CN108102715B

CN108102715B - A kind of processing method of heavy oil feedstock

Info

Publication number: CN108102715B
Application number: CN201611052852.0A
Authority: CN
Inventors: 刘铁斌; 耿新国; 翁延博; 李洪广
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2016-11-25
Filing date: 2016-11-25
Publication date: 2019-08-06
Anticipated expiration: 2036-11-25
Also published as: CN108102715A

Abstract

The invention discloses a kind of processing method of heavy charge, the method content includes: that the slurry oil of heavy charge and at least partly catalytic cracking unit is mixed into fluidized bed reactor and carries out hydrotreating；Successively reaction zone is handled by the fixed bed hydrogenation pretreatment reaction area being arranged in series and fixed bed hydrogenation after the recycle oil of obtained boiling bed hydrogenation processing reaction effluent, at least partly catalytic cracking unit and hydrogen mixing to be reacted；Obtained generation oil enters catalytic cracking unit as the raw material of catalytic cracking unit, and the catalytic cracking reaction product that catalytic cracking unit fractionating column obtains includes gasoline fraction, diesel oil distillate, recycle oil and slurry oil.The method of the present invention can substantially extend the operation cycle of processing unit.

Description

A kind of processing method of heavy oil feedstock

Technical field

The present invention relates to a kind of processing methods of heavy charge, specifically add boiling bed hydrogenation processing, fixed bed Hydrogen processing and catalytic cracking organic assembling process heavy charge to produce the scheme of fuel oil products.

Background technique

Currently, it will be in hold that demand of the refined products market to oil products such as steam coal bavins, which is especially the demand to motor petrol, both at home and abroad The continuous trend risen, and the demand to heavy oil products such as heavy fuel oils is then on a declining curve.Meanwhile crude oil in the world Matter is deteriorated increasingly, and environmental regulation is increasingly stringent, and increasingly strict requirement is proposed to oil quality.Therefore, how relatively to pass through Reasonable cost of helping realizes that heavy oil lighting and petrol and diesel oil product quality persistently upgrade and has become oil refining industry concern both at home and abroad Focus.

The main purpose of residual hydrocracking technique is to keep sulphur, nitrogen, metal in residual oil raw material etc. miscellaneous by hydrotreating Matter content is greatly reduced, the undesirable components hydro-conversion such as condensed-nuclei aromatics, colloid, asphalitine, improves hydrogen-carbon ratio, reduces carbon residue and contains Amount, make its cracking performance be improved significantly.Fixed bed residual hydrogenation technology is a kind of heavy oil deep processing technology, equipped with spy Determine in the fixed bed reactors of catalyst, under the hydro condition of high temperature and pressure, desulfurization is carried out to normal pressure or decompression residuum, is taken off Nitrogen, demetalization etc. are one of the important means of residual oil weight-lightenings to obtain light-end products to the maximum extent.Fixed bed residual oil adds Hydrogen technology is with its liquid product yield height, and good product quality, production chains are strong, and waste, waste material are few, environmental-friendly, invests back The advantages that report rate is high, has been more and more widely used.

The setting of fixed bed residual hydrocracking process reaction part reactor is generally connected by multiple reactors or bed It uses, requires to optimize the dosage form of catalyst according to the property of original oil, reaction condition and purpose product, according to different physical Matter, catalyst activity and all kinds of catalyst ratios carry out grading loading.Fixed bed residual hydrogenation technology although having many advantages, such as, But in process of production, but it is easy to appear the phenomenon that reactor pressure drop increases.Industrial operation shows that reactor pressure drop increases One of an important factor for being confining device full production and long-term operation.Especially more reactor series connection, preposition is anti- Answer device to react load due to assuming responsibility for 70% or more demetalization, metal sulfide is deposited on catalyst bed, into operation after Inevitably there is pressure drop rapid growth in phase, and subsequent reactor is since demetalization load is obviously relatively low, pressure drop increase compared with Slowly.This affects the cycle of operation and the device of device there have been front reactor and the distribution of rear portion reactor load are uneven Stable operation.

CN103059928A discloses a kind of hydrotreater and its application and process for hydrogenating residual oil.The invention mentions For a kind of and its processing unit, which includes primary concatenated plus hydrogen insured unit and main hydrotreating unit.Described adds Hydrogen protection location includes in parallel main hydrogenation protecting reactor and spare hydrogenation protecting reactor, and main hydrogenation protecting reactor Volume is greater than stand-by protection reactor.In hydroprocessing processes, main hydrogenation protecting reactor and spare hydrogenation protecting reactor It is used alternatingly.Main hydrogenation protecting reactor and spare hydrogenation protecting reactor handover operation can be processed height by the process The residual oil of calcium high metal content, the disadvantage is that the reactor that left unused, increasing investment reduces reactor utilization rate, and cannot Lead reactor pressure drop growing concern is solved from not catching up with.

CN1393515A discloses a kind of method of residual hydrocracking.This method is in heavy resid hydrogenation reaction system First reactor add one or more feed inlets, change simultaneously original catalyst grade and match, when an anticatalyst bed When pressure drop designs 0.4~0.8 times of pressure drop for device, next feed inlet is successively used instead, while original feed inlet can be into circulation The miscella of oil or recycle oil and original oil can be effectively prevented bed pressure drop with the technique and extend the operation cycle of device, And the processing capacity of device can be increased, help to improve flow distribution.The disadvantage is that inductor manufacturing cost increases, make initial Pressure drop increases, and device inner volume utilization rate reduces etc..

CN103059931A discloses a kind of method of residual hydrocracking.This method is in hydrotreating reaction condition Under, residual oil raw material and hydrogen once pass through concatenated more reactors, when device operation 700~4000 it is small when after carry out shunting behaviour Make, reduce an anti-inlet amount or keep an anti-inlet amount constant, increase that one is anti-and the last one reactor among each reactor Inlet amount, increased feed residue intermediate reactor entrance inject.This method is delayed by changing each anti-feed loading The growth of pressure drop is solved, but cannot fundamentally change the growth trend of lead reactor pressure drop, from the point of view of industrial actual motion, pressure drop The design upper limit can be quickly reached once increasing, and changes the stable operation that each anti-entrance charging is unfavorable for device.

CN1119397C discloses a kind of hydrogenation and catalystic cracking combined process for residual oil, in this method, residual oil Enter residual hydrogenation equipment together with clarified oil, reacted in the presence of hydrogen and hydrogenation catalyst, heavy-cycle oil is being catalyzed It is recycled inside cracking unit；Resulting slurry oil is reacted through the isolated clarified oil of separator, is back to hydrogenation plant.But oil Slurry enters residual hydrocracking device, and the easy green coke object in slurry oil will will increase the carbon deposit of hydrogenation catalyst, reduces plus hydrogen is urged The hydrogenation activity of agent and operation cycle, and heavy-cycle oil is inside catalytic cracking unit.Therefore, the method is to reduction coke Yield, raising product quality are limited.USP6277270 discloses a kind of handle comprising fixed bed hydrogenation, at boiling bed hydrogenation It manages with catalytic cracking combined technique and produces light-weight fuel oil.Fixed bed and ebullated bed process decompression residuum respectively, obtained production Product mix after air-distillation, and atmospheric fractions recycling, reduced crude is processed in Residue Catalytic Cracking.Patent processing is former Material is limited in scope, not applicable for the raw material of high metal content.

Fixed bed hydrogenation+heavy oil catalytic cracking is the mode often selected, and the route light oil yield is high, is able to satisfy relatively stringent Environmental requirement, under soaring oil prices have stronger competitiveness.The shortcoming of the route be it is not good enough to the adaptability of crude oil, It is suitable for handling matter sour crude oil in lightweight and part.In addition the fixed bed residual hydrogenation equipment cycle of operation is usually one to two Year, it has arrived situations such as end-of-run generally occurs within lead reactor pressure drop raising, hot spot device and has been forced to stop work.US4713221 is public Opened conventional residual hydrogenation and it is catalytic cracking combined on the basis of, the heavy-cycle oil of catalytic cracking is recycled to residual hydrogenation Device carries out adding hydrogen after mixing with residual oil, enters back into catalytic cracking unit.But catalytic cracked oil pulp does not obtain effective benefit With this method is limited to coke yield, raising product yield is reduced.Meanwhile the adaptability to raw material difference of fixed bed hydrogenation processing There is no solve for problem.

