CN110408432A - A kind of method of group technology processing poor residuum - Google Patents

A kind of method of group technology processing poor residuum Download PDF

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Publication number
CN110408432A
CN110408432A CN201910357644.9A CN201910357644A CN110408432A CN 110408432 A CN110408432 A CN 110408432A CN 201910357644 A CN201910357644 A CN 201910357644A CN 110408432 A CN110408432 A CN 110408432A
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catalyst
reaction
oil
reaction zone
catalytic cracking
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CN110408432B (en
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吴锐
刘涛
韩照明
黄新露
吴长安
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petrochemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only

Abstract

The invention discloses a kind of methods of group technology processing poor residuum.After heavy oil feedstock oil is saturated molten hydrogen, first by weighted BMO spaces area, hydrodemetallization and partial desulfurization reaction are carried out；Reaction effluent enters hydrotreating reaction area after being saturated molten hydrogen again, carries out hydrodesulfurization and hydrodenitrogeneration reaction；Wherein the reaction temperature of weighted BMO spaces reaction zone is higher than the reaction temperature in hydrotreating reaction area.In method of the invention, weighted BMO spaces reaction zone is reacted at higher temperatures, the most of metal impurities that can be stripped of in material, so that the deactivation cause of desulphurization catalyst and/or denitrification catalyst from previous metal deposit and coking deactivation becomes only coking deactivation in hydrotreating reaction area, so that desulphurization catalyst and denitrification catalyst can carry out regeneration treatment after using a cycle, extend the operation cycle of hydrogenation plant, to increase the operational efficiency of device, economy is improved.

Description

A kind of method of group technology processing poor residuum
Technical field
The present invention relates to petroleum refining field more particularly to a kind of use residual hydrocracking and catalytic cracking combined techniques The method for handling poor residuum.
Background technique
Currently, demand of the refined products market to light, middle matter oil product will be in continuous upward trend both at home and abroad, to fuel oil etc. The demand of heavy oil product is then on a declining curve.Further, since the pressure of environmental protection increasingly increases, various countries generally improve petroleum The quality criteria requirements of the especially automobile-used petrol and diesel oil product of product.It, can be with more economical reasonable generation under above-mentioned market trend Valence realize heavy oil lighting, can make again obtained product meet the oil Refining Technologies of the constantly petrol and diesel oil product specification of harshness at One of the technology of domestic and international oil Refining Technologies developer's focus development.
In the various processes of heavy oil product lighting, heavy oil product is subjected to hydrotreating, right back end hydrogenation first It is a kind of preferable technical process that tail oil, which carries out catalyzed cracking processing,.By adding hydrogen, significantly reduce metal in these raw materials, Sulphur, nitrogen, asphalt content improve hydrogen-carbon ratio, and then provide excellent raw material for devices such as catalytic cracking and delayed cokings.At present Main hydrogenation technique mainly has ebullated bed, suspension bed, moving bed and fixed-bed process, and wherein suspension bed and moving bed process be also It is very immature, and higher cost.Ebullated bed high investment, and operation difficulty is larger.Fixed bed is because at low cost, easy to operate And safety is small, technology maturation, thus develops very fast.
In the prior art, it is realized by being provided with multiple hydrogenators of multiple hydrogenation catalyst beds to heavy oil product Hydrotreating.But the usual viscosity of heavy oil product is larger, metal impurities or asphalitine are higher, in hydrogenation process, metal and Coke can be gradually deposited on catalyst, be easy to make rapid catalyst deactivation, bed blocking, pressure rise, this phenomenon is the One hydrogenator is especially serious, moreover, when the pressure drop in first reactor reaches or approaches the theoretical pressure drop upper limit, instead It answers and easily occurs hot spot in device, device can only be forced to stop work at this time, shorten the operation cycle of heavy oil product hydrotreater.
