CN108102715A

CN108102715A - A kind of processing method of heavy oil feedstock

Info

Publication number: CN108102715A
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: 2018-06-01
Anticipated expiration: 2036-11-25
Also published as: CN108102715B

Abstract

The invention discloses a kind of processing method of heavy charge, the method content includes：The slurry oil of heavy charge and at least part catalytic cracking unit is mixed into fluidized bed reactor and carries out hydrotreating；Obtained boiling bed hydrogenation processing reaction effluent, the recycle oil of at least part catalytic cracking unit is reacted after being mixed with hydrogen by the fixed bed hydrogenation pretreatment reaction area being arranged in series and fixed bed hydrogenation processing reaction zone successively；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 significantly extend the service 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 handle boiling bed hydrogenation, fixed bed adds Hydrogen processing and catalytic cracking organic assembling process heavy charge to produce the scheme of fuel oil products.

Background technology

At present, domestic and international refined products market will be in hold particularly to the demand of motor petrol to the demand of the oil products such as steam coal bavin The continuous trend risen, and it is then on a declining curve to the demand of the heavy oil products such as heavy fuel oil.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 with relatively warp The rational cost of helping realizes heavy oil lighting and petrol and diesel oil product quality persistently upgrades and become what oil refining industry both at home and abroad was paid close attention to Focus.

The main purpose of residual hydrocracking technique is by hydrotreating, makes sulphur, nitrogen, metal in residual oil raw material etc. miscellaneous 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 In the fixed bed reactors for determining 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 greatest extent.Fixed bed residual oil adds Hydrogen technology is high with its liquid product yield, and good product quality, production chains are strong, and waste, waste material are few, environmental-friendly, invest back The advantages that report rate is high, has been more and more widely used.

The setting of fixed bed residual hydrocracking process reaction partial reaction device is generally connected by multiple reactors or bed It uses, the dosage form of catalyst is optimized, according to different physical according to the requirement of the property of original oil, reaction condition and purpose product 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 the phenomenon that in process of production, being but susceptible to reactor pressure drop increase.Industrial operation shows reactor pressure drop increase One of an important factor for being confining device full production and long-term operation.Especially more reactor series connection, preposition is anti- Demetalization of the device due to assuming responsibility for more than 70% is answered to react load, metal sulfide is deposited on catalyst bed, into operation after Inevitably there is pressure drop rapid growth in phase, and reactor below is since demetalization load is substantially relatively low, pressure drop increase compared with Slowly.This affects the cycle of operation and the device of device there have been forepart 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 carries For a kind of and its processing unit, which includes the hydrogenation insured unit once connected and main hydrotreating unit.Described adds Hydrogen protection location includes main hydrogenation protecting reactor in parallel and spare hydrogenation protecting reactor, and main hydrogenation protecting reactor Volume is more 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, shortcoming are the reactors that left unused, and 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, while change original catalyst grade and match somebody with somebody, when an anticatalyst bed When pressure drop designs 0.4~0.8 times of pressure drop for device, next feed inlet is used instead successively, while original feed inlet can be into cycling The miscella of oil or recycle oil and original oil can be effectively prevented bed pressure drop with the technique and extend the service cycle of device, And the processing capacity of device can be increased, help to improve flow distribution.Shortcoming is that inductor manufacture cost increases, and is made 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 by more reactors of series connection, when device operation 700~4000 is small 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 With clarified oil together into residual hydrogenation equipment, reacted in the presence of hydrogen and hydrogenation catalyst, heavy-cycle oil is being catalyzed It is cycled inside cracking unit；The slurry oil of gained is reacted through the isolated clarified oil of separator, is back to hydrogenation plant.But oil It starches and enters residual hydrocracking device, the easy green coke object in slurry oil will increase the carbon deposit of hydrogenation catalyst, reduce hydrogenation and urge The hydrogenation activity of agent and operation cycle, and heavy-cycle oil is inside catalytic cracking unit.Therefore, the method is to reducing coke Yield, raising product quality are limited.USP6277270 discloses a kind of handled comprising fixed bed hydrogenation, at boiling bed hydrogenation It manages with catalytic cracking combined technique to produce light-weight fuel oil.Fixed bed processes decompression residuum respectively with ebullated bed, obtained production Product are mixed after air-distillation, and atmospheric fractions recycling, reduced crude is processed in Residue Catalytic Cracking.Patent processing is former Material is limited in scope, and is not applied to for the raw material of high metal content.

Fixed bed hydrogenation+heavy oil catalytic cracking is the pattern often selected, and the route light oil yield is high, can meet stringenter 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 rise, 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 is hydrogenated with after being mixed with residual oil, enters back into catalytic cracking unit.But catalytic cracked oil pulp does not obtain effective profit With this method is limited to reducing coke yield, raising product yield.Meanwhile the adaptability to raw material difference of fixed bed hydrogenation processing There is no solve for problem.

When being processed due to inferior heavy oil, volume space velocity is relatively low, therefore generally requires multiple reactors and be used in series（Series connection Each reactor is passed sequentially through using reaction mass is referred to）, 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 online（Evaluated half for accounting for boiling bed hydrogenation device gross investment or so）, It is complicated for operation, the failure rate of appearance also highest.