When due to inferior heavy oil processing, volume space velocity is lower, therefore generally requires multiple reactors and be used in series (series connection Using referring to that reaction mass passes sequentially through each reactor), while 2 or 2 or more parallel series are set.Therefore, inferior heavy oil Hydrogenation plant generally comprises multiple reactors, for the device of 2,000,000 tons of scales of year processing capacity, by current device fabrication Level usually requires 8 reactors.For fluidized bed reactor, each reactor is both needed to a set of catalyst and adds row system online System, this set catalyst add the investment of heat-extraction system very high (the evaluated half or so for accounting for boiling bed hydrogenation device gross investment) online, It is complicated for operation, the failure rate of appearance also highest.

Summary of the invention

In view of the deficiencies of the prior art, the present invention provides a kind of processing methods of heavy charge.This method process is simple, It only needs to carry out simple modifications to existing apparatus, so that it may substantially extend the operation cycle of device, and the benefit of catalyst can be made It is realized and is maximized with efficiency, poor residuum raw material can be handled using the technique, extend the operation cycle of residual hydrogenation equipment, reduced The investment and operating cost of device, technical process are simple.

Existing heavy Oil Hydrotreating Processes, all reactors use concatenated process flow, it is therefore desirable to anti-in First Device is answered to load a large amount of protective agent to deposit the impurity and dirt in raw material, operation will lead in First protection reactor in this way For the antigravity system of filling since activity is lower, demetalization load is lower, has arrived device end-of-run reactor in some cases Pressure drop is still very low, so that the ability that is de-, holding metallic compound of monolithic catalyst reduces.If improving its catalyst activity again It will cause the rapid growth of pressure drop, shorten the cycle of operation, and subsequent catalyst performance plays completely not yet, keeps First Protection reactor catalyst activity appropriate be difficult to control, and during residual hydrogenation equipment whole service there are it is many because Element such as Fe in urgent shutting down, feedstock property fluctuation or raw material, Ca impurity increases suddenly, therefore common practice is still It is to maintain an anti-protection lower reactivity of reactor catalyst, main function intercepts and deposit the impurity and dirt in raw material Object only carries out lower demetalization reaction, and the usually reactor reaction temperature rise is lower, and pressure drop maintains in the whole service period In lower level, this requires that loading a large amount of catalyst for demetalation in subsequent demetalization reactor is substantially carried out de- gold Belong to reaction and provide enough spaces to accommodate the metallic compound of hydrogenation and removing and carbon distribution, inevitably causes in this way The demetalization reactor deposits a large amount of metal, and demetalization reaction load is larger, usually the reactor reaction temperature rise highest, to the greatest extent Pipe initial operating stage reactor pressure decrease is lower, but the pressure drop to operation to the mid-term or later period pressure drop reactor at first increases It is long, and growth is most fast, becomes the principal element for restricting the cycle of operation.

The present invention provides a kind of processing method of heavy charge, and the processing method includes the following contents:

(1) slurry oil of heavy charge and at least partly catalytic cracking unit is mixed into fluidized bed reactor, in hydrogen and In the presence of boiling bed hydrogenation treatment catalyst, boiling bed hydrogenation processing is carried out；

(2) freshening of boiling bed hydrogenation processing reaction effluent obtained in step (1), at least partly catalytic cracking unit Oil successively handles reaction zone by the fixed bed hydrogenation pretreatment reaction area being arranged in series and fixed bed hydrogenation after mixing with hydrogen It is reacted；

(3) in step (2) fixed bed hydrogenation processing reaction zone obtain generation oil as catalytic cracking unit raw material into Enter catalytic cracking unit, the catalytic cracking reaction product that catalytic cracking unit fractionating column obtains include gasoline fraction, diesel oil distillate, Recycle oil and slurry oil；

Wherein, fixed bed hydrogenation pretreatment reaction area described in step (2) includes that at least two is being arranged in parallel plus hydrogen is pre- Treatment reactor, when the pressure drop of any one weighted BMO spaces reactor in fixed bed hydrogenation pretreatment reaction area reaches pre- When definite value, the weighted BMO spaces reactor that pressure drop reaches predetermined value is cut out from fixed bed hydrogenation pretreatment reaction area, and will Fixed bed hydrogenation pretreatment reaction area, the pressure drop reach the weighted BMO spaces reactor of predetermined value and the fixed bed adds Hydrogen processing reaction zone is connected in turn in series, wherein and the predetermined value designs the 50%~80% of the upper limit for pressure drop, Preferably 60%~70%.

In the processing method of the heavy charge, in the reaction initial stage, fixed bed hydrogenation pretreatment reaction area Setting 3~6, is preferably provided with 3~4 weighted BMO spaces reactors being arranged in parallel.

In the preferred case, when the pressure drop of a weighted BMO spaces reactor reaches the predetermined value, this plus hydrogen is pre- Treatment reactor is cut out from fixed bed hydrogenation pretreatment reaction area, which is named as to cut out plus hydrogen Preatreating reactors I, and by fixed bed hydrogenation pretreatment reaction area, the weighted BMO spaces reactor I cut out and institute It states fixed bed hydrogenation processing reaction zone to be connected in turn in series, at this time the weighted BMO spaces reactor I cut out Charging be remaining all weighted BMO spaces reactors in parallel reaction effluent；When next weighted BMO spaces reactor When pressure drop reaches the predetermined value, which is cut out from fixed bed hydrogenation pretreatment reaction area, by this Weighted BMO spaces reactor is named as the weighted BMO spaces reactor II cut out, and by the fixed bed hydrogenation pretreatment reaction Area, the weighted BMO spaces reactor II cut out, at the weighted BMO spaces reactor I and the fixed bed hydrogenation cut out Reason reaction zone is connected in turn in series；In the manner described above, until all weighted BMO spaces reactors are whole All it is connected in series to.

In the processing method of the heavy charge, all weighted BMO spaces are anti-in fixed bed hydrogenation pretreatment reaction area The pressure drop of device is answered not reach predetermined value simultaneously, it is two neighboring to reach closest to the weighted BMO spaces reactor for reaching pressure drop predetermined value 20% of the time difference of its pressure drop predetermined value not less than the whole device cycle of operation, preferably 20~60%.

In the processing method of the heavy charge, pass through the setting of operating condition and/or the difference of catalyst bed property It is different so that each weighted BMO spaces reactor does not reach pressure drop predetermined value simultaneously in fixed bed hydrogenation pretreatment reaction area, for example, Can by control catalyst packing height different in each weighted BMO spaces reactor, different inlet amounies, it is different into Expect to use one of different Catalyst packing density under the conditions of property, different operating conditions and identical filling height Or various ways make each weighted BMO spaces reactor in fixed bed hydrogenation pretreatment reaction area not reach pressure drop simultaneously to realize Predetermined value.

In the processing method of the heavy charge, when by controlling identical filling in each weighted BMO spaces reactor Under the conditions of height by the way of different Catalyst packing density to realize when, in fixed bed hydrogenation pretreatment reaction area In each weighted BMO spaces reactor in parallel, maximum loading density can be 400kg/m³~600kg/m³, preferably 450kg/ m³~550kg/m³；Minimum loading density can be 300kg/m³~550kg/m³, preferably 350kg/m³~450kg/m³.It is preferred that Ground, the Catalyst packing density difference of the immediate two weighted BMO spaces reactors of loading density are 50kg/m³~200kg/ m³, preferably 80kg/m³~150kg/m³.The difference loading density can be tamped by the way that different types of catalyst grade is equipped It is existing, it can such as realize that each adds in different proportions by hydrogenation protecting agent, Hydrodemetalation catalyst, Hydrobon catalyst Catalyst packing density in hydrogen pretreatment reactor is different.

In the processing method of the heavy charge, when by controlling charging different in each weighted BMO spaces reactor Come when realizing, the ratio between the feed volume air speed of the immediate two weighted BMO spaces reactors of inlet amount can be the mode of amount 1.1 ~ 3:1, preferably 1.1 ~ 1.5:1.

In the processing method of the heavy charge, when by controlling charging different in each weighted BMO spaces reactor The mode of property is come when realizing, the tenor difference of the immediate two weighted BMO spaces reactors of feed properties can be 5 μ The μ g/g of g/g ~ 50, preferably 10 μ of μ g/g ~ 30 g/g.