It is former that CN1349554A discloses a kind of up-flow reactor system hydrotreating heavy with stratiform catalyst bed The method of material.With the upflow fixed bed reactor hydrotreating metal of the catalyst of at least two different hydrogenation activities, sulphur and The heavy charge of carbon containing residual matter pollution.But this method cycle of operation is short, is usually no more than 1 year.
Itd is proposed in CN1484684A replaceable reactor and can short-circuit reaction device hydrotreatment of heavy hydrocarbon fraction method, should It is traditional down-type fixed-bed reactor that reactor is protected in patent, if Ca, Fe content are higher in raw material, due to reaction Logistics from top to bottom, if the gap between these solid impurity blocking catalysts, though in protective agent duct deposited metal energy When power does not arrive saturation capacity, this reactor pressure decrease can also be increased, so that another reactor must be switched to.
CN102453530A discloses a kind of method of hydrotreating of processing heavy oil product, heavy oil product feedstock oil and hydrogen mixing Enter hydrogenation protecting reaction zone afterwards, then immediately proceed to hydrotreating reaction area, setting at least two is in parallel in hydrogenation protecting area Can switch the up flow type hydrogenation protecting reactor used in turn.The method that the invention uses four kinds of hydrogenation protecting agent gradations, has Extend the operation cycle of device conducive to removing metal to prevent from blocking and improving the service life of major catalyst.But this method is to device The increase rate of the cycle of operation is still little.
Residual hydrogenation tail oil is obtained into more and more common application directly as the technique of Rfcc Feedstock, and One of most effective crude conversion technology, it can obtain more light-end products from residual oil.It is urged in traditional residual hydrogenation- Change in cracking group technology, catalytic cracking recycle oil is to be recycled in catalytic cracking unit to be further processed.Since recycle oil contains There is polycyclic aromatic hydrocarbon, thus light oil yield is low, green coke amount is big, increases regenerator load, reduces heavy oil catalytically cracking equipment Treating capacity and economic benefit.In addition the sulfur content of recycle oil is higher, is about higher by one times than hydrogenation tail oil, recycle oil circulation but also Product sulfur content rises.
CN106701190A disclose it is a kind of handle low grade oils process, including weighted BMO spaces reaction zone, plus Hydrogen handles reaction zone and catalytic cracking reaction zone；The process includes the following contents: residual oil raw material and hydrogen mixing after according to Secondary to pass through concatenated weighted BMO spaces reaction zone and hydrotreating reaction area, the reaction effluent in hydrotreating reaction area carries out gas Liquid separation, gas phase is recycled back to weighted BMO spaces reaction zone and/or hydrotreating reaction area, liquid phase are directly entered catalytic cracking reaction Area carries out catalytic cracking reaction, and catalytic cracking reaction effluent isolated dry gas, catalytically cracked gasoline fraction, is urged at liquefied gas Change cracked diesel oil fraction, heavy catalytic cycle oil and catalytic cracked oil pulp, wherein catalytic cracking diesel oil, catalytic cracking follow again Some or all of ring oil and slurry oil are recycled back to hydrotreating reaction area and carry out hydrotreating reaction area.This method can extend dress The stabilization operation period set, but this method operation is more complex.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of method of group technology processing poor residuum, and especially one Kind can give full play to differential responses area catalyst performance, and the heavy oil for increasing device operation cycle handles combined method.
