearing rate of conversion zone R10A is 30 ~50 weight %, at rear portion, the hot tearing rate of conversion zone R10B is 20~40 weight %.

The present invention, in general, the aromatic carbon rate of hydrogen-containing hydrocarbon stream RLKH is 0.4~0.6.

The present invention, hydrocarbon HDS inferior can a kind or several in following materials:

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

2. oil product logistics obtained by high temperature coal-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. oil product obtained by the distillate oil of direct hydrogenation liquefaction of coal process product or its hot procedure；Hot procedure is selected from Coking or catalytic cracking process or catalytic pyrolysis process or hydrogenation process；

4. oil product obtained by shale oil or its distillate or its hot procedure；Hot procedure is selected from coking or catalysis Cracking process or catalytic pyrolysis process or hydrogenation process；

5. oil product obtained by ethylene cracking tar or its hot procedure；Hot procedure is selected from coking or catalytic cracking Process or catalytic pyrolysis process or hydrogenation process；

6. oil product obtained by petroleum based heavy fuel oils or its hot procedure；Hot procedure is selected from coking or catalytic cracking Journey or catalytic pyrolysis process or hydrogenation process；

7. oil product hot procedure obtained by tar sand base weight oil or its hot procedure is selected from coking or catalytic cracking Process or catalytic pyrolysis process or hydrogenation process.

The present invention, in general, poor quality hydrocarbon HDS contains Hydrogenation catalyst granule solid.

The present invention, in general, front conversion zone product R10A-P is separated into containing hydrogen supply hydrocarbon or hydrogen supply in separation process MTHS The gas MTHS-V and liquid MTHS-L of the solvent hydrocarbon ADSC of hydrocarbon precursor, at least part gas MTHS-V are used as MTHS-VK Rear portion conversion zone R10B is not entered；

At least 40 weight % for the hydrocarbon component that the normal boiling point of front conversion zone product R10A-P is 230~400 DEG C enter Into gas MTHS-V.

The present invention is generally separated into separation process MTHS, front conversion zone product R10A-P containing hydrogen supply hydrocarbon or hydrogen supply The gas MTHS-V and liquid MTHS-L of the solvent hydrocarbon ADSC of hydrocarbon precursor, at least part gas MTHS-V are used as MTHS-VK Rear portion conversion zone R10B is not entered；

At least 70 weight % for the hydrocarbon component that the normal boiling point of front conversion zone product R10A-P is 230~400 DEG C enter Into gas MTHS-V.

The present invention, based on reaction process R10 product R10-P obtain containing normal boiling point be higher than 520 DEG C of hydro carbons material, Up flow type heat from hydrogenation cracking reaction process R10 can be entered and participate in reaction, contacted with hydrocarbon material R10F or its hydro-conversion object.

The present invention, based on reaction process R10 product R10-P obtain containing normal boiling point be higher than 520 DEG C of hydro carbons material, Front conversion zone R10A can be entered and participate in reaction, contacted with hydrocarbon material R10F or its hydro-conversion object.

The present invention, based on reaction process R10 product R10-P obtain containing normal boiling point be higher than 520 DEG C of hydro carbons material, Separation process MTHS can be entered and combine progress gas-liquid separation with front conversion zone product R10A-P.

The present invention, based on reaction process R10 product R10-P obtain containing normal boiling point be higher than 520 DEG C of hydro carbons material, Rear portion conversion zone R10B can be entered and participate in reaction.

The present invention, in general, up flow type hydro-upgrading reaction process RX, uses the upstream of 1 or 2 or more serial operation Formula reactor.

Front conversion zone R10A, uses the up-flow reactor of 1 or 2 or more serial operation；

Rear portion conversion zone R10B, uses the up-flow reactor of 1 or 2 or more serial operation.

The present invention, in general, hydrogen supply agent weight and hydrocarbon HDS inferior in up flow type hydro-upgrading reaction process RX, hydrocarbon HDS inferior The weight ratio of the hydrocarbon component of the middle normal boiling point higher than 530 DEG C is 0.3~3.0.

The weight of the hydrocarbon component of the normal boiling point higher than 530 DEG C in front conversion zone R10A, hydrogen supply agent weight and hydrocarbon material R10F The ratio between amount R10A-DSK is 0.07~2.0；

The weight of the hydrocarbon component of the normal boiling point higher than 530 DEG C in rear portion conversion zone R10B, hydrogen supply agent weight and hydrocarbon material R10F The ratio between amount R10B-DSK is 0.03~1.0, and R10B-DSK is lower than R10A-DSK at least 10%.

Invention, solvent hydrocarbon ADSC can be selected from a kind or several in following conventional boiling range:

1. the conventional liquid hydrocarbon that normal boiling point is 230~400 DEG C；

2. the conventional liquid hydrocarbon that normal boiling point is 230~350 DEG C；

3. the conventional liquid hydrocarbon that normal boiling point is 230~300 DEG C.

The up flow type heat from hydrogenation cracking reaction process R10 of group technology of the invention, hydrocarbon material R10F can be coal hydrogenation Direct liquefaction reaction process, a kind or several for being selected from during following process:

1. using the direct hydrogenation liquefaction of coal liquefaction process of hydrogen supply dissolvent oil；

2. not using the direct hydrogenation liquefaction of coal liquefaction process of hydrogen supply dissolvent oil；

3. kerosene refines process altogether；

4. coal faces hydrogen thermosol liquefaction process.

The present invention, up flow type heat from hydrogenation the cracking reaction process R10, the hydrogenator XR10E used of hydrocarbon material R10F Working method can a kind or several in following:

1. suspended-bed reactor, that is, paste state bed reactor；

2. fluidized bed reactor；

3. suspension bed and ebullated bed combination type reactor.

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

Option 2, reactor XR10E, forced circulation returns after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of reactor XR10E material inlet；

Option 3, reactor XR10E, forced circulation returns after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of reactor XR10E material inlet；

Option 4, reactor XR10E, forced circulation returns after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of reactor XR10E material inlet, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 5, reactor XR10E, forced circulation returns after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of reactor XR10E material inlet, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 6, reactor XR10E, forced circulation returns after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of reactor XR10E material inlet is collected simultaneously other collection liquids of cup discharge by other dedicated feedings Pump downstream transport liquid material product；

Option 7, reactor XR10E, forced circulation returns after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of reactor XR10E material inlet is collected simultaneously other collection liquids of cup discharge by other dedicated feedings Pump downstream transport liquid material product；

Option 8, reactor XR10E, top are arranged liquid collecting cup and liquid material product are discharged by dedicated feeding engine downstream transport Liquid material product is not provided with the fluidized bed reactor system of liquid material product forced circulation；

Option 9, reactor XR10E, top are arranged liquid collecting cup and liquid material product are discharged by dedicated feeding engine downstream transport Liquid material product is not provided with the suspended-bed reactor system of liquid material product forced circulation；

Option 10, reactor XR10E, 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 XR10E material inlet and the combination type reactor of ebullated bed；

Option 11, reactor XR10E, 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 XR10E 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 XR10E, 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 XR10E material inlet and the combination type reactor of ebullated bed are collected simultaneously other collection liquids of cup discharge By 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.

The present invention, hydrocarbon HDS inferior is in up flow type hydro-upgrading reaction process RX, the work of the hydrogenator XRXE used Mode can a kind or several in following:

1. suspended-bed reactor, that is, paste state bed reactor；

2. fluidized bed reactor；

3. suspension bed and ebullated bed combination type reactor.

Option 2, reactor XRXE, 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 XRXE material inlet；

Option 3, reactor XRXE, 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 XRXE material inlet；

Option 4, reactor XRXE, 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 XRXE material inlet is answered, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 5, reactor XRXE, 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 XRXE material inlet is answered, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 6, reactor XRXE, 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 XRXE material inlet, be collected simultaneously cup discharge other collection liquids by other dedicated feeding engines to Downstream conveys liquid material product；

Option 7, reactor XRXE, 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 XRXE material inlet, be collected simultaneously cup discharge other collection liquids by other dedicated feeding engines to Downstream conveys liquid material product；

Option 8, reactor XRXE, 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 XRXE, 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 XRXE, 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 XRXE material inlet and the combination type reactor of ebullated bed；

Option 11, reactor XRXE, 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 XRXE 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 XRXE, 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 XRXE 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；

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

The present invention, reaction process R10 can convey the liquid that the possibility containing heavy oil contains solid to hydrogenation process RX Body hydrocarbon material.