In the processing method of the heavy charge, when by controlling operation different in each weighted BMO spaces reactor The mode of condition controls the operation item of operating pressure and the immediate two weighted BMO spaces reactors of volume space velocity come when realizing In part, operation temperature difference can be 2 DEG C ~ 30 DEG C, preferably 5 DEG C ~ 20 DEG C；Or control operating pressure and operation temperature most connect In the operating condition of two close weighted BMO spaces reactors, volume space velocity difference is 0.1 h^-1~10 h^-1, preferably 0.2 h^-1 ~5 h^-1。

In the processing method of the heavy charge, according to Flow of Goods and Materials direction, in each weighted BMO spaces reactor according to Secondary filling hydrogenation protecting agent, Hydrodemetalation catalyst and optional Hydrobon catalyst；The hydrotreating reaction area Reactor successively load Hydrobon catalyst and hydrodenitrogeneration carbon residue reforming catalyst.

In the processing method of the heavy charge, the operating condition in fixed bed hydrogenation pretreatment reaction area are as follows: temperature Degree is 370 DEG C~420 DEG C, preferably 380 DEG C~400 DEG C；Pressure is 10MPa~25MPa, preferably 15MPa~20MPa；Hydrogen Oil volume ratio is 300~1500, preferably 500~800；Volume space velocity is 0.15h when raw material oil liquid^-1~2h^-1, preferably 0.3h^-1~1h^-1.The residuum hydrogenating and metal-eliminating that the average reaction temperature of weighted BMO spaces reaction zone is apparently higher than the prior art is anti- The reaction temperature of device is answered, the residuum hydrogenating and metal-eliminating reaction temperature of the prior art is usually 350 DEG C~390 DEG C.Before in this method The fixed bed hydrogenation pretreatment reaction area of portion's setting eliminates pressure drop and increases the stable fortune of limits device by the optimization of process flow The unfavorable factor of turn-week phase can operate at high temperature, and in addition relatively high reaction temperature is conducive to loaded caltalyst It is the performance of performance, is conducive to the removing of the hydro-conversion and impurity of macromolecular.

In the processing method of the heavy charge, the fixed bed hydrogenation processing reaction zone may include 1~5 series connection The hydrotreating reactor of setting preferably includes 1~2 hydrotreating reactor being arranged in series.

In the processing method of the heavy charge, the operating condition of the fixed bed hydrogenation processing reaction zone are as follows: temperature It is 370 DEG C~430 DEG C, preferably 380 DEG C~410 DEG C；Pressure is 10MPa~25MPa, preferably 15MPa~20MPa；Hydrogen oil Volume ratio is 300~1500, preferably 400~800；Volume space velocity is 0.15h when raw material oil liquid^-1~0.8h^-1, preferably 0.2h^-1~0.6h^-1。

In the processing method of the heavy charge, heavy charge involved in step (1) includes what crude distillation obtained The inferior heavy oil in decompression residuum or other sources, the tenor in heavy charge are at least 120 μ g/g, preferably 180 μ g/g More than, most preferably 220 μ g/g or more.

In the processing method of the heavy charge, fluidized bed reactor as described in step (1) can use existing skill Conventional fluidized bed reactor in art.The fluidized bed reactor that can be set 1 or more is preferably provided with 1 or 2 and is arranged in series Fluidized bed reactor is arranged in series the reactor for referring to that reaction mass passes sequentially through setting.Boiling bed hydrogenation treatment conditions can root According to feedstock property and reaction conversion ratio require it is specific determine, generally are as follows: reaction temperature is 370~450 DEG C, preferably 380~430 ℃；Reaction pressure is 8~25MPa, preferably 8.0~16MPa；Hydrogen to oil volume ratio 100:1 ~ 1000:1, preferably 500:1 ~ 1000:1；Liquid volume air speed (LHSV) is 0.3~5.0h^-1, preferably 0.3-2.0h^-1；Boiling bed hydrogenation processing is not with conversion Rate (lighting) and desulfurization removing nitric are main target, but it is main that by fixed bed hydrogenation of demetalization, processing, which provides qualified charging, Target, tenor requires to be lower than 100 μ g/g, preferably shorter than 80 μ g/g in product liquid after boiling bed hydrogenation processing reaction, most Preferably shorter than 60 μ g/g.

Due to containing a large amount of resin and asphalt, and asphalitine in the de-oiled asphalt of boiling bed hydrogenation processing unit processing Chemical structure it is extremely complex, be made of polymerization aromatic hydrocarbons, alkane chain, cycloalkane, molecular weight is very big, mean molecule size about 6 ~9nm.Also containing the hetero atoms such as sulphur, nitrogen, metal in structure of asphaltene, 80%~90% metal is enriched in asphalitine in crude oil In.These impurity " hide " portion in the molecule deeply, and needing could imurity-removal under harsh operating condition.Asphalitine is adding hydrogen The resolution ratio of process and the aperture of used catalyst are related.Catalyst aperture is at least greater than 10nm, and asphalitine is possible to spread Into catalyst duct.Therefore there must be more macropore to boiling-bed catalyst.Boiling bed hydrogenation treatment reactor of the present invention Boiling bed hydrogenation catalyst specific surface is 80~200m²/ g, the Kong Rong of 30~300nm of bore dia account for the 35%~60% of total pore volume (mercury injection method), the average pore diameter of catalyst are 20nm or more, preferably 22 ~ 40nm.In catalyst, by weight, catalyst Containing VI B family metal oxide (such as MoO₃) 1.0%~10.0%, preferably 1.5%~8.5%, oxide containing group VIII metal is (such as NiO or CoO) 0.1%~8.0%, preferably 0.5%~5.0%.Carrier can be aluminium oxide, aluminium oxide-silicon oxide, aluminium oxide-oxygen Change the one or more of titanium, the shape of catalyst can be bar shaped or spherical shape, and particle diameter is 0.1~0.8mm.

In the processing method of the heavy charge, fixed bed hydrogenation pretreatment reaction area involved in step (2) is used Raw material be ebullated bed reaction effluent and catalytic cracking recycle oil, can also be added other is suitable for using at fixed bed The heavy charge of reason.Tenor in the liquid phase feeding of fixed bed hydrogenation processing will be lower than 100 μ g/g, preferably shorter than 80 μ g/ g。

In the processing method of the heavy charge, into fluidized bed reactor catalytic cracked oil pulp can be all or Part, catalytic cracked oil pulp can first isolate solid impurity, can also be directly entered fluidized bed reactor, catalytic cracked oil pulp The 20% of fluidized bed reactor combined feed weight is typically constituted from hereinafter, generally 2%~20%, preferably 5%~10%.Into fixed bed Catalytic cracking recycle oil can be all or part, catalytic cracking recycle oil can also first remove solid impurity, can also be with boiling The modes imurity-removal such as filter or sump is taken again after rising a reactor reaction effluent mixing, into fixed bed reactors Catalytic cracking recycle oil typically constitute from the 30% of fixed bed combined feed weight hereinafter, generally 5%~30%, preferably 10%~20%.

In the processing method of the heavy charge, catalytic cracking can use this field routine techniques.Catalytic cracking dress Setting can be more than a set of or a set of, and every covering device at least should include a reactor, a regenerator.Catalytic cracking unit is set Fractionating column is set, can be set separately, can also be shared with every set catalytic cracking unit.Catalytic cracking fractionating tower is by catalytic cracking reaction Effluent fractionation is dry gas, liquefied gas, catalytically cracked gasoline, recycle oil and slurry oil etc..Catalytic cracking unit is by this field Conditional operation: reaction temperature is generally 450~600 DEG C, preferably 480~550 DEG C；Regeneration temperature is 600~800 DEG C, best It is 650~750 DEG C, agent oil (catalyst and feedstock oil) weight ratio 2:1~30:1, preferably 4:1~10:1；It is contacted with catalyst Time 0.1~15 second, best 0.5~5 second；0.1~0.5MPa of pressure.Used catalytic cracking catalyst includes being commonly used in The catalyst of catalytic cracking, the carclazyte and X-type, Y type, ZSM-5, M type, layer handled such as silica-alumina catalyst, silica-magneia cataslyst, acid The molecular sieve cracking catalysts such as column, preferably molecular sieve cracking catalyst, this is because the activity of molecular sieve cracking catalyst is high, Green coke is few, and gasoline yield is high, high conversion rate.The reactor of the catalytic cracking unit can be the catalytic cracking of various types Reactor, preferably riser reactor or riser add bed reactor.Process flow is general are as follows: feedstock oil is anti-from riser It answers device bottom to inject, contacts with the high-temperature regenerated catalyst from regenerator, the oil gas and deposit coke that cracking reaction generates Catalyst mixture is moved up along riser reactor, completes the catalytic cracking reaction of entire feedstock oil.