A kind of method of group technology processing poor residuum provided by the present invention, including the following contents:
(1) at least one weighted BMO spaces reaction zone, a hydrotreating reaction area and a catalytic cracking reaction zone are provided；Add Include hydrogenation protecting catalyst and Hydrodemetalation catalyst in hydrogen pretreatment reaction zone, includes adding hydrogen in hydrotreating reaction area Desulphurization catalyst and hydrodenitrogeneration (carbon residue conversion) catalyst include catalytic cracking catalyst in catalytic cracking reaction zone；
(2) inferior feedstock oil, the recycle oil of hydrotreating zone, catalytic cracked oil pulp, partially catalyzed cracking recycle oil and hydrogen one It rises and enters the molten hydrogen logistics of mixer formation saturation；
(3) the molten hydrogen logistics of saturation from step (2) enters weighted BMO spaces reaction zone, and liquid is carried out under the conditions of weighted BMO spaces Metal impurities are removed 40wt%~90wt% by phase hydrogenation reaction, and sulphur is removed 20wt%~70wt%, obtain tenor reduction Reaction effluent；
(4) enter mixed hydrogen tank after the reaction effluent that step (3) obtains is mixed with partially catalyzed cracking recycle oil without isolation, satisfy Enter liquid-phase hydrogenatin treatment reactor with the miscella after molten hydrogen, carry out hydrogenation reaction under hydroprocessing conditions, obtains sulphur and contain The reaction effluent that amount and nitrogen content reduce；
(5) liquid-phase hydrogenatin reaction effluent a part that step (4) obtains is recycled back to weighted BMO spaces reaction zone, another part into Enter separator and carry out gas-liquid separation, obtains hydrogen-rich gas and the first liquid；Separating obtained hydrogen-rich gas ejector, it is separating obtained First product liquid enters fractionating system；
(6) separating obtained first product liquid of step (5) enters fractionating column, obtains gas, naphtha, hydrogenated diesel oil and adds hydrogen tail Oil；
(7) hydrogenation tail oil obtained by step (6) enters catalytic cracking reaction zone, and it is anti-that cracking is carried out in the presence of catalytic cracking catalyst It answers, reaction generates after oil is fractionated and obtains dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytic cracking recycle oil And catalytic cracked oil pulp；
(8) catalytic cracking recycle oil from step (7) is divided into two parts, and a part is used as dilution after mixing with catalytic cracked oil pulp Oil, is recycled back to weighted BMO spaces reaction zone, and another part is recycled back to the mixed hydrogen tank in hydrotreating reaction area and carries out mixed hydrogen.
According to the method for the present invention, it in step (8) can also include wherein the following contents: catalysis obtained by step (7) is split At least part for changing diesel oil is recycled back to hydrotreating reaction area second and mixes hydrogen tank.
Wherein the average reaction temperature t1 of step (3) weighted BMO spaces reaction zone is higher than step (4) hydrotreating reaction area Average reaction temperature t2,5~40 DEG C of t2 high of preferably t1 ratio, more preferable t1 ratio t2 high is 10~30 DEG C high.
In the present invention, more than two weighted BMO spaces reaction zones are preferably provided in step (1), the more than two plus hydrogen Pretreatment reaction area is usually the reaction zone that is arranged in parallel, can be switched operation.Therefore, method of the invention can also include step (9), after one of weighted BMO spaces reaction zone is not able to satisfy service requirement, it can cut out to reaction process, and by In two weighted BMO spaces reaction zone incision process flows, the weighted BMO spaces reaction zone cut out can carry out setting for catalyst It changes, that is, draws off the old catalyst of inactivation, reload fresh and/or regenerated catalyst.
The weighted BMO spaces reaction zone is not able to satisfy service requirement and refers to: the effluent of weighted BMO spaces reaction zone can not The pressure drop for meeting at least one catalyst bed in the feed needs or weighted BMO spaces reaction zone of downstream hydrogenation treatment region reaches There is hot spot in the pressure drop upper limit or catalyst bed.
The standard of the feed needs for being unable to satisfy downstream hydrogenation processing reaction zone can be with are as follows: weighted BMO spaces reaction zone Exporting the tenor in product liquid is more than specified value.Specifically, judging weighted BMO spaces reaction zone outlet product liquid is The standard of the no feed needs for meeting downstream hydrogenation treatment region is, tenor in effluent liquid (refer to W metal, V, Fe, The summation of Na and Ca equal size) it has been more than the 8 μ g/g of μ g/g~50, preferably 10 μ of μ g/g~30 g/g.