The content 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 flow is simple, It only needs to carry out simple modifications to existing apparatus, it is possible to significantly extend the service cycle of device, and the profit of catalyst can be made It is realized and maximized with efficiency, poor residuum raw material can be handled using the technique, extend the service cycle of residual hydrogenation equipment, reduced The investment of device and operating cost, technical process are simple..

Existing heavy Oil Hydrotreating Processes, all reactors are using the technological process connected, it is therefore desirable to anti-in First Device is answered to load substantial amounts of protective agent to deposit the impurity in raw material and dirty object, so operation can cause in First protection reactor For the antigravity system of filling since activity is relatively low, demetalization load is relatively low, 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 improve its catalyst activity again The rapid growth of pressure drop can be caused, shortens the cycle of operation, and subsequent catalyst performance plays completely not yet, keeps First The appropriate activity of protection reactor catalyst is difficult control, and during residual hydrogenation equipment whole service there are it is many because Fe in element such as urgent shutting down, feedstock property fluctuation or raw material, Ca impurity increases suddenly, therefore common practice is still The relatively low reactivity of an anti-protection reactor catalyst is to maintain, main function intercepts and deposit the impurity and dirt in raw material Object only carries out relatively low demetalization reaction, is typically that reactor reaction temperature liter is relatively low, and pressure drop maintains in the whole service cycle In relatively low level, this requires that loading substantial amounts 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, so inevitably cause The demetalization reactor deposits substantial amounts of metal, and demetalization reaction load is larger, is typically that the reactor reaction temperature rises highest, to the greatest extent Pipe initial operating stage reactor pressure decrease is relatively low, but the pressure drop to operation to the mid-term or later stage 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 herein below：

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

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

（3）Step（2）The generation oil that middle fixed bed hydrogenation processing reaction zone obtains 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, step（2）Described in fixed bed hydrogenation pretreatment reaction area include at least two weighted BMO spaces being arranged in parallel Reactor, when the pressure drop of any one weighted BMO spaces reactor in the fixed bed hydrogenation pretreatment reaction area reaches predetermined value When, the weighted BMO spaces reactor that pressure drop is reached to predetermined value is cut out from fixed bed hydrogenation pretreatment reaction area, and by described in 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, preferably For 60%~70%.

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

In the preferred case, it is when the pressure drop of a weighted BMO spaces reactor reaches the predetermined value, the hydrogenation is pre- Treatment reactor is cut out from fixed bed hydrogenation pretreatment reaction area, which is named as to the hydrogenation cut out Preatreating reactors I, and by the 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 At area, the weighted BMO spaces reactor II cut out, the weighted BMO spaces reactor I cut out and the fixed bed hydrogenation 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 Reach predetermined value during the pressure drop difference for answering device, it is two neighboring to reach closest to the weighted BMO spaces reactor for reaching pressure drop predetermined value The time difference of its pressure drop predetermined value is not less than the 20% of the whole device cycle of operation, is 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 reach pressure drop predetermined value during each weighted BMO spaces reactor difference 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 Using one kind in different Catalyst packing density under the conditions of material property, different operating conditions and identical filling height Or various ways make to reach pressure drop during each weighted BMO spaces reactor difference in fixed bed hydrogenation pretreatment reaction area to realize Predetermined value.

In the processing method of the heavy charge, when by controlling filling identical in each weighted BMO spaces reactor Come when realizing by the way of different Catalyst packing density under the conditions of height, in the fixed bed hydrogenation pretreatment reaction area In each weighted BMO spaces reactor in parallel, maximum loading density can be 400kg/m³~600kg/m³, it is preferably 450kg/ m³~550kg/m³；Minimum loading density can be 300kg/m³~550kg/m³, it is 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 is 50kg/m³~200kg/ m³, it is preferably 80kg/m³~150kg/m³.The difference loading density can be equipped with by different types of catalyst grade tamps 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 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, it is 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 are preferably the μ g/g of 10 μ g/g ~ 30.

In the processing method of the heavy charge, when by controlling operation different in each weighted BMO spaces reactor The mode of condition is come when realizing, the operation item of control operation pressure and the immediate two weighted BMO spaces reactors of volume space velocity In part, operation temperature difference can be 2 DEG C ~ 30 DEG C, be preferably 5 DEG C ~ 20 DEG C；Or control operation pressure and operation temperature most connect In the operating condition of two near weighted BMO spaces reactors, volume space velocity difference is 0.1 h^-1~10 h^-1, it is 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 load Hydrobon catalyst and hydrodenitrogeneration carbon residue reforming catalyst successively.