The operating condition of the present invention, the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F are usual are as follows: reaction temperature Degree is 400~480 DEG C, reactor pressure is 6~30MPa, and gas-liquid volume ratio is 100~1500Nm³/ t, catalyst loading are 0.001~5 mass % of heavy oil FD weight, co-catalyst additive amount are sulphur/catalyst activity metal mole in co-catalyst Than being 1.0~2.0, reaction time is 0.1~5 hour, the hydrogen supply hydrocarbon weight ratio in the charging of reaction process total hydrocarbon It is 0.07~0.50.

The operating condition of the present invention, the up flow type hydro-upgrading reaction process RX of hydrocarbon HDS inferior are usual are as follows: reaction temperature is 380~480 DEG C, reactor pressure be 6~30MPa, gas-liquid volume ratio be 100~1500Nm³/ t, reaction process total hydrocarbon into Hydrogen supply hydrocarbon weight ratio in material is 0.20~0.80.

The present invention, in general, separating the final hydrogenation products of the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F And/or the final hydrogenation products of hydrocarbon HDS up flow type hydro-upgrading reaction process RX inferior obtain mainly being higher than 530 by normal boiling point DEG C the possibility of the hydrocarbon component composition contain the outer of solid particle and get rid of residual oil ZVR；

Coking reaction process R90 can be removed by getting rid of residual oil ZVR outside, be converted into coke, coking generates oil, cooking gas；

In general, getting rid of residual oil ZVR whereabouts pyrogenetic reaction process R90 outside, one of the following or several can be selected from:

1. as coking raw material devulcanization coking；

2. going delayed coking to process as blending raw material；

3. going coal coking process to process as blending raw material；

The coke that the coal gas that pyrogenetic reaction process R90 is generated is generated as hydrogen feedstock hydrogen making, pyrogenetic reaction process R90 The distillate of oil or tar enters the upper of the up flow type heat from hydrogenation cracking reaction process R10 and/or hydrocarbon HDS inferior of hydrocarbon material R10F Streaming hydro-upgrading reaction process RX joint processing, to constitute big group of a kind of process of coking and heavy-oil hydrogenation thermal cracking process It closes；

Get rid of oil containing solid slag as coal coking process ingredient outside in use, as room temperature solid containing solid slag oil individually crushing after It is used as coking raw material or room temperature with coking coal blending and is used as refining to crush together after oil containing solid slag and the coking coal blending of solid Burnt raw material.

The present invention, in general, the richness that heavy oil catalytic cracking reaction process or heavy-oil catalytic thermal cracking reaction process can be generated The wax slop that hydrocarbon ils and/or hydrocarbon material up flow type heat from hydrogenation cracking process containing 2~4 ring structure aromatic hydrocarbons generate oil is modified as hydrogen supply Solvent uses, and the up flow type into the up flow type heat from hydrogenation cracking reaction process R10 and/or hydrocarbon HDS inferior of hydrocarbon material R10F adds hydrogen Modify reaction process RX；

Separate the final hydrogenation products and/or hydrocarbon inferior of the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F The final hydrogenation products of HDS up flow type hydro-upgrading reaction process RX obtain mainly being higher than by normal boiling point 530 DEG C of the hydrocarbon component The possibility of composition contains the outer of solid particle and gets rid of residual oil ZVR, goes coking reaction process R90 to process as coking raw material.

The present invention, in general, hydrocarbon material R10F is mainly to be higher than the heavy oil that 500 DEG C of hydro carbons form, carbon residue by normal boiling point Value is 15~35%.

The present invention, in general, poor quality hydrocarbon HDS is mainly to be higher than the heavy oil that 500 DEG C of hydro carbons form, carbon residue by normal boiling point It is 20~60%.

Liquid collecting cup is arranged in last reactor KRE100 inner top of front conversion zone R10A, makes KRE100 reaction product It is separated into collection liquid KRE100-L and gas-liquid mixed phase material KRE100-M, it is anti-that at least part collection liquid KRE100-L enters rear portion A section R10B is answered to be reacted, at least one of the obstructed portion conversion zone R10B later of at least part gas-liquid mixed phase material KRE100-M Divide reaction process, shortens residence time of the gas phase in mixed phase material KRE100-M in the conversion zone R10B of rear portion；

In rear portion hydrogenation reaction section R10B, there are hydrogen, conventional liq hydrocarbon, there may be the mixed phases of solid particle simultaneously Under the conditions of material, at least part collection liquid KRE100-L carries out hydrogenation reaction R10B-R and at least part heat from hydrogenation cracking occurs Reaction is converted into hydrogenation reaction product R10B-P；Rear portion hydrogenation reaction section R10B, may the other hydrocarbon materials of joint processing.

The present invention makes in general, liquid collecting cup is arranged in last reactor KRE100 inner top of front conversion zone R10A KRE100 reaction product is separated into collection liquid KRE100-L and gas-liquid mixed phase material KRE100-M, at least part collection liquid KRE100- enters rear portion conversion zone R10B and is reacted, and at least part gas-liquid mixed phase material KRE100-M is obstructed, and portion later is anti- At least part reaction process of section R10B is answered, shortens the gas phase in mixed phase material KRE100-M in the conversion zone R10B of rear portion Residence time；

In rear portion hydrogenation reaction section R10B, setting collection at the top of the reactor KRE200 of gas-liquid mixed phase material KRE100-M is received Liquid cup, forced circulation returns to upstream reaction space KK and makes upstream reaction space KK product after so that collection liquid is pressurizeed by circulating pump Liquid collecting cupule at the top of reactor KRE200 is flowed through, so that at least part liquid material in gas-liquid mixed phase material KRE100-M is made For collection liquid by the gas in gas-liquid mixed phase material KRE100-M can not by reaction compartment.

The present invention makes in general, liquid collecting cup is arranged in last reactor KRE100 inner top of front conversion zone R10A KRE100 reaction product is separated into collection liquid KRE100-L and gas-liquid mixed phase material KRE100-M, is more than reactor KRE100 net liquid The collection liquid KRE100-L of body product 50% enters rear portion conversion zone R10B and is reacted, and gas-liquid mixed phase material KRE100-M is obstructed Later at least part reaction process of portion's conversion zone R10B shortens the gas phase in mixed phase material KRE100-M in rear portion conversion zone Residence time in R10B；

In rear portion hydrogenation reaction section R10B, setting collection at the top of the reactor KRE200 of gas-liquid mixed phase material KRE100-M is received Liquid cup, forced circulation returns to upstream reaction space after so that at least the 50% of whole liquid materials is pressurizeed as collection liquid by circulating pump KK simultaneously makes liquid collecting cupule at the top of the reacted device KRE200 of upstream reaction space KK product stream, so that gas-liquid mixed phase material At least part liquid material in KRE100-M can not pass through as collection liquid by the gas in gas-liquid mixed phase material KRE100-M Reaction compartment.

The present invention makes in general, liquid collecting cup is arranged in last reactor KRE100 inner top of front conversion zone R10A KRE100 reaction product is separated into collection liquid KRE100-L and gas-liquid mixed phase material KRE100-M, is more than reactor KRE100 net liquid The collection liquid KRE100-L of body product 70% enters rear portion conversion zone R10B and is reacted, and gas-liquid mixed phase material KRE100-M is obstructed Later at least part reaction process of portion's conversion zone R10B shortens the gas phase in mixed phase material KRE100-M in rear portion conversion zone Residence time in R10B；

In rear portion hydrogenation reaction section R10B, setting collection at the top of the reactor KRE200 of gas-liquid mixed phase material KRE100-M is received Liquid cup, forced circulation returns to upstream reaction space after so that at least the 66% of whole liquid materials is pressurizeed as collection liquid by circulating pump KK simultaneously makes liquid collecting cupule at the top of the reacted device KRE200 of upstream reaction space KK product stream, so that gas-liquid mixed phase material At least part liquid material in KRE100-M can not pass through as collection liquid by the gas in gas-liquid mixed phase material KRE100-M Reaction compartment.

The reaction process of last reactor of separation process MTHS and front conversion zone R10A can be combined at one It is completed in equipment；

Specific embodiment

The present invention described in detail below.

Pressure of the present invention, refers to absolute pressure.

Normal boiling point of the present invention refers to vapour of the substance under an atmospheric pressure, liquid equilibrium temperature.

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

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

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

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

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

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

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

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

Diesel component of the present invention refers to that normal boiling point is 200~350 DEG C of hydro carbons.

Wax oil component of the present invention refers to that normal boiling point is 350~530 DEG C of hydro carbons.

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

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

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

Hydrogenation reaction space refers to the fluid circulation space that the hydrogenation reaction occurs, and can be the interior space of reaction such as Empty barrel reactor area, air lift hydrogen mixed zone, liquid collection cups upper space region etc., can be the reactor external space such as pipeline Space in interior space, 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.

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. 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 The enough work for crossing hydrogen supply the hydrocarbon component DS transmitting more 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 is to refer at this It leads and proposes under thought.