In the processing method of the heavy charge, it can specifically be determined according to raw material sources property and processing request specific Process conditions, the optimization and determination of process conditions are contents well known to those skilled in the art.

In the processing method of the heavy charge, the catalytic cracking recycle oil into fixed bed reactors can be carried out first Solid impurity processing is removed, carries out de- solid impurity processing after can also mixing with fluidized bed reactor reaction effluent again, so After enter back into fixed bed reactors.

Compared with prior art, the processing method of the heavy charge provided by the invention has the advantages that

(1) in the method for the present invention, fluidized bed reactor generally only needs setting one, its purpose is that fixed bed hydrogenation reactor Pretreatment of raw material is carried out, needs the operation purpose of higher conversion different from current boiling bed residual oil hydrogen addition technology, reduces and set Standby investment, combines the comprehensive advantage of fixed bed and ebullated bed, avoids conventional fluidized bed reactor in high conversion operation Obtained residual oil (after fractionating out light fraction) quality is worse, is not suitable for the problem of bed hydroprocessing processing is fixed again.

It (2) include multiple weighted BMO spaces reactors in parallel in fixed bed hydrogenation pretreatment reaction area, so that whole A catalyst system takes off/holds metal ability and is increased dramatically.

(3) in the processing method of heavy charge of the present invention, when the pressure drop of a weighted BMO spaces reactor increases When to predetermined value, it is cut out from fixed bed hydrogenation pretreatment reaction area, and by the change of process flow, make its pressure drop no longer Rapid growth, but slowly increase can control in range until device is stopped work, and then makes some weighted BMO spaces reactor Pressure drop will not restrict cycle of operation of whole device.

(4) in the processing method of heavy charge of the present invention, by will in fixed bed hydrogenation pretreatment reaction area it is each To solve weighted BMO spaces reactor pressure decrease fast from the adjustment for being parallel to series connection handover operation mode for a weighted BMO spaces reactor The problem that speed increases, while increasing the operating flexibility and raw material adaptability of device.

(5) in the processing method of heavy charge of the present invention, by the way that weighted BMO spaces reactor parallel form is arranged The appearance amount of metal of catalyst system is significantly increased, so that the stability of system enhances, the growth of device pressure drop is obtained Control extends the device cycle of operation.

(6) processing method of heavy charge of the present invention can utmostly realize the synchronous inactivation of all kinds of catalyst, To improve the operational efficiency of device, increase economic efficiency.

(7) in the processing method of heavy charge of the present invention, by weighted BMO spaces reaction zone catalyst performance With optimizing and revising for technological parameter, the cooperation of carbon residue catalyst is taken off with subsequent high activity desulfurization, so that improving whole catalysis Desulfurization takes off carbon residue performance and is guaranteed while de-/appearance metal ability of agent.

(8) in the processing method of heavy charge of the present invention, by the way that catalytic cracked oil pulp circulation is added to boiling In bed reactor, diluting effect can be played to de-oiled asphalt, improve its property, reduced boiling bed residual oil and add hydrogen anti- Answer difficulty and processing severity；Heavy catalytic cycle oil can be in the further imurity-removal of fixed bed hydrogenation reaction zone, and aromatic hydrocarbons is full With, be conducive to improve catalytic cracking product quality.

Detailed description of the invention

Fig. 1 is the processing method flow diagram of heavy charge of the present invention.

Fig. 2 is that fixed bed hydrogenation pretreatment reaction area and fixed bed add in the processing method of heavy charge of the present invention The schematic diagram of hydrogen processing reaction zone.

Specific embodiment

Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.

The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.

Fluidized bed reactor boiling bed hydrogenation catalyst specific surface of the present invention is 80~200m²/ g, 30~300nm of bore dia Kong Rong account for 35%~60%(mercury injection method of total pore volume), the average pore diameter of catalyst is 20nm or more, preferably 22 ~ 40nm. In catalyst, by weight, catalyst contains VI B family metal oxide (such as MoO₃) 1.0%~10.0%, preferably 1.5%~ 8.5%, oxide containing group VIII metal (such as NiO or CoO) 0.1%~8.0%, preferably 0.5%~5.0%.Carrier can be oxidation Aluminium, aluminium oxide-silicon oxide, the one or more of aluminium oxide-titanium oxide, the shape of catalyst can be bar shaped or spherical shape, particle Diameter is 0.1~0.8mm.

In heavy charge processing method of the present invention, fixed bed preatreating reactors area's predetermined value is pressure drop Design the upper limit 50%~80%, for example, 50%, 52%, 54%, 55%, 56%, 57%, 58%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 74%, 75%, 76%, 78%, 80% and model composed by any two value in them Arbitrary value between enclosing.In the preferred case, the predetermined value designs the 60%~70% of the upper limit for pressure drop.In the present invention, institute The maximum value that the pressure drop design upper limit refers to reactor pressure decrease is stated, when reactor pressure decrease reaches the value, reaction system needs to stop work, The pressure drop design upper limit is usually the MPa of 0.7 MPa ~ 1.

In heavy charge processing method of the present invention, the pressure drop of all fixed bed hydrogenation preatreating reactors is not Reach predetermined value simultaneously.In the preferred case, two neighboring to be reached closest to the weighted BMO spaces reactor for reaching pressure drop predetermined value To its pressure drop predetermined value time difference be not less than the whole service period 20%, the preferably 20-60% in whole service period, example Such as, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%.In the present invention, the whole service period refers to that heavy oil adds Hydrogen processing system is from bringing into operation to the time experienced of stopping work.

In heavy charge processing method of the present invention, each plus hydrogen in fixed bed hydrogenation pretreatment reaction area It is residual that hydrogenation protecting agent, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrogeneration can be loaded in preatreating reactors One of charcoal reforming catalyst is a variety of, can load hydrodesulfurization in the reactor of the fixed bed hydrogenation processing reaction zone One of catalyst and hydrodenitrogeneration carbon residue reforming catalyst are a variety of.

In a preferred embodiment, it according to Flow of Goods and Materials direction, is successively loaded in each weighted BMO spaces reactor Hydrogenation protecting agent, Hydrodemetalation catalyst and optional Hydrobon catalyst；The reaction in the hydrotreating reaction area Device successively loads Hydrobon catalyst and hydrodenitrogeneration carbon residue reforming catalyst.It is filled according to the catalyst of the preferred embodiment Embankment formula, so that de-/appearance metal ability of whole system is increased dramatically, while the adjustment matched by catalyst grade is so that each The pressure drop of a weighted BMO spaces reactor increases in control range.In fixed bed hydrogenation pretreatment reaction area it is in parallel each plus The catalyst system of hydrogen pretreatment reactor filling with it is de-/hold based on metal function so that while demetalization performance boost, by force Change the ability to the hydro-conversion of such as gum asphalt of macromolecular in raw material, establishes base for successive depths desulfurization and the conversion of carbon residue Plinth, so that hydrodesulfurizationreaction reaction zone is conducive to further deep reaction, therefore, compared with routine techniques, side of the present invention Although the ratio of Hydrodemetalation catalyst improves in method, the hydro-conversion of whole desulphurizing activated and carbon residue Performance is not only improved without reducing instead.

In the present invention, the hydrogenation protecting agent, the Hydrodemetalation catalyst, the Hydrobon catalyst and institute Stating hydrodenitrogeneration carbon residue reforming catalyst all can be the conventional use of catalyst of fixed bed heavy-oil hydrogenation treatment process.These are urged Agent usually with porous refractory inorganic oxide (such as aluminium oxide) for carrier, group VIB and/or group VIII metal (such as W, Mo, Co, Ni etc.) oxide be active component, be selectively added the catalyst of the elements such as various other auxiliary agents such as P, Si, F, B. For example, the FZC series heavy oil hydrogenating treatment catalyst produced by Sinopec Group's catalyst branch.

In heavy charge processing method of the present invention, the heavy oil feedstock can be the decompression that crude distillation obtains The inferior heavy oil in residual oil or other sources, the tenor in heavy oil feedstock are at least 120 μ g/g, preferably 180 μ g/g or more, Most preferably 220 μ g/g or more.