In the processing method of the heavy charge, the operating condition in the fixed bed hydrogenation pretreatment reaction area is：Temperature It spends for 370 DEG C~420 DEG C, is preferably 380 DEG C~400 DEG C；Pressure is 10MPa~25MPa, is preferably 15MPa~20MPa；Hydrogen Oil volume ratio is 300~1500, is preferably 500~800；Volume space velocity is 0.15h during raw material fluid^-1~2h^-1, it is preferably 0.3h^-1~1h^-1.The residuum hydrogenating and metal-eliminating of the average reaction temperature of weighted BMO spaces reaction zone 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 that portion is set eliminates pressure drop and increases limits device stabilization fortune by the optimization of technological process 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 can 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 is：Temperature It it is preferably 380 DEG C~410 DEG C for 370 DEG C~430 DEG C；Pressure is 10MPa~25MPa, is preferably 15MPa~20MPa；Hydrogen oil Volume ratio is 300~1500, is preferably 400~800；Volume space velocity is 0.15h during raw material fluid^-1~0.8h^-1, it is preferably 0.2h^-1~0.6h^-1。

In the processing method of the heavy charge, step（1）Involved in heavy charge include crude distillation and obtain Decompression residuum or the inferior heavy oil in other sources, the tenor in heavy charge are at least 120 μ g/g, are preferably 180 μ g/g More than, it is most preferably more than 220 μ g/g.

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

Due in the de-oiled asphalt of boiling bed hydrogenation processing unit processing containing substantial amounts of resin and asphalt, and asphalitine Chemical constitution 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, it is necessary to could imurity-removal under harsh operating condition deeply.Asphalitine is being hydrogenated with The resolution ratio of process is related with the aperture of used catalyst.Catalyst aperture is at least greater than 10nm, and asphalitine is it is possible that diffusion 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 pore volume of 30~300nm of bore dia account for the 35%~60% of total pore volume （Mercury injection method）, the average pore diameter of catalyst is more than 20nm, is preferably 22 ~ 40nm.In catalyst, by weight, catalyst Containing VI B family metal oxides（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 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, step（2）Involved in fixed bed hydrogenation pretreatment reaction area use Raw material for the reaction effluent of ebullated bed and catalytic cracking recycle oil, can also add in other suitable for using at fixed bed The heavy charge of reason.Tenor in the liquid phase feeding of fixed bed hydrogenation processing will be less than 100 μ g/g, preferably shorter than 80 μ g/ g。

In the processing method of the heavy charge, the catalytic cracked oil pulp into fluidized bed reactor 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 Less than the 20% of fluidized bed reactor combined feed weight is typically constituted from, generally 2%~20%, it is preferably 5%~10%.Into fixed bed Catalytic cracking recycle oil can be all or part of, catalytic cracking recycle oil also can 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 less than the 30% of fixed bed combined feed weight, generally 5%~30%, be preferably 10%~20%.

In the processing method of the heavy charge, this field routine techniques may be employed in catalytic cracking.Catalytic cracking fills It can be more than a set of or a set of to put, and a reactor, a regenerator should be at least included per covering device.Catalytic cracking unit is set Fractionating column is put, can respectively be set, can also 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 For 650~750 DEG C, agent is oily（Catalyst and feedstock oil）Weight ratio 2：1~30：1, preferably 4：1~10：1；It is contacted with catalyst 0.1~15 second time, 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, such as silica-alumina catalyst, silica-magneia cataslyst, the carclazyte of acid treatment and X-type, Y types, ZSM-5, M type, layer Column equimolecular sieves Cracking catalyst, 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.Technological process is generally：Feedstock oil is anti-from riser Device bottom is answered to inject, is contacted with the high-temperature regenerated catalyst from regenerator, the oil gas and deposit coke of cracking reaction generation 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, can specifically it be determined according to raw material sources property and processing request specific Process conditions, the optimization of process conditions and determine it is content 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 being mixed 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 following advantages that：

（1）In the method for the present invention, fluidized bed reactor normally only needs to set one, its purpose is that fixed bed hydrogenation reactor carries out Pretreatment of raw material, it is different from the operation purpose that current boiling bed residual oil hydrogen addition technology needs higher conversion, reduce equipment throwing Money, combines fixed bed and the comprehensive advantage of ebullated bed, avoids conventional fluidized bed reactor and obtained when high conversion operates Residual oil（After fractionating out light fraction）Quality is worse, the problem of being not suitable for that bed hydroprocessing processing is fixed again.

（2）The fixed bed hydrogenation pretreatment reaction area includes multiple weighted BMO spaces reactors in parallel 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 During to predetermined value, it from fixed bed hydrogenation pretreatment reaction area is cut out, and passes through the change of technological process, makes its pressure drop no longer Rapid growth, but can be slowly to increase in control 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 add the operating flexibility of device and raw material adaptability.

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

（6）The processing method of heavy charge of the present invention can utmostly realize that all kinds of catalyst synchronously inactivate, So as 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 Xun Huan is added to boiling In bed reactor, diluting effect can be played to de-oiled asphalt, be improved its property, it is anti-to reduce boiling bed residual oil hydrogenation Answer difficulty and processing severity；Heavy catalytic cycle oil can satisfy in the further imurity-removal of fixed bed hydrogenation reaction zone, aromatic hydrocarbons With, be conducive to improve catalytic cracking product quality.

Description of the drawings

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

Fig. 2 be heavy charge of the present invention processing method in fixed bed hydrogenation pretreatment reaction area and fixed bed add Hydrogen handles the schematic diagram of reaction zone.