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, the process for losing hydrogen solvent is being converted into, equably to the free radical in liquid phase reactor space Reactive hydrogen is quickly provided, there is hydrogen supply capacity, have the function of hydrogen supply agent, coking inhibitor；

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

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

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

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

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

1. the reaction process time can be shortened, catalyst efficiency is improved；

2. 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；

3. reaction overall temperature rise can be reduced；

4. operational stability can be improved, extend the operation cycle；

5. 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 It is grasped under the reaction condition that MR-CAT volume space velocity is 0.05~10.0hr-1, hydrogen/feedstock oil volume ratio is 300: 1~3000: 1 Make.

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

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: 1~1200: 1.

The aromatic hydrogenation fractional saturation that the hydroconversion reaction zone MR of the present invention for being prepared as target with hydrogen supply hydrocarbon occurs is anti- It answers, refers to 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 the same as often greater than greater than 6 weight %, generally higher than 10 weight %.

The hydroconversion reaction zone MR that target is prepared as with hydrogen supply hydrocarbon, because (tenor, oxygen content contain feedstock property Amount, olefin(e) centent, sulfur content, nitrogen content, arene content, boiling range, specific gravity) difference and hydrogenation reaction (hydrogenation deoxidation plus hydrogen 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..

In the up flow type heat from hydrogenation cracking reaction of the up flow type hydrogenation process RX, hydrocarbon material R10F of hydrocarbon HDS inferior Journey R10 uses hydrogen supply dissolvent, can quickly eliminate free radical, can be improved hot cracked product hydrogen content, but therefore can also inhibit Heat cracking reaction reduces thermal cracking conversion ratio；And the up flow type hydrogenation process RX of hydrocarbon HDS inferior, hydrocarbon material R10F's is upper The raising of the residual oil quality of streaming heat from hydrogenation cracking reaction process R10 allows its further heat from hydrogenation cracking (such as circulation plus hydrogen Thermal cracking) to improve overall thermal cracking conversion ratio.With regard to the hot again of thermal cracking tail oil of thermal cracking of heavy oil and heavy oil For the general effect of cracking, overall heat from hydrogenation cracking conversion rate can effectively improve using hydrogen supply dissolvent, outer get rid of is effectively reduced Yield containing solid tail oil, to improve the economy of process.

The up flow type hydrogenation process RX of hydrocarbon HDS inferior of the invention described in detail below.

Poor quality hydrocarbon HDS of the present invention, usually heavy hydrocarbon inferior, common to be meant that: not use hydrogen supply dissolvent condition Under, in other operating conditions (reaction pressure, reaction temperature, catalyst composition and additive amount and amount, residence time, hydrogen oil Volume ratio, way of operation) under the same conditions, coking tendency of the hydrocarbon HDS inferior during heat from hydrogenation cracking reaction, Coking tendency of the heavy oil R10FL for including than hydrocarbon material R10F during heat from hydrogenation cracking reaction is more serious, i.e., coking yield is more High and/or heat from hydrogenation cracking conversion rate is lower；In general, the normal boiling point in hydrocarbon HDS inferior is higher than the carbon residue ratio of 530 DEG C of hydro carbons The carbon residue that normal boiling point in hydrocarbon material R10F is higher than 530 DEG C of hydro carbons is higher.

The up flow type hydrogenation process RX of poor quality hydrocarbon HDS of the present invention, main target are, with conventional heat from hydrogenation Cracking reaction process is compared, and under catalyst and hydrogen supply dissolvent existence condition, makes hydrocarbon HDS inferior that more plus hydrogen occur first full With reaction and the reaction of sufficient thermal cracking free radical stabilized hydrogenation, so that the carbon residue of hydrocarbon HDS inferior be effectively reduced, make therein Normal boiling point higher than 530 DEG C hydro carbons become appropriate heat from hydrogenation cracking severity heat from hydrogenation cracking reaction process raw material.

In group technology of the invention, the first of the up flow type hydrogenation process RX of poor quality hydrocarbon HDS of the present invention Reaction task 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, while hydrofining reaction can occur (including demetalization plus hydrogen hydrogenolysis, olefins hydrogenation reaction plus hydrogen is de- Impurity (oxygen, sulphur, nitrogen) reaction plus hydrogen aromatic hydrocarbons saturation or fractional saturation reaction, removal of ccr by hydrotreating reaction) and/or be hydrocracked anti- It answers.The typical feedstock of the up flow type hydrogenation process RX of hydrocarbon HDS inferior is exactly the up flow type heat from hydrogenation cracking of hydrocarbon material R10F Tail oil component in reaction process R10, in general, in the tower bottom residual oil that it is enriched in vacuum fractionation tower in product fractionation process, this Kind residual oil R10-HO usually contains catalyst conversion product such as molybdenum sulfide of addition etc., the R10 product metal sulphur from heavy oil R10FL Compound, the coke that may be accumulated.

When hydrocarbon HDS inferior includes in the up flow type heat from hydrogenation cracking reaction process R10 product R10-P from hydrocarbon material R10F Normal boiling point when being higher than 530 DEG C of hydro carbons R10-VR, the carbon residue content of part heavy oil R10-VR is usually above liquid material R10FL, the liquid phase in hydrocarbon material up flow type heat from hydrogenation cracking reaction process R10 is adapted as adding for hydrocarbon HDS inferior in other words Hydrogen thermal cracking solution, therefore, the present invention draw the heavy hydrocarbon in the up flow type hydrogenation process RX reaction product of hydrocarbon HDS inferior The second half section for entering the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F carries out appropriate heat from hydrogenation cracking reaction, can be with The thermal cracking depth for controlling hydro carbons poor quality hydrocarbon HDS simultaneously, prevents excessively high hot tearing rate from leading to thermal condensation object such as asphalitine Yield is more than the generation for limiting the quantity and causing second liquid phase (pitch phase).

In the up flow type hydrogenation process RX of hydrocarbon HDS inferior, when reactive hydrogen is supplied not in time, colloid, pitch Condensation reaction will occur for the thermal cracking free radical of matter, production molecular weight bigger molecule or structure group, repeatedly dehydrogenation with The final result of condensation reaction is to generate coke, and certainly, this is the negative reaction for needing inhibition or reduction.

The reactor types of the up flow type hydrogenation process RX of poor quality hydrocarbon HDS of the present invention, can be any appropriate Form, can be one of combination cot reactor of fluidized bed reactor, suspended-bed reactor, ebullated bed and suspension bed or Several combinations.

The up flow type hydrogenation process RX of poor quality hydrocarbon HDS of the present invention, the reactor used can be 1 or 2 Or more, reactor working method can be any suitable form, usually up flow type expanded bed reactor or carrying liqs product The up flow type expanded bed reactor of circulation, the W-response area of separate unit up flow type expanded bed reactor, may be considered that and be divided into 2 A 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 with It is the temperature and/or flow for adjusting hydrogen, can be the temperature and/or flow for adjusting oil product.

The up flow type hydrogenation process RX of hydrocarbon HDS inferior, the reactor used, liquid phase in reaction compartment, gas phase (or Vapour phase) volume ratio, can be with liquid phase the case where being main, define " the liquid phase actual volume/(liquid phase is real in reaction compartment Border volume+gas phase actual volume) " be reaction compartment liquid phase fraction KL, a point rate KL is typically larger than 0.5, generally higher than 0.65, 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 The different height of reactor position 2 times or repeatedly add hydrogen.

It, can be former by a part of liquid in order to adjust reaction feed property, or in order to control reaction process property of liquid phase Expect that R10FL introduces the up flow type hydrogenation process RX of hydrocarbon HDS inferior.

It, can be by hydrocarbon material R10F's in order to adjust reaction feed property, or in order to control reaction process property of liquid phase A part of product liquid of the intermediate liquid product such as front conversion zone of up flow type heat from hydrogenation cracking reaction process R10 introduces bad The up flow type hydrogenation process RX of matter hydrocarbon HDS, especially when the up flow type hydrogenation process RX reaction product of hydrocarbon HDS inferior Heavy oil component in RX-P is introduced directly into the rear portion conversion zone of the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F R10B and when being processed without front conversion zone R10A.

The residue fraction in up flow type heat from hydrogenation cracked reaction product R10-P in order to shorten hydrocarbon material R10F enters poor quality The path of the up flow type hydrogenation process RX of hydrocarbon HDS, when the distillate (normal boiling point that the liquid phase of reaction product R10-P contains Hydro carbons lower than 530 DEG C) be rich in hydrogen supply agent or precursor of hydrogen donor when, can be directly by the liquid phase of part reaction product R10-P The up flow type hydrogenation process RX for introducing hydrocarbon HDS inferior, at this point, foring the short circulation loop of tail oil high pressure；Work as reaction product The distillate (normal boiling point is lower than 530 DEG C of hydro carbons) that the liquid phase of R10-P contains only contains a small amount of hydrogen supply agent or hydrogen supply agent predecessor When object, it usually needs obtain the mixing of residual oil or residual oil and wax slop in the oily separation and recovery system of the generation of reaction product R10-P Oil introduces up flow type hydrogenation process RX as heavy hydrocarbon inferior, at this point, foring conventional tail oil long circulating circuit.