Heavy charge processing method of the present invention is further described below with reference to Fig. 1, Fig. 2, but not because This and limit the present invention., fixed bed hydrogenation processing reaction zone generation oil M2

As shown in Figure 1 and Figure 2, the processing method of heavy charge of the present invention includes following content: heavy charge M1 is pre- After heat with from catalytic cracking unit R5 catalytic cracked oil pulp M9 and hydrogen M2 mix after enter fluidized bed reactor R1, boiling Carry out hydrogenation reaction under bed hydrogenation catalyst and process conditions, the hetero atoms such as removing metal, sulphur, make asphalitine be converted into colloid or More small molecule reduces product viscosity.Ebullating bed reactor effluent M3 and FCC recycle oil M8 and hydrogen from catalytic cracking unit The material M10 obtained after gas M2 mixing enters fixed bed hydrogenation device R2, and hydrogenation reaction is carried out under catalyst and reaction condition, Reaction effluent M4 is obtained, is further separated in gas-liquid separator R3, is made after the isolated further depriving hydrogen sulphide of gas phase M5 Reaction system, reaction raw materials of the isolated liquid phase directly as catalytic cracking unit, catalytic cracking are recycled back to for recycle hydrogen Device includes catalyst cracker R4 and catalytic cracking fractionating tower R5, obtains gasoline M6, bavin after catalytic cracking fractionating tower separation Oily M7, recycle oil M8 and slurry oil M9.Ebullating bed reactor effluent enters back into after can entering filter SR after mixing with recycle oil Fixed bed reactors remove solid impurity that may be present etc..Above-mentioned apparatus is a serial process flow, is advised according to device Two or more series can be set side by side in the requirement of mould.Fixed bed hydrogenation reaction zone R2 includes that the fixed bed of tandem adds Hydrogen pretreatment reaction zone and fixed bed hydrogenation handle reaction zone.Fixed bed hydrogenation pretreatment reaction area as shown in Figure 2 includes Three weighted BMO spaces reactors being arranged in parallel, respectively weighted BMO spaces reactor A, weighted BMO spaces reactor B plus hydrogen Preatreating reactors C, the charging of the weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C Mouth is connect with feeding line 1, feeding line 2 and feeding line 3 respectively, three tunnels of outlet point of the weighted BMO spaces reactor A, The first via is connect through pipeline 6 with the feed inlet of weighted BMO spaces reactor B, and the second tunnel is through pipeline 7 and weighted BMO spaces reactor C Feed inlet connection, third road is connect through pipeline 10 with the feed inlet of hydrotreating reactor D；The weighted BMO spaces reactor Three tunnels of the outlet of B point, the first via are connect through pipeline 4 with the feed inlet of weighted BMO spaces reactor A, and the second tunnel is through pipeline 5 and adds Hydrogen pretreatment reactor C obtains feed inlet connection, and third road is connect through pipeline 11 with the feed inlet of hydrotreating reactor D；It is described Three tunnels of the outlet of weighted BMO spaces reactor C point, the first via are connect through pipeline 8 with the feed inlet of weighted BMO spaces reactor A, the Two tunnels are connect through pipeline 9 with the feed inlet of weighted BMO spaces reactor B, and third road is through pipeline 12 and hydrotreating reactor D's Feed inlet connection；It is provided with valve 101 on the pipeline 1, valve 102 is provided on the pipeline 2, is arranged on the pipeline 3 There is valve 103, valve 104 is provided on the pipeline 4, valve 105 is provided on the pipeline 5, is provided on the pipeline 6 Valve 106 is provided with valve 107 on the pipeline 7, valve 108 is provided on the pipeline 8, is provided with valve on the pipeline 9 Door 109 is provided with valve 1010 on the pipeline 10, valve 1011 is provided on the pipeline 11, is arranged on the pipeline 12 There is valve 1012, the generation oil M4 that the hydrotreating reactor obtains enters catalyst cracker and carries out cracking reaction.Institute It states and is each provided in weighted BMO spaces reactor A, the weighted BMO spaces reactor B and the weighted BMO spaces reactor C For monitoring the sensing unit (not shown) of pressure drop, and the heavy-oil hydrogenation processing system further includes control unit (figure In be not shown), add hydrogen pre- with each for receiving the pressure drop signal from the sensing unit, and according to pressure drop signal control The corresponding valve for the treatment of reactor.

In above-mentioned heavy charge processing method, weighted BMO spaces reactor A, weighted BMO spaces reactor B and add hydrogen it is pre- Treatment reactor C can be inactivated in any order, it is preferred to use following six kinds of modes switch over operation:

Mode 1: according to weighted BMO spaces reactor A, weighted BMO spaces reactor B, the sequence of weighted BMO spaces reactor C Reach pressure drop predetermined value.

(1) when going into operation, pipeline 1, pipeline 2, pipeline 3, pipeline 10, pipeline 11, the valve 101 on pipeline 12, valve 102, Valve 103, valve 1010, valve 1011, valve 1012 are opened, pipeline 4, pipeline 5, pipeline 6, pipeline 7, pipeline 8, on pipeline 9 Valve 104, valve 105, valve 106, valve 107, valve 108, valve 109 close；

(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spaces The pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor A reaches predetermined value from the weighted BMO spaces are corresponded to The pressure drop signal of the sensing unit of device A passes to control unit, and control unit is received to execute after the signal and be adjusted to valve Control specifically closes valve 101, the valve 1011 of pipeline 11 and the valve 1012 of pipeline 12 of feeding line 1, opens pipeline 8 On valve 108 and pipeline 4 on valve 104 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor B and plus Hydrogen pretreatment reactor C), weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connection To concatenated handover operation；

(3) it when the pressure drop of weighted BMO spaces reactor B reaches predetermined value, is reacted from the weighted BMO spaces are corresponded to The pressure drop signal of the sensing unit of device B passes to control unit, and control unit is received to execute after the signal and be adjusted to valve Control specifically closes the valve 102 of feeding line 2, the valve 108 of pipeline 8, the valve 109 on pipeline 9 is opened, so that plus hydrogen Preatreating reactors C, weighted BMO spaces reactor B, weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, this When complete the 2nd time by being parallel to concatenated handover operation；

(4) when the pressure drop of weighted BMO spaces reactor C reaches the design upper limit, entire reaction system needs shutdown process.

Mode 2: according to weighted BMO spaces reactor A, weighted BMO spaces reactor C, weighted BMO spaces reactor B sequence Reach pressure drop predetermined value.

(3) it when the pressure drop of weighted BMO spaces reactor C reaches predetermined value, is reacted from the weighted BMO spaces are corresponded to The pressure drop signal of the sensing unit of device C passes to control unit, and control unit is received to execute after the signal and be adjusted to valve Control specifically closes the valve 103 of feeding line 3, the valve 104 of pipeline 4, the valve 105 on pipeline 5 is opened, so that plus hydrogen Preatreating reactors B, weighted BMO spaces reactor C, weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, this When complete the 2nd time by being parallel to concatenated handover operation；

(4) when the pressure drop of weighted BMO spaces reactor C reaches predetermined value, entire reaction system needs shutdown process.

Mode 3: according to weighted BMO spaces reactor B, weighted BMO spaces reactor C, weighted BMO spaces reactor A sequence Reach pressure drop predetermined value.

(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spaces The pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor B reaches predetermined value from the weighted BMO spaces are corresponded to The pressure drop signal of the sensing unit of device B passes to control unit, and control unit is received to execute after the signal and be adjusted to valve Control specifically closes valve 102, the valve 1010 of pipeline 10 and the valve 1012 of pipeline 12 of feeding line 2, opens pipeline 9 On valve 109 and pipeline 6 on valve 106 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor A and plus Hydrogen pretreatment reactor C), weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connection To concatenated handover operation；

(3) it when the pressure drop of weighted BMO spaces reactor C reaches predetermined value, is reacted from the weighted BMO spaces are corresponded to The pressure drop signal of the sensing unit of device C passes to control unit, and control unit is received to execute after the signal and be adjusted to valve Control specifically closes the valve 103 of feeding line 3, the valve 106 of pipeline 6, the valve 107 on pipeline 7 is opened, so that plus hydrogen Preatreating reactors A, weighted BMO spaces reactor C, weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, this When complete the 2nd time by being parallel to concatenated handover operation；

(4) when the pressure drop of weighted BMO spaces reactor A reaches predetermined value, entire reaction system needs shutdown process.

Mode 4: according to weighted BMO spaces reactor B, weighted BMO spaces reactor A, the sequence of weighted BMO spaces reactor C Reach pressure drop predetermined value.