The pressure drop upper limit is 0.4~0.8 times, preferably 0.5~0.8 times of reactor design maximum pressure drop.It is described Hot spot is that the radial temperature difference at least one catalyst bed is 15~50 DEG C, preferably 15~30 DEG C.
In the method for the present invention, the heavy oil feedstock oil refer to by topped crude, petroleum residual oil, oil-sand, pitch, shale oil, The hydro carbons for the high asphalt content that liquefaction coal or reclaimed oil obtain.Heavy oil feedstock oil usually contains various pollutants, carbon residue The impurity contents such as height, sulphur and nitrogen are high, and tenor is typically larger than 30mg/g.The method of the present invention is especially suitable for processing high metal and contains The heavy oil feedstock of amount, be especially suitable for processing metal (nickel+vanadium) content be greater than 60mg/g and/or iron content be greater than 10mg/g and/or Calcium content is greater than the heavy oil feedstock of 10mg/g.
In the method for the present invention, the hydrogenation protecting catalyst that weighted BMO spaces reaction zone uses can be protected for residual hydrogenation Agent, or prepared according to feedstock property by conventional method in that art.Residual hydrogenation protective agent is this field conventional catalyst, can be with Using commercial goods.The hydrogenation protecting agent using porous refractory inorganic oxide such as aluminium oxide as carrier, group VIB and/or The oxide of VIII race's metal such as W, Mo, Co, Ni etc. is the catalyst of active component, such as by the limited public affairs of Sinopec's share Take charge of the FZC series residual hydrogenation protective agent of catalyst branch production.
The Hydrodemetalation catalyst can be residuum hydrogenating and metal-eliminating catalyst, or according to feedstock property by this The preparation of field conventional method.These catalyst are typically all the group VIB using porous refractory inorganic oxide such as aluminium oxide as carrier And/or VIII one or more of oxides of race's metal such as W, Mo, Co, Ni etc. be active component, be selectively added other each The catalyst of the elements such as kind auxiliary agent such as P, Si, F, B.The Hydrodemetalation catalyst, on the basis of the total weight of catalyst, And in terms of oxide, the content of molybdenum and/or tungsten is 0.5~15 weight %, and the content of cobalt and/or nickel is 0.3~8 weight %, remaining Amount is alumina support.The alumina support be a kind of bimodal hole alumina support, 0.5~2.0 milliliter of Kong Rongwei/ Gram, specific surface area is 120~350 meters2/ gram, aperture accounts for total pore volume 30~90% in 10~30 nanometers of Kong Rong, and aperture is 100 ~2000 nanometers of Kong Rong accounts for total pore volume 10~50%, and bore dia is less than 10 nanometers, between 30-100 nanometers and be greater than 2000 nanometers of the sum of Kong Rong accounts for 20% or less total pore volume.It is arrived needed for the diffusion process and reaction of reactant molecule in order to balance The catalyst of active surface, the bimodal pore distribution with macropore and mesoporous is shown in weighted BMO spaces reaction zone reaction process Preferable performance.In weighted BMO spaces reaction zone, the admission space ratio of hydrogenation protecting catalyst and Hydrodemetalation catalyst Generally 5:95~95:5, preferably 10:90~60:40.
In the weighted BMO spaces reaction zone, it preferably can also include in the downstream of Hydrodemetalation catalyst plus hydrogen is de- Sulfur catalyst.The loadings of Hydrobon catalyst are the 5%~30% of Hydrodemetalation catalyst loadings.