Hydrogen supply in the up flow type hydrogenation process RX reaction product RX-P of hydrocarbon HDS inferior of the invention described in detail below The whereabouts of solvent composition, heavy oil component.

Crucial purpose of the invention is to reuse hydrogen supply dissolvent component in reaction product RX-P (to be recycled, series connection follows Ring use), and make the heavy oil component in reaction product RX-P in the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F (rear portion conversion zone) carries out Unionfining thermal cracking, and working method can be any suitable form, and the present invention lists some normal Use scheme.

The up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F of the invention described in detail below.

The heavy oil that the up flow type heat from hydrogenation cracking reaction process R10 of the hydrocarbon material R10F of the present invention, which is described below, can be carried out adds Hydrogen heat cracking reaction process.

The hydrocarbon of the raw material heavy oil R10FL of the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F of the present invention 470 DEG C of the usual > of the normal boiling point of class, 500 DEG C of general >, particularly 530 DEG C of >；The upstream of hydrocarbon material R10F of the present invention Formula heat from hydrogenation cracking reaction process R10, heat cracking reaction, the thermal cracking free radical that at least part heavy oil R10FL occurs add hydrogen Stablize reaction, generates the lower hydrocarbon product of at least part boiling point；Heavy oil up flow type heat from hydrogenation cracking reaction process R10 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 R10-P, and outer in order to reduce Arrange tail oil quantity, it is often necessary to the heat from hydrogenation cracking reaction process such as RX of tail oil is set, and in order to simplify overall procedure, reduce The up flow type heat from hydrogenation cracking reaction process R10 of RX and hydrocarbon material R10F is usually formed group technology by investment and energy consumption.

Although the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F 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 heat from hydrogenation cracking reaction of hydrocarbon material R10F Journey R10 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 heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F, also necessarily to occur Some hydrofining reactions.

In the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F, when reactive hydrogen is supplied not in time, glue Matter, asphalitine thermal cracking free radical will occur condensation reaction, production molecular weight bigger molecule or structure group, repeatedly The final result of 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 heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F, is used Reactor can be 1 or 2 or more, and usually used reactor is 2~4；The up flow type heat from hydrogenation of hydrocarbon material R10F The reactor working method of cracking reaction process R10 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 heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F, 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 R10B of the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F combines processing When heavy oil component RX-PVR in the reaction product RX-P of the up flow type hydrogenation process RX of hydrocarbon HDS inferior, the second half reaction The residence time of process R10B usually meets the requirement of the heat from hydrogenation cracking rate of control heavy oil component RX-PVR first, is usually arranged The heat from hydrogenation cracking rate upper limit of heavy oil component RX-PVR is to prevent conversion per pass excessively high.

The reactor types of heavy oil up flow type heat from hydrogenation cracking reaction process R10 of the present invention, can be any appropriate Form, there are many known form, for example upflow fixed bed reactor, up flow type slight expanded-bed reactor, up flow type move Dynamic bed reactor, up flow type replace bed reactor, fluidized bed reactor, suspended-bed reactor, ebullated bed and suspension bed online The combination of combination cot reactor and its particular form, and it is most of have industrial application case, form relatively fixed technology Feature.

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 altogether process generate a large amount of polar impurity such as H2O, NH3, CO, CO2 can be strongly adsorbed in catalyst surface and form shadowing effect, therefore international well-known oil product technology suppliers CHEVRON Company is arranged the scheme of the timely impurity removal gas of gas-liquid separator and in subsequent floating bed hydrogenation between proposing in the reactor The lower part of reactor introduces high-purity hydrogen, but 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 direct liquid of coal hydrogenation that the hydrocarbon material up flow type heat from hydrogenation cracking reaction process R10 of the present invention can be carried out is described below Change process.

Direct hydrogenation liquefaction of coal process of the present invention, refers under solvent naphtha existence condition by adding hydrogen to make coal hydrogenation The method of direct liquefaction, according to the difference of solvent naphtha and catalyst, pyrolysis way and the difference and process conditions that add hydrogen mode Difference, following several techniques can be divided into:

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 1 and II (SRC-1 and SRC-II), Exxon donor solvent process EDS, Japanese New Energy Development Organization liquefaction process (NEDOL) etc., using hydrogen, but pressure is less high, and solvent naphtha has apparent work With；

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

4. coal and residual oil joint processing method (COprocessing): 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, and the outer oil extraction or direct hydrogenation liquefaction of coal that it is generated are oily, and (usually coal hydrogenation is straight Connect liquefaction light oil) or direct hydrogenation liquefaction of coal oil modified oil, as long as its composition has raw material compositing characteristic of the present invention, To use the method for the present invention to be processed.

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 direct hydrogenation liquefaction of coal reaction process and direct hydrogenation liquefaction of coal oil hydrogenation modification process totally two A process.In order to improve the conversion ratio of coal direct liquefaction and realize that coal feedstock enters direct hydrogenation liquefaction of coal reactor, coal Charcoal is usually made coal dust before entering direct hydrogenation liquefaction of coal reactor, is made into oily coal with the solvent naphtha for having good hydrogen supply capacity Slurry, coal is pressurized, enters direct hydrogenation liquefaction of coal reactor after heating.

Direct hydrogenation liquefaction of coal reaction process of the present invention is referred to coal and molecule hydrogen that may be present as original Material is hydrogen supply dissolvent oil with specific oil product (the usually hydrogenation modification oil of direct hydrogenation liquefaction of coal oil), in certain operation Condition (such as operation temperature, operating pressure, solvent naphtha/coal weight ratio, hydrogen/solvent naphtha volume ratio and suitable hydrogenation catalyst) Under, the reaction process of carbon-carbon bond thermal cracking plus hydrogen direct liquefaction directly occurs for coal.

Direct hydrogenation liquefaction of coal oil of the present invention, refers to the oil that the direct hydrogenation liquefaction of coal reaction process generates Product, it is present in direct hydrogenation liquefaction of coal reaction effluent, is based on hydrogen supply dissolvent oil, reaction consumption coal and reaction transfer The combined reaction product of hydrogen.

After direct hydrogenation liquefaction of coal reaction process works well, it is anti-that hydrogen supply dissolvent oil generallys use direct hydrogenation liquefaction of coal The hydrogenation modification oil for the direct hydrogenation liquefaction of coal oil (usually conventional distillate of the boiling range higher than 165 DEG C) for answering process self-produced, coal The main target for adding hydrogen direct liquefaction oil hydrogenation modification process is production direct hydrogenation liquefaction of coal reaction process solvent naphtha, specifically For be exactly improve in oil product " with good hydrogen supply function component " content, such as improve naphthenic base benzene class, bicyclic alkyl The content of benzene class component, the fact that a large amount of double ring arenes and a large amount of thrcylic aromatic hydrocarbons are contained based on direct hydrogenation liquefaction of coal oil, coal Adding hydrogen direct liquefaction oil hydrogenation modification process is the hydrogenation process of one " appropriate aromatic hydrocarbons saturation ".

The final goal of direct hydrogenation liquefaction of coal reaction process is the outer oil product supplied of production, usual direct hydrogenation liquefaction of coal oil The hydrogenation modification oil that hydrogenation modification process generates is two parts: a part is used as direct hydrogenation liquefaction of coal reaction process hydrogen supply Solvent naphtha, a part are used as the outer oil extraction of direct hydrogenation liquefaction of coal liquefaction process.In general, direct hydrogenation liquefaction of coal reaction process generates At least part direct hydrogenation liquefaction of coal light oil be used as the outer oil extraction A of coal oil process, remaining direct hydrogenation liquefaction of coal oil is used Make direct hydrogenation liquefaction of coal oil hydrogenation modification process feedstock oil production direct hydrogenation liquefaction of coal reaction process hydrogen supply dissolvent oil and There is the outer oil extraction of A and B two-way in outer oil extraction B, the final whereabouts of the outer oil extraction of A and B two-way is mentioned by deep hydrogenation at this time Matter process produces high-quality oil product such as diesel oil distillate, naphtha cut.