(3) it when the pressure drop of weighted BMO spaces reactor A reaches predetermined value, is reacted from the weighted BMO spaces are corresponded to The pressure drop signal of the sensing unit of device A passes to control unit, and control unit is received to execute after the signal and be adjusted to valve Control specifically closes the valve 101 of feeding line 1, the valve 109 of pipeline 9, the valve 108 on pipeline 8 is opened, so that plus hydrogen Preatreating reactors C, weighted BMO spaces reactor A, weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, this When complete the 2nd time by being parallel to concatenated handover operation；

Mode 5: according to weighted BMO spaces reactor C, weighted BMO spaces reactor B, the sequence of weighted BMO spaces reactor A Reach pressure drop predetermined value.

(2) it is reacted with sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spaces The pressure drop of device C is reacted when the pressure drop of weighted BMO spaces reactor C reaches predetermined value from the weighted BMO spaces are corresponded to The pressure drop signal of the sensing unit of device C passes to control unit, and control unit is received to execute after the signal and be adjusted to valve Control specifically closes valve 103, the valve 1010 of pipeline 10 and the valve 1011 of pipeline 11 of feeding line 3, opens pipeline 7 On valve 107 and pipeline 5 on valve 105 so that weighted BMO spaces reaction zone (including weighted BMO spaces reactor A and plus Hydrogen pretreatment reactor B), weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by parallel connection To concatenated handover operation；

(3) it when the pressure drop of weighted BMO spaces reactor B reaches predetermined value, is reacted from the weighted BMO spaces are corresponded to The pressure drop signal of the sensing unit of device B passes to control unit, and control unit is received to execute after the signal and be adjusted to valve Control specifically closes the valve 102 of feeding line 2, the valve 107 of pipeline 7, the valve 106 on pipeline 6 is opened, so that plus hydrogen Preatreating reactors A, weighted BMO spaces reactor B, weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, this When complete the 2nd time by being parallel to concatenated handover operation；

Mode 6: according to weighted BMO spaces reactor C, weighted BMO spaces reactor A, the sequence of weighted BMO spaces reactor B Reach pressure drop predetermined value.

(3) it when the pressure drop of weighted BMO spaces reactor A reaches predetermined value, is reacted from the weighted BMO spaces are corresponded to The pressure drop signal of the sensing unit of device A passes to control unit, and control unit is received to execute after the signal and be adjusted to valve Control specifically closes the valve 101 of feeding line 1, the valve 105 of pipeline 5, the valve 104 on pipeline 4 is opened, so that plus hydrogen Preatreating reactors B, weighted BMO spaces reactor A, weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, this When complete the 2nd time by being parallel to concatenated handover operation；

(4) when the pressure drop of weighted BMO spaces reactor B reaches predetermined value, entire reaction system needs shutdown process.

Illustrate effect of the invention below with reference to specific embodiment, it is used in embodiment of the present invention and comparative example Raw material includes three kinds, and respectively raw material A, raw material B, raw material C, specific nature is shown in Table 1, and boiling bed hydrogenation cracking reaction area is set 1 boiling bed hydrogenation cracker is set, the catalyst loaded in the boiling bed hydrogenation cracker is boiling bed hydrogenation Catalyst.

The type of feed of catalyst is shown in Table 2 in the Examples 1 to 4, the filling side of catalyst in the comparative example 1~4 Formula is shown in Table 3, and the reaction condition of the Examples 1 to 4 is shown in Table 4, and the reaction condition of the comparative example 1~4 is shown in Table 5, the implementation The reaction result of example 1~4 and comparative example 1~4 is shown in Table 6.Using conventional tandem process, other difference in the comparative example 1-4 It is corresponding identical as Examples 1 to 4.Weighted BMO spaces reactor A described in the embodiment of the present invention, weighted BMO spaces reactor B, Weighted BMO spaces reactor C is pattern, the identical reactor of size, reactor A, reactor B, reactor in the comparative example C is pattern, the identical reactor of size.

Slag is carried out using ebullated bed, fixed bed and the catalytic cracking combined technique in residual hydrocracking in the method for the present invention Oily hydro-conversion.Residual oil raw material is mixed with catalytic cracked oil pulp first and is mixed into boiling bed hydrogenation processing with hydrogen after preheating Device carries out hydrogenation reaction under prepared different boiling bed hydrogenation catalysts mixing and process conditions, removes in raw material Hetero atoms such as sulphur, nitrogen, metal, while asphalitine being made to be converted into colloid or more small molecule, reduce product viscosity, hydrogenation products with urge Change cracking recycle oil enters fixed bed hydrogenation device and is reacted, and is generated under fixed bed gradation catalyst and reaction condition Oil.The generation oil enters the further cracking of catalytic cracking unit and is converted into dry gas, catalytically cracked gasoline, catalytic cracking diesel oil, urges Change cracking recycle oil and catalytic cracked oil pulp, catalytic cracking recycle oil is recycled into fixed bed reactors after filtering and is carried out Hydrogenation reaction, catalytic cracked oil pulp are recycled into fluidized bed reactor after filtering and carry out hydrogenation reaction.

Boiling bed hydrogenation treatment catalyst can be needed according to performance using existing method prepare, such as with reference to US7074740, The prior art preparations such as US5047142, US4549957, US4328127, CN200710010377.5.The property of catalyst compares table Area 142m²/ g, Kong Rong 1.45mL/g(mercury injection method), the Kong Rong of 30~300nm of bore dia accounts for the 52%(mercury injection method of total pore volume), MoO₃Content is that 6.02%, NiO content is 1.54%, spherical particle diameters 0.4mm.Catalytic cracking in fluidized bed reactor charging Slurry oil accounts for 8wt%(weight, similarly hereinafter).Catalytic cracking recycle oil accounts for 10wt%(weight in the charging of fixed bed hydrogenation device, similarly hereinafter).

Boiling bed hydrogenation catalyst prepares the spherical carrier of catalyst that average pore size is 13nm, and spherical catalyst particles are 0.1-0.3mm, other catalyst preparation process are carried out referring to US7074740 and CN200710010377.5 method.Routinely side Method prepares Mo-Co-P solution, MoO in solution₃Quality meter content is 18.00%, and content is that 3.50%, P mass contains in terms of CoO mass Amount is 1.05%.Above-mentioned carrier, which is impregnated, by incipient impregnation method with the solution obtains final catalyst.

Catalytic cracking catalyst is the catalyst that 3,500,000 tons/year of heavy oil catalytically cracking equipments of Dalian Company use, For industrial equilibrium catalyst.Its fresh dose composition are as follows: 95wt%LBO-16 olefine lowering catalyst+5wt%LBO-A improves octane number and helps Agent.

Raw material oil nature used in the embodiment of the present invention and comparative example is shown in Table 1.Catalyst in embodiment 1- embodiment 3 Type of feed is shown in Table 2, and process conditions are shown in Table 3 and 4, and reaction result is shown in Table 5 and table 10.Catalyst in comparative example 1- comparative example 3 Type of feed is shown in Table 6, and process conditions are shown in Table 7 and 8, and reaction result is shown in Table 9 and table 10.

Embodiment 1

Fixed bed pre-processing hydrogenated of residue petroleums reactor is formed by three in the fixed bed reaction area, is respectively plus hydrogen is located in advance Reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C are managed, the weighted BMO spaces reactor A plus hydrogen are located in advance It is identical with inlet amount to manage reactor B, the catalyst inventory of weighted BMO spaces reactor C, feed properties, described plus hydrogen is pre- Treatment reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C, hydrodesulphurisatioreactors reactors D catalyst according to table Mode in 2 is loaded.

Embodiment 2

In embodiment 2, the weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C are each Anti- Feed space velocities are different, and volume space velocity is 0.20h when the weighted BMO spaces reactor A liquid^-1, weighted BMO spaces reactor B liquid When volume space velocity be 0.32h^-1, volume space velocity is 0.44h when weighted BMO spaces reactor C liquid^-1.Weighted BMO spaces reactor A, Identical catalyst loading pattern, catalyst loading pattern are used in weighted BMO spaces reactor B, weighted BMO spaces reactor C It is shown in Table 2.

Embodiment 3

In embodiment 3, the weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C into Doses is identical.The weighted BMO spaces reactor A average reaction temperature is 370 DEG C, weighted BMO spaces reactor B is average anti- The average response that answering temperature is 378 DEG C, weighted BMO spaces reactor C average reaction temperature is 383 DEG C, hydrodesulphurisatioreactors reactors D Temperature is 383 DEG C, and catalyst loading pattern is shown in Table 2.