The Hydrobon catalyst can be the common residuum hydrodesulfurization catalyst in this field, or according to raw material Property is prepared by conventional method in that art.Catalyst is typically all using porous refractory inorganic oxide such as aluminium oxide as carrier the The oxide of VI B race and/or VIII race's metal such as W, Mo, Co, Ni etc. are active component, are selectively added various other auxiliary agents such as P, the catalyst of the elements such as Si, F, B.Due in this technology in weighted BMO spaces reaction zone product it is restricted to tenor, be The more preferable overall performance optimization for playing catalyst system uses improved Hydrobon catalyst, the overall performance of the catalyst Between conventional Hydrodemetalation catalyst and Hydrobon catalyst, i.e., the aperture of the catalyst is compared with conventional hydrodesulfurization Catalyst is bigger, holds metal ability with preferable, activity is slightly higher compared with conventional hydro catalyst for demetalation, has stronger add Hydrogen desulphurizing ability.
The Hydrobon catalyst, on the basis of the total weight of catalyst, and in terms of oxide, molybdenum and/or tungsten Content is 10~25 weight %, and the content of cobalt and/or nickel is 1~6 weight %, and surplus is alumina support.The aluminium oxide Kong Rong is not less than 0.35 ml/g, and specific surface area is 150~350 meters2/ gram, aperture accounts for total pore volume in 6~15 nanometers of Kong Rong 70% or more.
In the method for the present invention, reaction condition can be according to the reaction effect that the property and requirement of raw material reach by this field General knowledge determines.In general the reaction condition of weighted BMO spaces reaction zone is that reaction pressure is 5MPa~35MPa, preferably It is 10MPa~20MPa, average reaction temperature is to be operated at 340 DEG C~430 DEG C, preferably 340 DEG C~420 DEG C, volume is empty when liquid Speed is generally in 0.1h-1~5.0h-1, preferably 0.3h-1~3.0h-1In the range of, liquid phase circulation ratio (recycle oil/fresh feed oil Mass ratio) be 0.1:1~10:1, preferably 0.2:1~3:1.
In method of the invention, the reaction of one or more hydrogenation protecting is can be set in the weighted BMO spaces reaction zone Device, each hydrogenation protecting reactor is at least provided with a hydrogenation protecting catalyst bed, if being provided with multiple catalyst beds, The recycle oil for being saturated molten hydrogen can be squeezed into, between reaction bed to reach reduction catalyst bed temperature rise and reaction is replenished in time The purpose of required hydrogen.
In the method for the present invention, the mixer used can be eddy mixer, be also possible to static mixer, jet mixing Device etc. mixer.
In the method for the present invention, catalyst used in hydrotreating reaction area can be the common heavy oil product in this field and add Hydrogen handles catalyst, and optimum catalyst property can be optimized according to feedstock property.Catalyst generally comprise it is a variety of, such as plus hydrogen Desulphurization catalyst and hydrodenitrogenation catalyst etc..These catalyst are typically all to be with porous refractory inorganic oxide such as aluminium oxide The oxide of carrier, group VIB and/or VIII race's metal such as W, Mo, Co, Ni etc. are active component, are selectively added other each The catalyst of the elements such as kind auxiliary agent such as P, Si, F, B.
In the hydrotreating reaction area, the admission space of Hydrobon catalyst and hydrodenitrogenation catalyst is than general For 20:80~80:20, preferably 40:60~70:30.
The hydrodenitrogenation catalyst, on the basis of the total weight of catalyst, and in terms of oxide, molybdenum and/or tungsten Content is 12~30 weight %, and the content of cobalt and/or nickel is 3~12 weight %, and surplus is alumina support.The aluminium oxide Kong Rong is not less than 0.35 ml/g, and specific surface area is 150~350 meters2/ gram, aperture accounts for total pore volume in 6~15 nanometers of Kong Rong 40~75%.
According to the method for the present invention, wherein it can also add hydrogen including Hydrodemetalation catalyst in hydrotreating reaction area Catalyst for demetalation is seated in the upstream of Hydrobon catalyst, and the loadings of Hydrodemetalation catalyst are hydrotreating reaction The 2%~30% of area's catalyst total filling amount.