Up to the present, a variety of direct hydrogenation liquefaction of coal techniques have been had already appeared, wherein the set direct liquid of modern age coal hydrogenation The typical process changing advanced technologies feature and being innovated, is applied in a set of of Chinese Shenhua Erdos coal oil branch company Chinese Shenhua direct hydrogenation liquefaction of coal technique on commercialized 1,000,000 tons/year of direct hydrogenation liquefaction of coal devices, it was in 2009 It goes into operation, continuously the normal production run period alreadys exceed 8000 hours longest single.

Chinese Shenhua Erdos coal oil branch company possesses the unique a set of commercialized 1,000,000 tons/year of coals in the world and adds Hydrogen direct liquefaction device, the direct hydrogenation liquefaction of coal project include direct hydrogenation liquefaction of coal reaction process RU, hydrogen supply dissolvent oil Stabilized hydrogenation process, stabilized hydrogenation distillate plus hydrogen grading process, a document for recording this kind of data is shown in: 1. publishing name Claim: " coal direct liquefaction technique and engineering "；2. retrieval is encoded with books: ISBN coding: 9-78703-04308-23；3. compiling It writes: Wu Xiuzhang, Shu Geping, Li Kejian, Xie Shunmin；4. publishing house: Science Press.

Chinese Shenhua Erdos coal oil branch company possesses the unique a set of commercialized 1,000,000 tons/year of coals in the world and adds The agent coal weight ratio of hydrogen direct liquefaction device, coal slurry is about hydrogen supply dissolvent: coal dust=54.95: 45.05；Its coal slurry suspension bed 2 coal floating bed hydrogenation reactors are arranged in hydrogenation reaction system, and every coal floating bed hydrogenation reactor uses one Returning in the Reactor inlet raw material containing solid-liquid stream for the high concentration of reactor outlet product is formed liquid by platform coal circulating pump Stream circulation prevents solid in reactor from depositing to control liquid flowing speed in reactor, while reactor outlet logistics being carried Reaction heat is brought into the feed stream of Reactor inlet and heats it, and medium is that the gas, liquid, solid three-phase complexity containing a small amount of gas is situated between Matter system, and cross flow medium and also persistently carry out heat from hydrogenation cracking reaction in pump housing runner.The production practices of many years show Under the operating conditions such as the efficient direct hydrogenation liquefaction of coal catalyst that it is used, the coal hydrogenation of the coal of the agent coal weight ratio is straight It is sufficient, superfluous for connecing the quantity of the hydrogen supply dissolvent during liquefaction reaction, because continuous normal production operation 8000 hours Long-cycle production stop work after find, the deposit on distribution plate, liquid collecting cup, wall in reactor be not coking deposit and It is granular deposit.That is, the device is successfully long in device by the control of thermal condensation coking reaction using hydrogen supply dissolvent In the range of period run license.The successful commercialization of 1,000,000 tons/year of direct hydrogenation liquefaction of coal devices of Shenhua, mark person are modern The success of large-scale floating bed hydrogenation technology.

For direct hydrogenation liquefaction of coal reaction process, in order to reduce liquefying reactor rear portion system corrosion, Ke Nengxu Sodium carbonate is injected, into final reacting product to neutralize corrosive component such as hydrogen chloride, hydrogen fluoride, hydrogen sulfide etc., Jiang Qiyin Ion is fixed.

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

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

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

1. floating bed hydrogenation reactor；

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

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

4. slight expanded-bed.

Characteristic of the invention described in detail below.

The present invention, in general, hydrocarbon HDS inferior, may contain solid.

3. kerosene refines process altogether；

4. coal faces hydrogen thermosol liquefaction process.

1. suspended-bed reactor, that is, paste state bed reactor；

2. fluidized bed reactor；

3. suspension bed and ebullated bed combination type reactor.

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

1. suspended-bed reactor, that is, paste state bed reactor；

2. fluidized bed reactor；

3. suspension bed and ebullated bed combination type reactor.

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

1. as coking raw material devulcanization coking；

2. going delayed coking to process as blending raw material；

3. going coal coking process to process as blending raw material；

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

For direct hydrogenation liquefaction of coal reaction process RU, because of conventional gas hydrocarbon, CO, CO₂Yield is huge, usually most of Cold high score gas of the cold high score gas than such as from about 70~100%, after being purified as membrane separation process obtained by permeated hydrogen pressurization after return Hydrogenation process does not permeate gas by PSA and mentions hydrogen or pressurization return plus hydrogen after " steam reforming hydrogen manufacturing+PSA mentions hydrogen " Reaction process is recycled.

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.

Claims

1. the hydrogen supply dissolvent application method of heavy hydrocarbon up flow type hydro-upgrading reaction process inferior, it is characterised in that include following step It is rapid:

In up flow type hydro-upgrading reaction process RX, there are hydrogen, hydrogen supply hydrocarbon, other conventional liq hydrocarbon, there may be solid simultaneously Under the conditions of the mixed phase material of body particle, the hydrocarbon HDS inferior of the hydrocarbon component containing normal boiling point higher than 500 DEG C is added at least partially At least part aromatic hydrogenation saturated reaction, at least part heat cracking reaction, at least part occur for hydrogen modification reaction RX-R The stabilized hydrogenation reaction of free radical is converted into hydrogenation reaction product RX-P；Reaction process RX is received and is contained hydrogen supply hydrocarbon or hydrogen supply hydrocarbon The material of the solvent hydrocarbon ADSC of precursor；

Separation process S10, RX-P be separated into the solvent hydrocarbon ADSC containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor gas S10-V and Liquid S10-L obtains the logistics DS10's or logistics DS10 of the ADSC of hydrocarbon containing solvent based at least part gas S10-V plus hydrogen is steady The stabilized hydrogenation object DSH10 of earnest DSH10, at least part logistics DS10 or logistics DS10 return to RX and participate in reaction, with poor quality Hydrocarbon HDS or hydrocarbon HDS hydro-conversion object contact inferior；

The solvent hydrocarbon ADSC component of hydrogenation process is the outer for hydrogen supply hydrocarbon or outside for the mistake hydrogen of hydrogen supply hydrocarbon of hydrogenation process The self-produced hydro carbons of conversion product and/or other raw materials；

The stabilized hydrogenation object DSH10 of the logistics DS10 refers to making the hydrogen supply hydrocarbon in logistics DS10 in stabilized hydrogenation process MR Mistake hydrogen conversion product occur hydrogenation reaction be converted into hydrogen supply capacity enhancing hydrogen supply hydrocarbon.

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

The weight flow of the stabilized hydrogenation object DSH10 of logistics DS10 or logistics DS10 is up flow type hydro-upgrading reaction process RX 0.05~50 times of the outer weight flow for hydrogen supply hydrocarbon DSF.

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

The weight flow of the stabilized hydrogenation object DSH10 of logistics DS10 or logistics DS10 is up flow type hydro-upgrading reaction process RX 0.10~10 times of the outer weight flow for hydrogen supply hydrocarbon DSF.

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

The weight flow of the stabilized hydrogenation object DSH10 of logistics DS10 or logistics DS10 is up flow type hydro-upgrading reaction process RX 0.50~5 times of the outer weight flow for hydrogen supply hydrocarbon DSF.

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

Hydrocarbon HDS inferior, mainly the hydrocarbon component by normal boiling point higher than 500 DEG C forms.

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

Hydrocarbon HDS inferior, may contain solid.

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

Hydrocarbon HDS inferior, mainly the hydrocarbon component by normal boiling point higher than 530 DEG C forms, and contains solid.

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

Hydrocarbon HDS inferior, mainly the hydrocarbon component by normal boiling point higher than 500 DEG C, which forms and contain solid, is added from residual oil up flow type The logistics that the separation process of the reaction product of hydrogen heat cracking reaction process obtains.

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

Hydrocarbon HDS inferior, mainly the hydrocarbon component by normal boiling point higher than 500 DEG C, which forms and contain solid, is added from residual oil up flow type The logistics that the fractional distillation process of the generation oil of hydrogen heat cracking reaction process obtains.

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

Hydrocarbon HDS inferior, mainly the hydrocarbon component by normal boiling point higher than 500 DEG C forms and containing solid molybdenum sulfide, is to use to divide certainly Dissipate the logistics that the fractional distillation process of the generation oil of the residual oil up flow type heat from hydrogenation cracking reaction process of property molybdenum catalyst obtains.