Specific embodiment

The specific embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or Value should be understood to comprising the value close to these scopes or value.For numberical range, between the endpoint value of each scope, respectively It between the endpoint value of a scope and individual point value and can be individually combined with each other 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 Pore volume account for the 35%~60% of total pore volume（Mercury injection method）, the average pore diameter of catalyst is more than 20nm, is preferably 22 ~ 40nm. In catalyst, by weight, catalyst contains VI B family metal oxides（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 A diameter of 0.1~0.8mm.

In heavy charge processing method of the present invention, the fixed bed preatreating reactors area 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%th, 67%, 68%, 69%, 70%, 71%, 72%, 74%, 75%, 76%, 78%, 80% and any two value is formed in them model 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 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, it is two neighboring to be reached closest to the weighted BMO spaces reactor for reaching pressure drop predetermined value Time difference to its pressure drop predetermined value is not less than the 20% of the whole service cycle, the preferably 20-60% in whole service cycle, example Such as, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%.In the present invention, the whole service cycle refers to that heavy oil adds Hydrogen processing system is from bringing into operation to the undergone time of stopping work.

In heavy charge processing method of the present invention, each hydrogenation in the 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 or more in charcoal reforming catalyst, the fixed bed hydrogenation, which is handled in the reactor of reaction zone, can load hydrodesulfurization One or more in catalyst and hydrodenitrogeneration carbon residue reforming catalyst.

In a preferred embodiment, according to Flow of Goods and Materials direction, loaded successively in each weighted BMO spaces reactor Hydrogenation protecting agent, Hydrodemetalation catalyst and optional Hydrobon catalyst；The reaction in the hydrotreating reaction area Device loads Hydrobon catalyst and hydrodenitrogeneration carbon residue reforming catalyst successively.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 somebody with somebody by catalyst grade is 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 is based on de-/appearance 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, base is established for successive depths desulfurization and the conversion of carbon residue Plinth so that hydrodesulfurizationreaction reaction zone is conducive to further deep reaction, therefore, and 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 instead without reducing.

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 processing procedure.These are urged Agent is usually with porous refractory inorganic oxide（Such as aluminium oxide）For carrier, group VIB and/or group VIII metal（As W, Mo, Co, Ni etc.）Oxide for active component, be selectively added the catalyst of the elements such as other various auxiliary agents such as P, Si, F, B. For example, the FZC series heavy oil hydrogenating treatment catalysts produced by catalyst branch company of Sinopec Group.

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

Heavy charge processing method of the present invention is further described 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：After heavy charge M1 preheatings Add after being mixed with the catalytic cracked oil pulp M9 from catalytic cracking unit R5 and hydrogen M2 into fluidized bed reactor R1, ebullated bed Hydrogenation reaction is carried out under hydrogen catalyst and process conditions, the hetero atoms such as removing metal, sulphur make asphalitine be converted into colloid or smaller Molecule reduces product viscosity.Ebullating bed reactor effluent M3 and FCC recycle oil M8 and hydrogen M2 from catalytic cracking unit The material M10 obtained after mixing enters fixed bed hydrogenation device R2, and hydrogenation reaction is carried out under catalyst and reaction condition, is obtained Reaction effluent M4 is further separated in gas-liquid separator R3, is used as and is followed after the isolated further depriving hydrogen sulphides of gas phase M5 Ring hydrogen is recycled back to reaction system, and isolated liquid phase is directly as the reaction raw materials of catalytic cracking unit, catalytic cracking unit Including catalyst cracker R4 and catalytic cracking fractionating tower R5, catalytic cracking fractionating tower separation after obtain gasoline M6, diesel oil M7, Recycle oil M8 and slurry oil M9.Ebullating bed reactor effluent enters back into fixed bed after can entering filter SR after being mixed with recycle oil Reactor removes solid impurity that may be present etc..Above device is a serial technological process, according to wanting for unit scale It asks, two or more series can be set up in parallel.The fixed bed hydrogenation that fixed bed hydrogenation reaction zone R2 includes tandem is located in advance Manage reaction zone and fixed bed hydrogenation processing reaction zone.The fixed bed hydrogenation pretreatment reaction area as shown in Figure 2 is set including parallel connection The three weighted BMO spaces reactors put are respectively weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces Reactor C, the weighted BMO spaces reactor A, weighted BMO spaces reactor B, the feed inlet difference of weighted BMO spaces reactor C It is connected with feeding line 1, feeding line 2 and feeding line 3, three tunnels of outlet point of the weighted BMO spaces reactor A, the first via It is connected through pipeline 6 with the feed inlet of weighted BMO spaces reactor B, charging of second tunnel through pipeline 7 Yu weighted BMO spaces reactor C Mouth connection, the 3rd tunnel is connected through pipeline 10 with the feed inlet of hydrotreating reactor D；The weighted BMO spaces reactor B goes out Tri- tunnels of Kou Fen, the first via are connected through pipeline 4 with the feed inlet of weighted BMO spaces reactor A, and the second tunnel is through pipeline 5 and the pre- place of hydrogenation Reason reactor C obtains feed inlet connection, and the 3rd tunnel is connected through pipeline 11 with the feed inlet of hydrotreating reactor D；The hydrogenation is pre- Three tunnels of the outlet for the treatment of reactor C point, the first via are connected through pipeline 8 with the feed inlet of weighted BMO spaces reactor A, the second road warp Pipeline 9 is connected with the feed inlet of weighted BMO spaces reactor B, feed inlet of the 3rd tunnel through pipeline 12 Yu hydrotreating reactor D Connection；Valve 101 is provided on the pipeline 1, valve 102 is provided on the pipeline 2, valve is provided on the pipeline 3 103, valve 104 is provided on the pipeline 4, and valve 105 is provided on the pipeline 5, valve is provided on the pipeline 6 106, valve 107 is provided on the pipeline 7, and valve 108 is provided on the pipeline 8, valve is provided on the pipeline 9 109, valve 1010 is provided on the pipeline 10, and valve 1011 is provided on the pipeline 11, is provided on the pipeline 12 Valve 1012, the generation oil M4 that the hydrotreating reactor obtains enter catalyst cracker and carry out cracking reaction.It is described It is each provided with using in weighted BMO spaces reactor A, the weighted BMO spaces reactor B and the weighted BMO spaces reactor C In the sensing unit of monitoring pressure drop（It is not shown in figure）, and the heavy-oil hydrogenation processing system further includes control unit（In figure It is not shown）, for receiving the pressure drop signal from the sensing unit, and according to pressure drop signal control and the pre- place of each hydrogenation Manage the corresponding valve of reactor.