In hydrotreating reaction area catalyst filling sequence be usually make reaction stream successively with hydrodemetallisation catalyst Agent, Hydrobon catalyst and hydrodenitrogenation catalyst contact, also have certainly by the technology of these types of catalyst mixed packing.On State the technology contents that Catalyst packing technology is well known to those skilled in the art.Catalyst can use commercial goods, as in The FZC series residuum hydrogenating and metal-eliminating catalysts of petrochemical industry Fushun Petrochemical Research Institute, state development and production, desulphurization catalyst and de- Nitrogen catalyst can also be prepared according to this field existing method.
In method of the invention, the reaction condition of weighted BMO spaces reaction zone is that reaction pressure is 5MPa~35MPa, excellent It is selected as 10MPa~20MPa, average reaction temperature is to operate at 320 DEG C~420 DEG C, preferably 330 DEG C~410 DEG C, volume when liquid Air speed is generally 0.1h-1~5.0h-1, preferably 0.3h-1~3.0h-1, liquid phase circulation ratio (recycle oil/fresh feed oil quality Than) it is 0.1:1~10:1, preferably 0.2:1~3:1.
In the method for the present invention, weighted BMO spaces and hydrotreating two reaction zones belong to serial operation, therefore two reactions The pressure in area is the same pressure rating, because the presence of pressure drop might have difference slightly.
In the method for the present invention, hydrodemetallization and partial hydro-desulfurization reaction are substantially carried out in weighted BMO spaces reaction zone, It is operated at a higher temperature, is conducive to the progress of demetalization reaction, to enable the activity of Hydrodemetalation catalyst It is fully used.The material for being stripped of a large amount of metal impurities enters hydrotreating reaction area and is further reacted.Due to A large amount of metal impurities are stripped of, the material into hydrotreating reaction area is greatly lowered the murder by poisoning of hydrotreating zone catalyst, The utilization rate of Hydrobon catalyst and hydrodenitrogenation catalyst can be significantly improved, the use of hydrotreating zone catalyst is extended Service life, and then effectively extend the operation cycle of a whole set of hydrotreater.For the operation of Proper Match two reaction zones, add hydrogen The average reaction temperature in pretreatment reaction area is 5~40 DEG C high compared with the average reaction temperature in hydrotreating reaction area, preferably high by 10~ 30℃。
In method of the invention, a reactor is can be set in hydrotreating reaction area, and more reactors also can be set, Usually setting 2~5, is preferably provided with 2~3 reactors.The number of each catalyst in reactor bed is generally 1~5, It is preferred that 1~3, if more than two catalyst beds are arranged, the generation oil for being saturated molten hydrogen can be squeezed between bed, it can To further increase the dissolution hydrogen amount in reactor in liquid, the purpose of hydrodesulfurization, hydrodenitrogeneration is better achieved.Adding hydrogen It handles in reaction zone, successively load Hydrodemetalation catalyst, Hydrobon catalyst along the flow direction of reaction stream and adds hydrogen Denitrification catalyst.In the method for the present invention, the loadings of catalyst can be according to feedstock property, selected in each catalyst bed The requirement of catalyst and product property is specifically chosen.
To reach better effect, more than two changeable weighted BMO spaces reaction zones can be used.It is described changeable Meaning refers to provided with multiple weighted BMO spaces reaction zones, and each weighted BMO spaces reaction zone can individually be connected into subsequent add Hydrogen handles reaction zone, can also individually cut out from hydrotreating reaction area.
Hydrotreating method according to the present invention, be arranged multiple changeable weighted BMO spaces reaction zones purpose be in order to The catalyst in each reactor in hydrotreating reaction area is set to obtain lasting hydrogenation protecting, therefore, Mei Gejia by switching As long as the number and connection relationship of hydrogen pretreatment reaction zone setting reactor meet the purpose that switching uses.Preferably, institute The quantity for stating weighted BMO spaces reaction zone is 2, and 1 reactor is arranged in the weighted BMO spaces reaction zone, preferably with Mode in parallel connects, and two weighted BMO spaces reaction zones one and only one be in on-line machining state.Weighted BMO spaces Sequence filling hydrogenation protecting agent, Hydrodemetalation catalyst and Hydrobon catalyst, all kinds of protective agents and catalysis in reaction zone The gradation mode of agent can be determined according to the property of raw material by this field Conventional wisdom.