11. method described according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10, it is characterised in that:

The stabilized hydrogenation object DSH10 of the logistics DS10 refers to making the hydrogen supply hydrocarbon in logistics DS10 in stabilized hydrogenation process MR Mistake hydrogen conversion product occur hydrogenation reaction be converted into hydrogen supply capacity enhancing hydrogen supply hydrocarbon；

In the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F, there are hydrogen, conventional liq hydrocarbon may deposit simultaneously Under the conditions of the mixed phase material of solid particle, the hydrocarbon material R10F of at least part carries out hydrogenation reaction R10-R generation at least one Heat from hydrogenation cracking reaction is divided to be converted into hydrogenation reaction product R10-P；Reaction process R10, may receive it is other containing hydrogen supply hydrocarbon or The material of the solvent hydrocarbon ADSC of hydrogen supply hydrocarbon precursor；

In the following process process RX-P-P100 of hydrogenation reaction product RX-P, contain at least part based on gas S10-V Stabilized hydrogenation the object DSH20, at least part logistics DS20 or logistics DS20 of the logistics DS20 or logistics DS20 of solvent hydrocarbon ADSC Stabilized hydrogenation object DSH20 by at least partly reaction process of reaction process R10, with hydrocarbon material R10F or its hydro-conversion object Contact.

12. according to the method for claim 11, it is characterised in that:

In the following process process RX-P-P100 of hydrogenation reaction product RX-P, contain at least part based on gas S10-V Stabilized hydrogenation the object DSH20, at least part logistics DS20 or logistics DS20 of the logistics DS20 or logistics DS20 of solvent hydrocarbon ADSC Stabilized hydrogenation object DSH20 by at least partly reaction process of reaction process R10, with hydrocarbon material R10F or its hydro-conversion object Contact, working method, a kind or several in following:

1. gas or its stabilized hydrogenation product of at least part based on the obtained ADSC component of hydrocarbon containing solvent of gas S10-V, lead to Cross at least partly reaction process of reaction process R10；

2. at least part the possibility based on the obtained ADSC component of hydrocarbon containing solvent of gas S10-V containing the liquid of solid or its add hydrogen Stable product passes through at least partly reaction process of reaction process R10；

3. possibility gas-liquid mixed phase material containing solid of at least part based on the obtained ADSC component of hydrocarbon containing solvent of gas S10-V Or its stabilized hydrogenation product, pass through at least partly reaction process of reaction process R10.

13. according to the method for claim 11, it is characterised in that:

1. at least part gas S10-V or its stabilized hydrogenation product, pass through at least partly reaction process of reaction process R10；

2. the possibility of the ADSC component of hydrocarbon containing solvent that separation gas S10-V is obtained containing the liquid of solid or its stabilized hydrogenation product, Pass through at least partly reaction process of reaction process R10；

3. gas-liquid mixed phase material of the possibility of the ADSC component of hydrocarbon containing solvent that separation gas S10-V is obtained containing solid or its add hydrogen steady Fixed output quota object passes through at least partly reaction process of reaction process R10.

14. according to the method for claim 11, it is characterised in that:

In the following process process RX-P-P100 of hydrogenation reaction product RX-P, boil at least part in liquid S10-L routinely The hydrocarbon component S10-L-VRC of the point higher than 500 DEG C at least partly reacting by up flow type heat from hydrogenation cracking reaction process R10 Journey is contacted with hydrocarbon material R10F or its hydro-conversion object.

15. according to the method for claim 11, it is characterised in that:

In the following process process RX-P-P100 of hydrogenation reaction product RX-P, boil at least part in liquid S10-L routinely The hydrocarbon component S10-L-VRC of the point higher than 500 DEG C at least partly reacting by up flow type heat from hydrogenation cracking reaction process R10 Journey contacts, working method with hydrocarbon material R10F or its hydro-conversion object, and a kind or several in following:

2. possibility of at least part based on the obtained the hydrocarbon component S10-L-VRC containing normal boiling point higher than 500 DEG C of liquid S10-L Liquid containing solid passes through at least partly reaction process of reaction process R10；

3. possibility of at least part based on the obtained the hydrocarbon component S10-L-VRC containing normal boiling point higher than 500 DEG C of liquid S10-L Gas-liquid mixed phase material containing solid passes through at least partly reaction process of reaction process R10.

16. according to the method for claim 11, it is characterised in that:

2. liquid of the possibility containing solid for the hydrocarbon component S10-L-VRC containing normal boiling point higher than 500 DEG C that separation liquid S10-L is obtained Body passes through at least partly reaction process of reaction process R10；

3. gas of the possibility containing solid for the hydrocarbon component S10-L-VRC containing normal boiling point higher than 500 DEG C that separation liquid S10-L is obtained Liquid mixed phase material passes through at least partly reaction process of reaction process R10.

17. according to the method for claim 11, it is characterised in that:

The up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F points are front conversion zone R10A and rear portion conversion zone R10B；

In front conversion zone R10A, there are hydrogen, conventional liq hydrocarbon, there may be the mixed phase material conditions of solid particle simultaneously Under, the hydrocarbon material R10F of at least part carry out hydrogenation reaction R10B-R occur at least part heat from hydrogenation cracking reaction be converted into plus Hydroformylation reaction product R10A-P；Front conversion zone R10A may receive other solvent hydrocarbon containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor The material of ADSC；

The solvent hydrocarbon containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor is separated into separation process MTHS, front conversion zone product R10A-P The gas MTHS-V and liquid MTHS-L of ADSC, at least part gas MTHS-V are used as MTHS-VK and do not enter rear portion conversion zone R10B；

In rear portion hydrogenation reaction section R10B, there are hydrogen, conventional liq hydrocarbon, there may be the mixed phase materials of solid particle simultaneously Under the conditions of, at least part liquid MTHS-L carries out hydrogenation reaction R10B-R and at least part heat from hydrogenation cracking reaction conversion occurs For hydrogenation reaction product R10B-P；Rear portion hydrogenation reaction section R10B, may the other hydrocarbon materials of joint processing.

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

The material RLK of the ADSC of hydrocarbon containing solvent is obtained based on gas MTHS-VK or is obtained based on RLK hydrogenation process 2MR product 2MRP The hydrogen-containing hydrocarbon stream RLKH arrived, returns to up flow type hydro-upgrading reaction process RX and participates in reaction, adds hydrogen to turn with hydrocarbon HDS inferior or its Compound contact；Up flow type hydro-upgrading reaction process RX may receive other solvents containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor The material of hydrocarbon ADSC；

Hydrogenation process 2MR may receive the material of other solvent hydrocarbon ADSC containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor simultaneously；

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

The material RLK of the ADSC of hydrocarbon containing solvent is obtained based on gas MTHS-VK or is obtained based on RLK hydrogenation process 2MR product 2MRP The hydrogen-containing hydrocarbon stream RLKH arrived returns to front conversion zone R10A and participates in reaction, contacts with hydrocarbon material R10F or its hydro-conversion object； Front conversion zone R10A may receive the material of other solvent hydrocarbon ADSC containing hydrogen supply hydrocarbon or hydrogen supply hydrocarbon precursor；

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

In the following process process RX-P-P100 of hydrogenation reaction product RX-P, working method, a kind or several in following:

1. the material of the hydrocarbon component RX-P-VRC containing normal boiling point higher than 500 DEG C based on liquid S10-L, into reaction process R10A contacts participation reaction with hydrocarbon material R10F or its hydro-conversion object；

2. the material of the hydrocarbon component RX-P-VRC containing normal boiling point higher than 500 DEG C based on liquid S10-L, into separation process MTHS combines with front conversion zone product R10A-P carries out gas-liquid separation；

3. the material of the hydrocarbon component RX-P-VRC containing normal boiling point higher than 500 DEG C based on liquid S10-L, into rear portion conversion zone R10B participates in reaction；

4. the material of the hydrocarbon component RX-P-VRC containing normal boiling point higher than 500 DEG C based on liquid S10-L, with rear portion hydrogenation reaction The reaction product R10B-P mixing of section R10B.

21. according to the method for claim 11, it is characterised in that:

Hydrocarbon HDS inferior, it is high containing normal boiling point to be that the final hydrogenation products based on hydrocarbon HDS inferior and/or hydrocarbon material R10F are obtained In the material of 520 DEG C of hydro carbons, solid may be contained.

22. according to the method for claim 11, it is characterised in that:

Hydrocarbon HDS inferior, be the final hydrogenation products based on hydrocarbon HDS inferior and/or hydrocarbon material R10F separation process obtain it is main The material that 520 DEG C of hydro carbons form is higher than by normal boiling point, solid may be contained.

23. according to the method for claim 11, it is characterised in that:

Hydrocarbon HDS inferior, be the final hydrogenation products based on hydrocarbon HDS inferior and/or hydrocarbon material R10F separation process obtain it is main The material that 500 DEG C of hydro carbons form is higher than by normal boiling point, solid may be contained.

24. according to the method for claim 11, it is characterised in that:

Hydrocarbon HDS inferior, be the final hydrogenation products based on hydrocarbon HDS inferior and/or hydrocarbon material R10F separation process obtain it is main The material that 480 DEG C of hydro carbons form is higher than by normal boiling point, solid may be contained.