In above-mentioned heavy charge processing method, weighted BMO spaces reactor A, weighted BMO spaces reactor B and hydrogenation are 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：It is sequentially reached according to weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C 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）With sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spaces reactor C Pressure drop, when the pressure drop of weighted BMO spaces reactor A reaches predetermined value, from corresponding to the weighted BMO spaces reactor A The pressure drop signal of sensing unit passes to control unit, and control unit performs to regulate and control valve after receiving the signal, tool Body, valve 101, the valve 1011 of pipeline 11 and the valve 1012 of pipeline 12 of feeding line 1 are closed, is opened on pipeline 8 Valve 104 on valve 108 and pipeline 4 so that weighted BMO spaces reaction zone（It is pre- including weighted BMO spaces reactor B and hydrogenation Treatment reactor C）, weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by being parallel to string The handover operation of connection；

（3）When the pressure drop of weighted BMO spaces reactor B reaches predetermined value, from corresponding to the weighted BMO spaces reactor B The pressure drop signal of sensing unit pass to control unit, control unit performs to regulate and control valve after receiving the signal, Specifically, valve 102, the valve 108 of pipeline 8 of feeding line 2 are closed, opens the valve 109 on pipeline 9 so that hydrogenation is pre- Treatment reactor C, weighted BMO spaces reactor B, weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, at this time Complete the 2nd handover operation by being parallel to series connection；

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

Mode 2：It is sequentially reached according to weighted BMO spaces reactor A, weighted BMO spaces reactor C, weighted BMO spaces reactor B Pressure drop predetermined value.

（3）When the pressure drop of weighted BMO spaces reactor C reaches predetermined value, from corresponding to the weighted BMO spaces reactor C The pressure drop signal of sensing unit pass to control unit, control unit performs to regulate and control valve after receiving the signal, Specifically, valve 103, the valve 104 of pipeline 4 of feeding line 3 are closed, opens the valve 105 on pipeline 5 so that hydrogenation is pre- Treatment reactor B, weighted BMO spaces reactor C, weighted BMO spaces reactor A and hydrodesulfurizationreaction reaction zone form series connection, at this time Complete the 2nd handover operation by being parallel to series connection；

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

Mode 3：It is sequentially reached according to weighted BMO spaces reactor B, weighted BMO spaces reactor C, weighted BMO spaces reactor A Pressure drop predetermined value.

（2）With sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spaces reactor C Pressure drop, when the pressure drop of weighted BMO spaces reactor B reaches predetermined value, from corresponding to the weighted BMO spaces reactor B The pressure drop signal of sensing unit passes to control unit, and control unit performs to regulate and control valve after receiving the signal, tool Body, valve 102, the valve 1010 of pipeline 10 and the valve 1012 of pipeline 12 of feeding line 2 are closed, is opened on pipeline 9 Valve 106 on valve 109 and pipeline 6 so that weighted BMO spaces reaction zone（It is pre- including weighted BMO spaces reactor A and hydrogenation Treatment reactor C）, weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by being parallel to string The handover operation of connection；

（3）When the pressure drop of weighted BMO spaces reactor C reaches predetermined value, from corresponding to the weighted BMO spaces reactor C The pressure drop signal of sensing unit pass to control unit, control unit performs to regulate and control valve after receiving the signal, Specifically, valve 103, the valve 106 of pipeline 6 of feeding line 3 are closed, opens the valve 107 on pipeline 7 so that hydrogenation is pre- Treatment reactor A, weighted BMO spaces reactor C, weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, at this time Complete the 2nd handover operation by being parallel to series connection；

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

Mode 4：It is sequentially reached according to weighted BMO spaces reactor B, weighted BMO spaces reactor A, weighted BMO spaces reactor C Pressure drop predetermined value.