In method of the invention, described two weighted BMO spaces reaction zones one and only one be online it is specific It is meant that, when the first weighted BMO spaces reaction zone is unable to satisfy the feed needs or the first weighted BMO spaces of downstream hydrogenation treatment region The pressure drop of at least one catalyst bed reaches in reaction zone when there is hot spot in the pressure drop upper limit or catalyst bed, by first plus All reactors in hydrogen pretreatment reaction zone are cut out, while the reactor of the second weighted BMO spaces reaction zone being cut.When Two weighted BMO spaces reaction zones are unable to satisfy the feed needs or the second weighted BMO spaces reaction zone of downstream hydrogenation processing reaction zone In the pressure drop of at least one catalyst bed reach and occur hot spot in the pressure drop upper limit or catalyst bed and can not continue to operate When, protective agent and catalyst whole in all reactors are replaced after can stopping work with device.It can also be according to hydrotreating reaction The reactor of the second weighted BMO spaces reaction zone is cut out the case where catalyst activity in area, while protective agent will have been replaced and urged Reactor incision in first weighted BMO spaces reaction zone of agent, so recycles, until the catalyst in hydrotreating reaction area It is unable to satisfy running requirements.
There is no particular limitation to flow direction of the raw material in hydrogenation protecting area and hydrotreating zone by the present invention, weighted BMO spaces Each reactor in reaction zone and hydrotreating reaction area both can may be downflow reactor for up-flow reactor.
Catalytic cracking recycle oil in method of the invention, into hydrotreating reaction area and weighted BMO spaces reaction zone It can be the catalytic cracking recycle oil and catalytic cracking that catalytic cracking reaction zone in the method for the present invention obtains with catalytic cracked oil pulp Slurry oil also may include catalytic cracking recycle oil and catalytic cracked oil pulp that other catalytic cracking units obtain.The method of the present invention The catalytic cracking recycle oil that middle catalytic cracking reaction zone obtains is partly recycled to hydrotreating reaction area first and mixes hydrogen tank, another portion Divide after being mixed with catalytic cracked oil pulp and be recycled to weighted BMO spaces reaction zone, is recycled to hydrotreating reaction area first and mixes hydrogen tank Recycle oil accounts for 10% or more of the catalytic cracking recycle oil weight that catalytic cracking reaction zone obtains, and preferably 20 ~ 50%, it is recycled to plus hydrogen The recycle oil in pretreatment reaction area accounts for 10% or more of the catalytic cracking recycle oil weight that catalytic cracking reaction zone obtains, preferably 20 ~ 50%, be recycled to hydrotreating reaction area first mix hydrogen tank recycle oil and be recycled to weighted BMO spaces reaction zone recycle oil it is total Amount generally at least accounts for 20% or more, preferably 30 ~ 95% of the catalytic cracking recycle oil weight that catalytic cracking reaction zone obtains, remainder The catalytic cracking recycle oil divided is recycled back to catalytic cracking reaction zone.The catalytic cracked oil pulp that catalytic cracking reaction zone obtains is recycled to Weighted BMO spaces reaction zone, the catalytic cracked oil pulp for being recycled to weighted BMO spaces reaction zone generally at least account for catalytic cracking reaction zone 30% or more of obtained catalytic cracked oil pulp weight, preferably 50 ~ 80%, the catalytic cracked oil pulp outlet of remainder.