Residual oil is carried out using ebullated bed, fixed bed and the catalytic cracking combined technique in residual hydrocracking in comparative example 1 Hydro-conversion.Unlike all reactors in fixed bed hydrogenation pretreatment reaction area use traditional cascade, and with add hydrogen Treatment reactor series connection.Fixed bed catalyst totality admission space is consistent with embodiment, and catalyst grade is matched according to products material Matter adjusts accordingly.Catalytic cracked oil pulp accounts for 8wt% in fluidized bed reactor charging.It is catalyzed in the charging of fixed bed hydrogenation device Cracking recycle oil accounts for 10wt%.

Comparative example 1

Ebullating bed reactor condition in comparative example 1 is same as Example 1.Also 4 reactors are used in comparative example 1, respectively For reactor A, reactor B, reactor C, reactor D, reactor A, reactor B, reactor C and reactor D are used and are successively gone here and there The form of connection connects.Raw material property is shown in Table 1 in comparative example 1, inlet amount and feed properties and the embodiment 1 of reactor A Total feed is identical with feed properties.The reactor A, reactor B, reactor C and reactor D catalyst inventory Weighted BMO spaces reactor A corresponding with embodiment 1, weighted BMO spaces reactor B, weighted BMO spaces reactor C, hydrodesulfurization are anti- Answer device D identical, but the loadings of various species catalyst are different, load in the way of in table 6.

Comparative example 2

Ebullating bed reactor condition in comparative example 2 is same as Example 2.Also 4 reactors are used in comparative example 2, respectively For reactor A, reactor B, reactor C, reactor D, reactor A, reactor B, reactor C and reactor D are used and are successively gone here and there The form of connection connects.1 is shown in Table using feedstock property in comparative example 2, reactor A entrance and embodiment 2 total inlet amount and charging Property is identical.The reactor A, reactor B, the catalyst inventory of reactor C and reactor D are corresponding with embodiment 2 Weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C, hydrodesulphurisatioreactors reactors D it is identical, But the loadings of various species catalyst are different, load in the way of in table 6.

Comparative example 3

Ebullating bed reactor condition and embodiment 3 in comparative example 3 is consistent.Also 4 reactors are used in comparative example 3, respectively For reactor A, reactor B, reactor C, reactor D, reactor A, reactor B, reactor C and reactor D are used and are successively gone here and there The form of connection connects.Reactor A entrance is identical as the total inlet amount of embodiment 3 and feed properties.The reactor A, reactor B, the catalyst inventory of reactor C and reactor D weighted BMO spaces reactor A corresponding with embodiment, weighted BMO spaces reaction Device B, weighted BMO spaces reactor C, hydrodesulphurisatioreactors reactors D are identical, but the loadings of various species catalyst are different, It is loaded in the way of in table 6.

1 feedstock property of table

Catalyst loading pattern in 2 1~embodiment of embodiment 3 of table

3 embodiment 1- embodiment of table, 3 process conditions

The reaction condition in fixed bed reaction area in 4 1~embodiment of embodiment 3 of table

5 fixed bed hydrogenation of table generates oil nature

Catalyst loading pattern in 6 comparative example 1~3 of table

7 group technology experimental condition of table

The reaction condition of 8 comparative example 1~3 of table

9 comparative example 1- comparative example of table, 3 fixed bed hydrogenation generates oil nature

10 embodiment of table and comparative example steady running period compare

Can be seen that the method for the present invention from the stability experiment result of above-mentioned fixed bed reaction system may be implemented fixed bed The long period steady running of hydrotreater.

Claims

1. a kind of processing method of heavy charge, the processing method includes the following contents:

(1) slurry oil of heavy charge and at least partly catalytic cracking unit is mixed into fluidized bed reactor, in hydrogen and boiling In the presence of bed hydroprocessing handles catalyst, boiling bed hydrogenation processing is carried out；

(2) boiling bed hydrogenation obtained in step (1) processing reaction effluent, at least partly catalytic cracking unit recycle oil with It is successively carried out by the fixed bed hydrogenation pretreatment reaction area being arranged in series and fixed bed hydrogenation processing reaction zone after hydrogen mixing Reaction；

(3) the generation oil that fixed bed hydrogenation processing reaction zone obtains in step (2) enters as the raw material of catalytic cracking unit urges Change cracking unit, the catalytic cracking reaction product that catalytic cracking unit fractionating column obtains includes gasoline fraction, diesel oil distillate, freshening Oil and slurry oil；

Wherein, fixed bed hydrogenation pretreatment reaction area described in step (2) includes at least two weighted BMO spaces being arranged in parallel Reactor, when the pressure drop of any one weighted BMO spaces reactor in fixed bed hydrogenation pretreatment reaction area reaches predetermined value When, the weighted BMO spaces reactor that pressure drop reaches predetermined value is cut out from fixed bed hydrogenation pretreatment reaction area, and will be described Fixed bed hydrogenation pretreatment reaction area, the pressure drop reach at the weighted BMO spaces reactor and the fixed bed hydrogenation of predetermined value Reason reaction zone is connected in turn in series, wherein the predetermined value designs the 50%~80% of the upper limit for pressure drop.

2. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: the predetermined value designs for pressure drop The 60%~70% of limit.

3. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: it is reacting the initial stage, it is described solid 3~6 weighted BMO spaces reactors being arranged in parallel are arranged in fixed bed weighted BMO spaces reaction zone.

4. according to the processing method of heavy charge described in claim 1 or 3, it is characterised in that: it is reacting the initial stage, it is described 3~4 weighted BMO spaces reactors being arranged in parallel are arranged in fixed bed hydrogenation pretreatment reaction area.

5. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: when a weighted BMO spaces reactor Pressure drop when reaching the predetermined value, which is cut out from fixed bed hydrogenation pretreatment reaction area, will The weighted BMO spaces reactor is named as the weighted BMO spaces reactor I cut out, and by the fixed bed hydrogenation pretreatment reaction Area, the weighted BMO spaces reactor I cut out and fixed bed hydrogenation processing reaction zone are sequentially connected in series Get up, the charging of the weighted BMO spaces reactor I cut out at this time is the anti-of remaining all weighted BMO spaces reactors in parallel Answer effluent；When the pressure drop of next weighted BMO spaces reactor reaches the predetermined value, by the weighted BMO spaces reactor It is cut out from fixed bed hydrogenation pretreatment reaction area, which is named as to the weighted BMO spaces reaction cut out Device II, and by fixed bed hydrogenation pretreatment reaction area, the weighted BMO spaces reactor II cut out, it is described cut out plus Hydrogen pretreatment reactor I and fixed bed hydrogenation processing reaction zone are connected in turn in series；According to above-mentioned side Formula, until all weighted BMO spaces reactors are all connected in series to.

6. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: fixed bed hydrogenation pretreatment reaction area In the pressure drop of all weighted BMO spaces reactor do not reach predetermined value simultaneously, it is two neighboring closest to reaching pressure drop predetermined value The time difference that weighted BMO spaces reactor reaches its pressure drop predetermined value is not less than the 20% of the whole device cycle of operation.

7. according to the processing method of heavy charge described in claim 1 or 6, it is characterised in that: fixed bed hydrogenation pretreatment is anti- The pressure drop of weighted BMO spaces reactor all in area is answered not reach predetermined value simultaneously, it is two neighboring predetermined closest to pressure drop is reached The time difference that the weighted BMO spaces reactor of value reaches its pressure drop predetermined value is the 20~60% of the whole device cycle of operation.

8. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: by the setting of operating condition and/ Or the difference of catalyst bed property is when making each weighted BMO spaces reactor difference in fixed bed hydrogenation pretreatment reaction area Reach pressure drop predetermined value.

9. the processing method of heavy charge according to claim 8, it is characterised in that: by controlling each weighted BMO spaces Different catalyst packing heights, different inlet amounies, different feed properties, different operating condition and phase in reactor Add fixed bed using one of different Catalyst packing density or various ways under the conditions of same filling height to realize Each weighted BMO spaces reactor does not reach pressure drop predetermined value simultaneously in hydrogen pretreatment reaction zone.