（3）When the pressure drop of weighted BMO spaces reactor A reaches predetermined value, from corresponding to the weighted BMO spaces reactor A The pressure drop signal of sensing unit pass to control unit, control unit performs to regulate and control valve after receiving the signal, Specifically, valve 101, the valve 109 of pipeline 9 of feeding line 1 are closed, opens the valve 108 on pipeline 8 so that hydrogenation is pre- Treatment reactor C, weighted BMO spaces reactor A, weighted BMO spaces reactor B and hydrodesulfurizationreaction reaction zone form series connection, at this time Complete the 2nd handover operation by being parallel to series connection；

Mode 5：It is sequentially reached according to weighted BMO spaces reactor C, weighted BMO spaces reactor B, weighted BMO spaces reactor A Pressure drop predetermined value.

（2）With sensing unit detection weighted BMO spaces reactor A, weighted BMO spaces reactor B and weighted BMO spaces reactor C Pressure drop, when the pressure drop of weighted BMO spaces reactor C reaches predetermined value, from corresponding to the weighted BMO spaces reactor C's The pressure drop signal of sensing unit passes to control unit, and control unit performs to regulate and control valve after receiving the signal, tool Body, valve 103, the valve 1010 of pipeline 10 and the valve 1011 of pipeline 11 of feeding line 3 are closed, is opened on pipeline 7 Valve 105 on valve 107 and pipeline 5 so that weighted BMO spaces reaction zone（It is pre- including weighted BMO spaces reactor A and hydrogenation Treatment reactor B）, weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, complete at this time once by being parallel to string The handover operation of connection；

（3）When the pressure drop of weighted BMO spaces reactor B reaches predetermined value, from corresponding to the weighted BMO spaces reactor B The pressure drop signal of sensing unit pass to control unit, control unit performs to regulate and control valve after receiving the signal, Specifically, valve 102, the valve 107 of pipeline 7 of feeding line 2 are closed, opens the valve 106 on pipeline 6 so that hydrogenation is pre- Treatment reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, at this time Complete the 2nd handover operation by being parallel to series connection；

Mode 6：It is sequentially reached according to weighted BMO spaces reactor C, weighted BMO spaces reactor A, weighted BMO spaces reactor B Pressure drop predetermined value.

（3）When the pressure drop of weighted BMO spaces reactor A reaches predetermined value, from corresponding to the weighted BMO spaces reactor A The pressure drop signal of sensing unit pass to control unit, control unit performs to regulate and control valve after receiving the signal, Specifically, valve 101, the valve 105 of pipeline 5 of feeding line 1 are closed, opens the valve 104 on pipeline 4 so that hydrogenation is pre- Treatment reactor B, weighted BMO spaces reactor A, weighted BMO spaces reactor C and hydrodesulfurizationreaction reaction zone form series connection, at this time Complete the 2nd handover operation by being parallel to series connection；

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

Illustrate the effect of the present invention 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 the boiling bed hydrogenation cracking reaction area is set 1 boiling bed hydrogenation cracker is put, 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 with Examples 1 to 4.Weighted BMO spaces reactor A, weighted BMO spaces reactor B described in the embodiment of the present invention, Weighted BMO spaces reactor C is pattern, the identical reactor of size, reactor A, reactor B in the comparative example, reactor 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.It is mixed first by residual oil raw material with catalytic cracked oil pulp 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 The hetero atoms such as sulphur, nitrogen, metal, while asphalitine is made to be converted into colloid or more small molecule, product viscosity is reduced, hydrogenation products are with urging Change cracking recycle oil enters fixed bed hydrogenation device and is reacted, and is generated under fixed bed grading catalyst and reaction condition Oil.Generation oil is converted into dry gas, catalytically cracked gasoline into the further cracking of catalytic cracking unit, catalytic cracking diesel oil, urges Change cracking recycle oil and catalytic cracked oil pulp, catalytic cracking recycle oil is entered fixed bed reactors by filtering Posterior circle carries out Hydrogenation reaction, catalytic cracked oil pulp enters by filtering Posterior circle carries out hydrogenation reaction in fluidized bed reactor.

Boiling bed hydrogenation treatment catalyst can be needed according to performance using existing method prepare, such as with reference to US7074740, It is prepared by the prior arts such as US5047142, US4549957, US4328127, CN200710010377.5.The property of catalyst compares table Area 142m²/ g, pore volume 1.45mL/g（Mercury injection method）, the pore volume of 30~300nm of bore dia accounts for the 52% of total pore volume（Mercury injection method）, MoO₃Content is that 6.02%, NiO contents are 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% in the charging of fixed bed hydrogenation device（Weight, 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 with reference to US7074740 and CN200710010377.5 methods.Routinely side Method prepares Mo-Co-P solution, MoO in solution₃Quality meter content is 18.00%, counts content using CoO mass and contains as 3.50%, P mass It measures as 1.05%.Above-mentioned carrier is impregnated by incipient impregnation method obtain final catalyst with the solution.