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

The hydrocarbon component of the hydrocarbon HDS inferior mainly by normal boiling point higher than 530 DEG C forms.

26. according to the method for claim 11, it is characterised in that:

Hydrocarbon material R10F is heavy oil and/or coal, and the heavy oil is mainly higher than 530 DEG C of the hydrocarbon component by normal boiling point.

27. according to the method for claim 11, it is characterised in that:

Up flow type hydro-upgrading reaction process RX and may by up flow type heat from hydrogenation cracking reaction process R10 in, it is inferior The overall hot tearing rate of the hydrocarbon component of the normal boiling point higher than 530 DEG C is 15~65 weight % in hydrocarbon HDS.

28. according to the method for claim 11, it is characterised in that:

Up flow type hydro-upgrading reaction process RX and may by up flow type heat from hydrogenation cracking reaction process R10 in, it is inferior The overall hot tearing rate of the hydrocarbon component of the normal boiling point higher than 530 DEG C is 20~75 weight % in hydrocarbon HDS；

In up flow type heat from hydrogenation cracking reaction process R10, the heat of the hydrocarbon component of the normal boiling point higher than 530 DEG C in hydrocarbon material R10F Cracking rate is 50~85 weight %；

In up flow type heat from hydrogenation cracking reaction process R10 and the up flow type hydro-upgrading reaction process RX of possible combined application, The overall hot tearing rate of the hydrocarbon component of the normal boiling point higher than 530 DEG C is 80~97 weight % in hydrocarbon HDS inferior.

29. according to the method for claim 11, it is characterised in that:

Up flow type hydro-upgrading reaction process RX and may by up flow type heat from hydrogenation cracking reaction process R10 in, it is inferior The overall hot tearing rate of the hydrocarbon component of the normal boiling point higher than 530 DEG C is 40~60 weight % in hydrocarbon HDS；

In up flow type heat from hydrogenation cracking reaction process R10, the heat of the hydrocarbon component of the normal boiling point higher than 530 DEG C in hydrocarbon material R10F Cracking rate is 60~78 weight %；

In up flow type heat from hydrogenation cracking reaction process R10 and the up flow type hydro-upgrading reaction process RX of possible combined application, The overall hot tearing rate of the hydrocarbon component of the normal boiling point higher than 530 DEG C is 88~95 weight % in hydrocarbon HDS inferior.

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

Normal boiling point is higher than 530 DEG C of the hydrocarbon component in hydrocarbon material R10F, in the hot tearing of up flow type heat from hydrogenation cracking reaction process R10 Rate is 50~85 weight %；

Normal boiling point is higher than 530 DEG C of the hydrocarbon component in hydrocarbon material R10F, and in front, the hot tearing rate of conversion zone R10A is 30~50 Weight %, at rear portion, the hot tearing rate of conversion zone R10B is 20~40 weight %.

31. method described in 8 or 19 according to claim 1, it is characterised in that:

The aromatic carbon rate of hydrogen-containing hydrocarbon stream RLKH is 0.4~0.6.

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

Hydrocarbon HDS inferior, a kind or several in following materials:

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

2. oil product logistics obtained by high temperature coal-tar or its distillate or its hot procedure；Hot procedure be selected from coking or Catalytic cracking process or catalytic pyrolysis process or hydrogenation process；

3. oil product obtained by the distillate oil of direct hydrogenation liquefaction of coal process product or its hot procedure；Hot procedure is selected from coking Process or catalytic cracking process or catalytic pyrolysis process or hydrogenation process；

4. oil product obtained by shale oil or its distillate or its hot procedure；Hot procedure is selected from coking or catalytic cracking Process or catalytic pyrolysis process or hydrogenation process；

6. oil product obtained by petroleum based heavy fuel oils or its hot procedure；Hot procedure be selected from coking or catalytic cracking process or Catalytic pyrolysis process or hydrogenation process；

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

Hydrocarbon HDS inferior, contains Hydrogenation catalyst granule solid.

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

At least 40 weight % for the hydrocarbon component that the normal boiling point of front conversion zone product R10A-P is 230~400 DEG C enter gas In body MTHS-V.

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

At least 70 weight % for the hydrocarbon component that the normal boiling point of front conversion zone product R10A-P is 230~400 DEG C enter gas In body MTHS-V.

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

Based on the material for being higher than 520 DEG C of hydro carbons containing normal boiling point that reaction process R10 product R10-P is obtained, into up flow type Heat from hydrogenation cracking reaction process R10 participates in reaction, contacts with hydrocarbon material R10F or its hydro-conversion object.

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

It is anti-into front based on the material for being higher than 520 DEG C of hydro carbons containing normal boiling point that reaction process R10 product R10-P is obtained It answers section R10A to participate in reaction, is contacted with hydrocarbon material R10F or its hydro-conversion object.

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

Based on the material for being higher than 520 DEG C of hydro carbons containing normal boiling point that reaction process R10 product R10-P is obtained, into separating Journey MTHS combines with front conversion zone product R10A-P carries out gas-liquid separation.

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

It is anti-into rear portion based on the material for being higher than 520 DEG C of hydro carbons containing normal boiling point that reaction process R10 product R10-P is obtained Section R10B is answered to participate in reaction.

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

Up flow type hydro-upgrading reaction process RX, uses the up-flow reactor of 1 or 2 or more serial operation.

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

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

Hydrogen supply agent weight is higher than with normal boiling point in hydrocarbon HDS inferior in up flow type hydro-upgrading reaction process RX, hydrocarbon HDS inferior The weight ratio of 530 DEG C of the hydrocarbon component is 0.3~3.0.

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

In front conversion zone R10A, hydrogen supply agent weight and hydrocarbon material R10F the weight of the hydrocarbon component of the normal boiling point higher than 530 DEG C it It is 0.07~2.0 than R10A-DSK；

In rear portion conversion zone R10B, hydrogen supply agent weight and hydrocarbon material R10F the weight of the hydrocarbon component of the normal boiling point higher than 530 DEG C it It is 0.03~1.0 than R10B-DSK, and R10B-DSK is lower than R10A-DSK at least 10%.

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

Solvent hydrocarbon ADSC, a kind or several in following conventional boiling range:

45. according to the method for claim 11, it is characterised in that:

The up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F is direct hydrogenation liquefaction of coal reaction process, selected from following 1 kind or several in technical process:

3. kerosene refines process altogether；

4. coal faces hydrogen thermosol liquefaction process.

46. according to the method for claim 11, it is characterised in that:

The working method of up flow type heat from hydrogenation the cracking reaction process R10, the hydrogenator XR10E used of hydrocarbon material R10F are selected 1 kind or several in following:

1. suspended-bed reactor, that is, paste state bed reactor；

2. fluidized bed reactor；

3. suspension bed and ebullated bed combination type reactor.

47. according to the method for claim 11, it is characterised in that:

Option 2, reactor XR10E, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of device XR10E material inlet；

Option 3, reactor XR10E, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of device XR10E material inlet；

Option 4, reactor XR10E, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of device XR10E material inlet, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 5, reactor XR10E, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of device XR10E material inlet, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 6, reactor XR10E, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The fluidized bed reactor of device XR10E material inlet, be collected simultaneously cup discharge other collection liquids by other dedicated feeding engines to Downstream conveys liquid material product；

Option 7, reactor XR10E, forced circulation returns to reaction after the collection liquid that liquid collecting cup is arranged in top is pressurizeed by circulating pump The suspended-bed reactor of device XR10E material inlet, be collected simultaneously cup discharge other collection liquids by other dedicated feeding engines to Downstream conveys liquid material product；

Option 10, reactor XR10E, 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 XR10E material inlet and the combination type reactor of ebullated bed；

Option 11, reactor XR10E, 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 XR10E 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 XR10E, 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 XR10E material inlet and the combination type reactor of ebullated bed, the other collection liquids for being collected simultaneously cup discharge are passed through Other dedicated feeding engine downstream transport liquid material products；

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.

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

Hydrocarbon HDS inferior is selected from down in up flow type hydro-upgrading reaction process RX, the working method of the hydrogenator XRXE used 1 kind or several in column:

1. suspended-bed reactor, that is, paste state bed reactor；

2. fluidized bed reactor；

3. suspension bed and ebullated bed combination type reactor.

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

Option 2, reactor XRXE, 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 XRXE material inlet；

Option 3, reactor XRXE, 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 XRXE material inlet；

Option 4, reactor XRXE, 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 XRXE material inlet, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 5, reactor XRXE, 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 XRXE material inlet, while circulating pump conveys circulation fluid, downstream transport liquid material product；

Option 6, reactor XRXE, 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 XRXE 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 XRXE, 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 XRXE 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 XRXE, 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 XRXE, 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 XRXE, 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 XRXE material inlet and the combination type reactor of ebullated bed；

Option 11, reactor XRXE, 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 XRXE 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 XRXE, 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 XRXE 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；

50. according to the method for claim 11, it is characterised in that:

Reaction process R10 contains the liquid hydrocarbon material of solid to possibility of the hydrogenation process RX conveying containing heavy oil.