10. the processing method of heavy charge according to claim 9, it is characterised in that: when pre- by controlling each plus hydrogen In treatment reactor under the conditions of identical filling height by the way of different Catalyst packing density to realize when, described In each weighted BMO spaces reactor of fixed bed hydrogenation pretreatment reaction area parallel connection, maximum loading density is 400kg/m³~ 600kg/m³, minimum loading density is 300kg/m³~550kg/m³。

11. the processing method of heavy charge according to claim 10, it is characterised in that: when pre- by controlling each plus hydrogen In treatment reactor under the conditions of identical filling height by the way of different Catalyst packing density to realize when, described In each weighted BMO spaces reactor of fixed bed hydrogenation pretreatment reaction area parallel connection, maximum loading density is 450kg/m³~ 550kg/m³；Minimum loading density is 350kg/m³~450kg/m³。

12. according to the processing method of heavy charge described in claim 10 or 11, it is characterised in that: loading density is immediate The Catalyst packing density difference of two weighted BMO spaces reactors is 50kg/m³~200kg/m³。

13. according to the processing method of heavy charge described in claim 10 or 11, it is characterised in that: loading density is immediate The Catalyst packing density difference of two weighted BMO spaces reactors is 80kg/m³~150kg/m³。

14. the processing method of heavy charge according to claim 9, it is characterised in that: when pre- by controlling each plus hydrogen The mode of different inlet amounies is in treatment reactor come when realizing, the immediate two weighted BMO spaces reactors of inlet amount into Expect that the ratio between volume space velocity is 1.1 ~ 3:1.

15. according to the processing method of heavy charge described in claim 9 or 14, it is characterised in that: when by controlling each add The mode of different inlet amounies is in hydrogen pretreatment reactor come when realizing, the immediate two weighted BMO spaces reactors of inlet amount The ratio between feed volume air speed be 1.1 ~ 1.5:1.

16. the processing method of heavy charge according to claim 9, it is characterised in that: when pre- by controlling each plus hydrogen The mode of different feed properties is in treatment reactor come when realizing, the immediate two weighted BMO spaces reactors of feed properties Tenor difference be 5 μ of μ g/g ~ 50 g/g.

17. according to the processing method of heavy charge described in claim 9 or 16, it is characterised in that: when by controlling each add The mode of different feed properties is in hydrogen pretreatment reactor come when realizing, immediate two weighted BMO spaces of feed properties are anti- The tenor difference for answering device is 10 μ of μ g/g ~ 30 g/g.

18. the processing method of heavy charge according to claim 9, it is characterised in that: when pre- by controlling each plus hydrogen The mode of different operating conditions adds in treatment reactor when realizing, to control operating pressure and volume space velocity immediate two In the operating condition of hydrogen pretreatment reactor, operation temperature difference is 2 DEG C ~ 30 DEG C, or control operating pressure and operation temperature In the operating condition of immediate two weighted BMO spaces reactors, volume space velocity difference is 0.1h^-1~10h^-1。

19. according to the processing method of heavy charge described in claim 9 or 18, it is characterised in that: when by controlling each add The mode of different operating conditions controls operating pressure and volume space velocity immediate two come when realizing in hydrogen pretreatment reactor In the operating condition of platform weighted BMO spaces reactor, operation temperature difference is 5 DEG C ~ 20 DEG C, or control operating pressure and operation In the operating condition of the immediate two weighted BMO spaces reactors of temperature, volume space velocity difference is 0.2 h^-1~5 h^-1。

20. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: each according to Flow of Goods and Materials direction Hydrogenation protecting agent, Hydrodemetalation catalyst and optional hydrodesulfurization catalytic are successively loaded in weighted BMO spaces reactor Agent；The reactor in the hydrotreating reaction area successively loads Hydrobon catalyst and hydrodenitrogeneration carbon residue reforming catalyst.

21. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: the fixed bed hydrogenation pretreatment The operating condition of reaction zone are as follows: temperature be 370 DEG C~420 DEG C, pressure be 10MPa~25MPa, hydrogen to oil volume ratio be 300~ 1500, volume space velocity is 0.15h when raw material oil liquid^-1~2h^-1。

22. according to the processing method of heavy charge described in claims 1 or 21, it is characterised in that: the fixed bed hydrogenation is pre- Handle reaction zone operating condition are as follows: temperature be 380 DEG C~400 DEG C, pressure be 15MPa~20MPa, hydrogen to oil volume ratio be for 500~800, volume space velocity is 0.3h when raw material oil liquid^-1~1h^-1。

23. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: the fixed bed hydrogenation processing is anti- Answering area includes 1~5 hydrotreating reactor being arranged in series.

24. according to the processing method of heavy charge described in claims 1 or 23, it is characterised in that: at the fixed bed hydrogenation Managing reaction zone includes 2 hydrotreating reactors being arranged in series.

25. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: the fixed bed hydrogenation processing is anti- Answer the operating condition in area are as follows: temperature is 370 DEG C~430 DEG C, and pressure is 10MPa~25MPa, and hydrogen to oil volume ratio is 300~1500, Volume space velocity is 0.15h when raw material oil liquid^-1~0.8h^-1。

26. according to the processing method of heavy charge described in claims 1 or 25, it is characterised in that: at the fixed bed hydrogenation Manage reaction zone operating condition are as follows: temperature be 380 DEG C~410 DEG C, pressure be 15MPa~20MPa, hydrogen to oil volume ratio be 400~ 800, volume space velocity is 0.2h when raw material oil liquid^-1~0.6h^-1。

27. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: heavy as described in step (1) is former Material includes the inferior heavy oil of decompression residuum or other sources that crude distillation obtains, and the tenor in heavy charge is at least 120μg/g。

28. according to the processing method of heavy charge described in claims 1 or 27, it is characterised in that: as described in step (1) heavy Matter raw material includes the inferior heavy oil of the decompression residuum that crude distillation obtains or other sources, and the tenor in heavy charge is 180 μ g/g or more.

29. according to the processing method of heavy charge described in claims 1 or 27, it is characterised in that: as described in step (1) heavy Matter raw material includes the inferior heavy oil of the decompression residuum that crude distillation obtains or other sources, and the tenor in heavy charge is 220 μ g/g or more.

30. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: ebullated bed as described in step (1) Reactor reaction temperature is 370~450 DEG C, and reaction pressure is 8~25MPa, hydrogen to oil volume ratio 100:1 ~ 1000:1, liquid volume Air speed (LHSV) is 0.3~5.0h^-1。

31. according to the processing method of heavy charge described in claim 1 or 30, it is characterised in that: boiling as described in step (1) Rising a reactor reaction temperature is 380~430 DEG C；Reaction pressure is 8.0~16MPa；Hydrogen to oil volume ratio 500:1 ~ 1000:1；Liquid Body volume space velocity (LHSV) is 0.3-2.0h^-1。

32. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: after boiling bed hydrogenation processing reaction Tenor is lower than 100 μ g/g in product liquid.

33. according to the processing method of heavy charge described in claim 1 or 32, it is characterised in that: boiling bed hydrogenation processing is anti- Tenor is lower than 80 μ g/g in product liquid after answering.

34. according to the processing method of heavy charge described in claim 1 or 32, it is characterised in that: boiling bed hydrogenation processing is anti- Tenor is lower than 60 μ g/g in product liquid after answering.

35. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: catalytic cracked oil pulp accounts for ebullated bed 20% or less total reactor feed weight.

36. according to the processing method of heavy charge described in claim 1 or 35, it is characterised in that: catalytic cracked oil pulp accounts for boiling Rise the 2%~20% of total reactor feed weight.

37. according to the processing method of heavy charge described in claim 1 or 35, it is characterised in that: catalytic cracked oil pulp accounts for boiling Rise the 5%~10% of total reactor feed weight.

38. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: into the catalytic cracking of fixed bed Recycle oil accounts for 30% or less fixed bed combined feed weight.

39. according to the processing method of heavy charge described in claim 1 or 38, it is characterised in that: into the catalysis of fixed bed Cracking recycle oil accounts for the 5%~30% of fixed bed combined feed weight.

40. according to the processing method of heavy charge described in claim 1 or 38, it is characterised in that: into the catalysis of fixed bed Cracking recycle oil accounts for the 10%~20% of fixed bed combined feed weight.

41. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that: catalytic cracking unit reaction condition Are as follows: reaction temperature is 450~600 DEG C, and regeneration temperature is 600~800 DEG C, and agent oil weight ratio is 2:1~30:1, is connect with catalyst The touching time 0.1~15 second, 0.1~0.5MPa of pressure.

42. according to the processing method of heavy charge described in claim 1 or 41, it is characterised in that: catalytic cracking unit reaction Condition are as follows: reaction temperature is 480~550 DEG C, and regeneration temperature is 650~750 DEG C, and agent oil weight ratio is 4:1~10:1, with catalysis Agent time of contact 0.5~5 second, 0.1~0.5MPa of pressure.