Catalytic cracking catalyst is the catalyst that 3,500,000 tons/year of heavy oil catalytically cracking equipments of Dalian Company use, and is work Industry equilibrium catalyst.Its fresh dose composition be：95wt%LBO-16 olefine lowering catalysts+5wt%LBO-A improves octane enhancing additive.

Raw material oil nature used is shown in Table 1 in the embodiment of the present invention and comparative example.Catalyst in embodiment 1- embodiments 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 examples 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 that weighted BMO spaces are anti-respectively Device A, weighted BMO spaces reactor B, weighted BMO spaces reactor C are answered, the weighted BMO spaces reactor A, weighted BMO spaces are anti- Answer device B, the catalyst inventory of weighted BMO spaces reactor C, feed properties identical with inlet amount, the weighted BMO spaces Reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C, the catalyst of hydrodesulphurisatioreactors reactors D are according in table 2 Mode load.

Embodiment 2

In embodiment 2, the weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C it is each instead into Expect that air speed is different, volume space velocity is 0.20h during the weighted BMO spaces reactor A liquid^-1, body during weighted BMO spaces reactor B liquid Product air speed is 0.32h^-1, volume space velocity is 0.44h during weighted BMO spaces reactor C liquid^-1.Weighted BMO spaces reactor A, hydrogenation It is shown in Table in preatreating reactors B, weighted BMO spaces reactor C using identical catalyst loading pattern, catalyst loading pattern 2。

Embodiment 3

In embodiment 3, the weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C inlet amounies It is identical.The weighted BMO spaces reactor A average reaction temperature is 370 DEG C, weighted BMO spaces reactor B average response temperature Spend for 378 DEG C, weighted BMO spaces reactor C average reaction temperatures be 383 DEG C, the average reaction temperature of hydrodesulphurisatioreactors reactors D For 383 DEG C, 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 using traditional cascade, and with hydrogenation Treatment reactor is connected.Fixed bed catalyst totality admission space is consistent with embodiment, and catalyst grade is matched somebody with somebody 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.It is respectively anti-also using 4 reactors in comparative example 1 Device A, reactor B, reactor C, reactor D are answered, reactor A, reactor B, reactor C and reactor D use what is be sequentially connected in series Form connects.Raw materials used property is shown in Table 1 in comparative example 1, the inlet amount and feed properties of reactor A and embodiment 1 always into Doses is identical with feed properties.The reactor A, reactor B, the catalyst inventory and reality of reactor C and reactor D It applies example 1 and corresponds to weighted BMO spaces reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C, hydrodesulphurisatioreactors reactors D is identical, but the loadings of various species catalyst are different, is loaded in the way of in table 6.

Comparative example 2

Ebullating bed reactor condition in comparative example 2 is same as Example 2.It is respectively anti-also using 4 reactors in comparative example 2 Device A, reactor B, reactor C, reactor D are answered, reactor A, reactor B, reactor C and reactor D use what is be sequentially connected in series Form connects.1 is shown in Table using feedstock property, reactor A entrance and embodiment 2 total inlet amount and feed properties in comparative example 2 It is identical.The reactor A, reactor B, the catalyst inventory of reactor C and reactor D it is corresponding with embodiment 2 plus Hydrogen pretreatment reactor A, weighted BMO spaces reactor B, weighted BMO spaces reactor C, hydrodesulphurisatioreactors reactors D are identical, still The loadings of various species catalyst are different, loaded in the way of in table 6.

Comparative example 3

Ebullating bed reactor condition in comparative example 3 is consistent with embodiment 3.It is respectively anti-also using 4 reactors in comparative example 3 Device A, reactor B, reactor C, reactor D are answered, reactor A, reactor B, reactor C and reactor D use what is be sequentially connected in series Form connects.Reactor A entrance is identical with inlet amount and feed properties that embodiment 3 is total.It is the reactor A, reactor B, anti- Answer the catalyst inventory weighted BMO spaces reactor A corresponding with embodiment of device C and reactor D, weighted BMO spaces reactor B, Weighted BMO spaces reactor C, hydrodesulphurisatioreactors reactors D are identical, but the loadings of various species catalyst are different, according to Mode in table 6 is loaded.

1 feedstock property of table

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

3 embodiment 1- embodiments 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 examples of table, 3 fixed bed hydrogenation generates oil nature

10 embodiment of table and comparative example steady running cycle compare

Can be seen that the method for the present invention from the stability experiment result of above-mentioned fixed bed reaction system can realize fixed bed hydrogenation The long period steady running of processing unit.

Claims

1. a kind of processing method of heavy charge, the processing method includes herein below：

2. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that：It is reacting the starting stage, it is described solid Fixed bed weighted BMO spaces reaction zone sets 3~6, is preferably provided with 3~4 weighted BMO spaces reactors being arranged in parallel.

3. 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 the 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.