51. according to the method for claim 11, it is characterised in that:

The operating condition of the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F are as follows: reaction temperature be 400~480 DEG C, Reactor pressure is 6~30MPa, and gas-liquid volume ratio is 100~1500Nm³/ t, catalyst loading are heavy oil FD weight 0.001~5 mass %, co-catalyst additive amount are that sulphur in co-catalyst/catalyst activity metal molar ratio is 1.0~2.0, Reaction time is 0.1~5 hour, and the hydrogen supply hydrocarbon weight ratio in the charging of reaction process total hydrocarbon is 0.07~0.50.

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

The operating condition of the up flow type hydro-upgrading reaction process RX of hydrocarbon HDS inferior are as follows: reaction temperature is 380~480 DEG C, reacts Device pressure is 6~30MPa, and gas-liquid volume ratio is 100~1500Nm³/ t, reaction process total hydrocarbon charging in hydrogen supply hydrocarbon weight Amount ratio is 0.20~0.80.

53. according to the method for claim 11, it is characterised in that:

It separates on the final hydrogenation products and/or hydrocarbon HDS inferior of the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F What the hydrocarbon component that the final hydrogenation products of streaming hydro-upgrading reaction process RX obtain mainly by normal boiling point higher than 530 DEG C formed Residual oil ZVR may be got rid of containing the outer of solid particle；

Getting rid of residual oil ZVR removes coking reaction process R90 outside, is converted into coke, coking generates oil, cooking gas.

54. method according to claim 53, it is characterised in that:

Residual oil ZVR whereabouts pyrogenetic reaction process R90 is got rid of outside, is selected from one of the following or several:

1. as coking raw material devulcanization coking；

2. going delayed coking to process as blending raw material；

3. going coal coking process to process as blending raw material；

Pyrogenetic reaction process R90 generate coal gas be used as hydrogen feedstock hydrogen making, pyrogenetic reaction process R90 generation tar or The distillate of tar enters the up flow type of the up flow type heat from hydrogenation cracking reaction process R10 and/or hydrocarbon HDS inferior of hydrocarbon material R10F Hydro-upgrading reaction process RX joint processing, to constitute the big combination of a kind of process of coking and heavy-oil hydrogenation thermal cracking process；

Get rid of oil containing solid slag as coal coking process ingredient outside in use, as room temperature solid containing after solid slag oil individually crushing with refining Coking coal blending is as crushing is used as coking original together after the oil containing solid slag and coking coal blending that coking raw material or room temperature are solid Material.

55. according to the method for claim 11, it is characterised in that:

By heavy oil catalytic cracking reaction process or heavy-oil catalytic thermal cracking reaction process generate rich in 2~4 ring structure aromatic hydrocarbons The wax slop that hydrocarbon ils and/or hydrocarbon material up flow type heat from hydrogenation cracking process generate oil is modified as hydrogen supply dissolvent use, into hydrocarbon material The up flow type hydro-upgrading reaction process RX of the up flow type heat from hydrogenation cracking reaction process R10 of R10F and/or hydrocarbon HDS inferior；

It separates on the final hydrogenation products and/or hydrocarbon HDS inferior of the up flow type heat from hydrogenation cracking reaction process R10 of hydrocarbon material R10F What the hydrocarbon component that the final hydrogenation products of streaming hydro-upgrading reaction process RX obtain mainly by normal boiling point higher than 530 DEG C formed Residual oil ZVR may be got rid of containing the outer of solid particle, go coking reaction process R90 to process as coking raw material.

56. according to the method for claim 11, it is characterised in that:

Hydrocarbon material R10F is mainly to be higher than the heavy oil that 500 DEG C of hydro carbons form by normal boiling point, and carbon residue is 15~35%.

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

Hydrocarbon HDS inferior is mainly to be higher than the heavy oil that 500 DEG C of hydro carbons form by normal boiling point, and carbon residue is 20~60%.

58. according to the method for claim 11, it is characterised in that:

Liquid collecting cup is arranged in last reactor KRE100 inner top of front conversion zone R10A, separates KRE100 reaction product For collection liquid KRE100-L and gas-liquid mixed phase material KRE100-M, at least part collection liquid KRE100-L enters rear portion conversion zone R10B is reacted, and at least part of the obstructed portion conversion zone R10B later of at least part gas-liquid mixed phase material KRE100-M is anti- Process is answered, residence time of the gas phase in mixed phase material KRE100-M in the conversion zone R10B of rear portion is shortened；

In rear portion hydrogenation reaction section R10B, there are hydrogen, conventional liq hydrocarbon, there may be the mixed phase materials of solid particle simultaneously Under the conditions of, at least part collection liquid KRE100-L carries out hydrogenation reaction R10B-R and at least part heat from hydrogenation cracking reaction occurs It is converted into hydrogenation reaction product R10B-P；Rear portion hydrogenation reaction section R10B, may the other hydrocarbon materials of joint processing.

59. method according to claim 58, it is characterised in that:

Liquid collecting cup is arranged in last reactor KRE100 inner top that front reacts R10A sections, separates KRE100 reaction product For collection liquid KRE100-L and gas-liquid mixed phase material KRE100-M, at least part collection liquid KRE100- enters rear portion conversion zone R10B is reacted, and at least part of the obstructed portion conversion zone R10B later of at least part gas-liquid mixed phase material KRE100-M is anti- Process is answered, residence time of the gas phase in mixed phase material KRE100-M in the conversion zone R10B of rear portion is shortened；

In rear portion hydrogenation reaction section R10B, receives and liquid collecting is set at the top of the reactor KRE200 of gas-liquid mixed phase material KRE100-M Cup, forced circulation returns to upstream reaction space KK and makes upstream reaction space KK product stream after so that collection liquid is pressurizeed by circulating pump Liquid collecting cupule at the top of reacted device KRE200, so that at least part liquid material conduct in gas-liquid mixed phase material KRE100-M Collection liquid by the gas in gas-liquid mixed phase material KRE100-M can not by reaction compartment.

60. method according to claim 58, it is characterised in that:

Liquid collecting cup is arranged in last reactor KRE100 inner top of front conversion zone R10A, separates KRE100 reaction product For collection liquid KRE100-L and gas-liquid mixed phase material KRE100-M, more than the collection liquid of the net product liquid 50% of reactor KRE100 KRE100-L enters rear portion conversion zone R10B and is reacted, the obstructed portion conversion zone R10B's later of gas-liquid mixed phase material KRE100-M At least part reaction process shortens residence time of the gas phase in mixed phase material KRE100-M in the conversion zone R10B of rear portion；

In rear portion hydrogenation reaction section R10B, receives and liquid collecting is set at the top of the reactor KRE200 of gas-liquid mixed phase material KRE100-M Cup, forced circulation returns to upstream reaction space KK after so that at least the 50% of whole liquid materials is pressurizeed as collection liquid by circulating pump And make liquid collecting cupule at the top of the reacted device KRE200 of upstream reaction space KK product stream, so that gas-liquid mixed phase material At least part liquid material in KRE100-M can not pass through as collection liquid by the gas in gas-liquid mixed phase material KRE100-M Reaction compartment.

61. method according to claim 58, it is characterised in that:

Liquid collecting cup is arranged in last reactor KRE100 inner top of front conversion zone R10A, separates KRE100 reaction product For collection liquid KRE100-L and gas-liquid mixed phase material KRE100-M, more than the collection liquid of the net product liquid 70% of reactor KRE100 KRE100-L enters rear portion conversion zone R10B and is reacted, the obstructed portion conversion zone R10B's later of gas-liquid mixed phase material KRE100-M At least part reaction process shortens residence time of the gas phase in mixed phase material KRE100-M in the conversion zone R10B of rear portion；

In rear portion hydrogenation reaction section R10B, receives and liquid collecting is set at the top of the reactor KRE200 of gas-liquid mixed phase material KRE100-M Cup, forced circulation returns to upstream reaction space KK after so that at least the 66% of whole liquid materials is pressurizeed as collection liquid by circulating pump And make liquid collecting cupule at the top of the reacted device KRE200 of upstream reaction space KK product stream, so that gas-liquid mixed phase material At least part liquid material in KRE100-M can not pass through as collection liquid by the gas in gas-liquid mixed phase material KRE100-M Reaction compartment.

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

The reaction process of last reactor of separation process MTHS and front conversion zone R10A, it is complete in a unit equipment At；