4. 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 all weighted BMO spaces reactor pressure drop difference when reach predetermined value, 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, is preferably 20 ~60%.

5. 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 causing each weighted BMO spaces reactor difference in fixed bed hydrogenation pretreatment reaction area Reach pressure drop predetermined value.

6. according to the processing method of the heavy charge described in claim 5, 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 or more modes in different Catalyst packing density to realize under the conditions of same filling height Reach pressure drop predetermined value in hydrogen pretreatment reaction zone during each weighted BMO spaces reactor difference.

7. according to the processing method of the heavy charge described in claim 6, it is characterised in that：When by controlling the pre- place of each hydrogenation It manages in reactor under the conditions of identical filling height by the way of different Catalyst packing density come when realizing, described solid In each weighted BMO spaces reactor of fixed bed weighted BMO spaces reaction zone parallel connection, maximum loading density is 400kg/m³~ 600kg/m³, it is preferably 450kg/m³~550kg/m³；Minimum loading density is 300kg/m³~550kg/m³, it is preferably 350kg/ m³~450kg/m³；The Catalyst packing density difference of the immediate two weighted BMO spaces reactors of loading density is 50kg/m³ ~200kg/m³, it is preferably 80kg/m³~150kg/m³。

8. according to the processing method of the heavy charge described in claim 6, it is characterised in that：When by controlling the pre- place of each hydrogenation The mode of different inlet amount in reactor is managed come when realizing, the charging of the immediate two weighted BMO spaces reactors of inlet amount The ratio between volume space velocity is 1.1 ~ 3：1, it is preferably 1.1 ~ 1.5：1.

9. according to the processing method of the heavy charge described in claim 6, it is characterised in that：When by controlling the pre- place of each hydrogenation The mode of different feed properties in reactor is managed come when realizing, the immediate two weighted BMO spaces reactors of feed properties Tenor difference is the μ g/g of 5 μ g/g ~ 50, is preferably the μ g/g of 10 μ g/g ~ 30.

10. according to the processing method of the heavy charge described in claim 6, it is characterised in that：When by controlling each hydrogenation pre- The mode of different operating conditions is come when realizing, control operation pressure and immediate two of volume space velocity add in treatment reactor In the operating condition of hydrogen pretreatment reactor, operation temperature difference is 2 DEG C ~ 30 DEG C, is preferably 5 DEG C ~ 20 DEG C；Or control operation In pressure and the operating condition of the immediate two weighted BMO spaces reactors of operation temperature, volume space velocity difference is 0.1h^-1~ 10h^-1, it is preferably 0.2 h^-1~5 h^-1。

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

12. 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 is：Temperature is 370 DEG C~420 DEG C, is preferably 380 DEG C~400 DEG C；Pressure is 10MPa~25MPa, Preferably 15MPa~20MPa；Hydrogen to oil volume ratio is 300~1500, is preferably 500~800；Volume space velocity is during raw material fluid 0.15h^-1~2h^-1, it is preferably 0.3h^-1~1h^-1。

13. 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- Area is answered to include 1~5 hydrotreating reactor being arranged in series, preferably includes 1~2 hydrotreating reaction being arranged in series Device.

14. 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- The operating condition for answering area is：Temperature is 370 DEG C~430 DEG C, is preferably 380 DEG C~410 DEG C；Pressure is 10MPa~25MPa, excellent Elect 15MPa~20MPa as；Hydrogen to oil volume ratio is 300~1500, is preferably 400~800；Volume space velocity is during raw material fluid 0.15h^-1~0.8h^-1, it is preferably 0.2h^-1~0.6h^-1。

15. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that：Step（1）Described in heavy it is former Material includes the inferior heavy oil in the decompression residuum that crude distillation obtains or other sources, and the tenor in heavy charge is at least 120 μ g/g are preferably more than 180 μ g/g, are most preferably more than 220 μ g/g.

16. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that：Step（1）Described in ebullated bed Reactor reaction temperature is 370~450 DEG C, is preferably 380~430 DEG C；Reaction pressure is 8~25MPa, preferably 8.0~ 16MPa；Hydrogen to oil volume ratio 100：1~1000：1, it is preferably 500：1~1000：1；Liquid volume air speed（LHSV）For 0.3~ 5.0h^-1, it is preferably 0.3-2.0h^-1。

17. 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 less than 100 μ g/g, preferably shorter than 80 μ g/g, most preferably less than 60 μ g/g in product liquid.

18. 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 Less than the 20% of total reactor feed weight is preferably 2%~20%, again preferably 5%~10%.

19. 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 less than the 30% of fixed bed combined feed weight, is preferably 5%~30%, is most preferably 10%~20%.

20. the processing method of heavy charge described in accordance with the claim 1, it is characterised in that：Catalytic cracking unit reaction condition For：Reaction temperature is 450~600 DEG C, is preferably 480~550 DEG C；Regeneration temperature is 600~800 DEG C, is preferably 650~750 DEG C, agent weight of oil ratio is 2：1~30：1, it is preferably 4：1~10：1；With catalyst contact time 0.1~15 second, preferably 0.5~5 Second；0.1~0.5MPa of pressure.