According to the method for the present invention, wherein can also include: that can completely or partially be recycled to catalytic cracking diesel oil to add Hydrogen processing reaction zone second mixes hydrogen tank.The catalytic cracking diesel oil for being recycled to hydrotreating reaction area generally at least accounts for Catalytic Cracking Unit of Measure 10% or more of the catalytic cracking diesel oil fraction weight for answering area to obtain, preferably 20 ~ 80%, the catalytic cracking diesel oil of remainder can be with It is recycled back to catalytic cracking reaction zone or as desired as product outlet.It more preferably, can also include that will be catalyzed to split in the present invention Change the process that diesel oil is cut into light fraction and heavy distillat, the temperature of the cutting is 245 ~ 300 DEG C.The heavy distillat, which introduces, to be added Hydrogen handles the mixed hydrogen tank before the last one reactor of reaction zone, and the light fraction introduces the last one reaction of hydrotreating reaction area In the middle part of device.
It, can be further if there is solid impurity in catalytic cracking recycle oil and catalytic cracked oil pulp in the method for the present invention It is recycled after removing.Solid impurity content in the catalytic cracking recycle oil and catalytic cracked oil pulp of the removing solid impurity Less than 30 μ g/g, preferably smaller than 15 μ g/g, more preferably less than 5 μ g/g.
In method of the invention, catalytic cracking unit be can be more than a set of or a set of, and every covering device includes at least one Fractionating column need to be arranged in reactor, a regenerator, catalytic cracking unit, fractionation can be respectively set with every set catalytic cracking unit Tower can also share fractionating column.Fractionating column by catalytic cracking reaction effluent be fractionated for dry gas, liquefied gas, catalytically cracked gasoline, Catalytic cracking diesel oil, catalytic cracking recycle oil and catalytic cracked oil pulp etc., the cut point of each fraction can according to need specific true It is fixed.
In method of the invention, the operating condition of catalytic cracking reaction zone is general are as follows: 470~650 DEG C of reaction temperature, reaction 0.5~5 second time, catalyst and feedstock oil weight ratio 3~10,650~800 DEG C of catalyst regeneration temperature.Catalytic Cracking Unit of Measure Device is answered to be generally the combination of riser reactor or riser and bed reactor.Catalytic cracking catalyst includes zeolite, inorganic Oxide and optional clay, the weight content of each component are respectively as follows: zeolite 5%~50%, inorganic oxide 5%~95%, clay 0 ~70%.Zeolite as active component, can selected from y-type zeolite, rare earth Y type zeolite (REY), rare earth hydrogen y-type zeolite (REHY), One or more of ultrastable (USY), ZSM series zeolite and ZRP zeolite.Inorganic oxide is selected from as binder Silica (SiO2) and/or alchlor (AL2O3).The clay is selected from kaolin and/or more water as matrix, i.e. carrier Kaolin.
In the prior art, according to Flow of Goods and Materials direction in heavy oil hydroprocessing units, despite the presence of the influence of cold hydrogen, still Low early and high after trend is generally presented in reaction temperature, i.e., in from start of run to the whole cycle in operating latter stage, hydrogen is added to protect Protect a few class catalyst beds such as catalyst, Hydrodemetalation catalyst, Hydrobon catalyst and/or hydrodenitrogenation catalyst Average reaction temperature is successively raised.Meanwhile setting of the existing catalyst grade with system is with all anti-when operating latter stage Device is answered to reach synchronous inactivation, synchronize and change for the purpose of agent.Therefore, during operation, when the pressure drop rise of first reactor or Need horse back whole device out of service to replace when there is hot spot or when hydrogenation products are not able to satisfy downstream unit requirement Some catalyst.Catalyst in the hydrodesulfurization swum in such a case the lower and/or denitrification reactor also " has lost substantially It is living ".Therefore the operation cycle of package unit is limited by first catalyst reactor service life.And even for adding It is a whole set of for hydrogen protection is using the hydroprocessing technique (such as CN1484684A and CN102453530A) of reactor handover operation The operation cycle of device is similarly subjected to the limitation of first catalyst reactor service life.
After having carried out a large amount of research to existing hydrotreating method, present inventor is surprised to find that: existing In technology, after residual hydrocracking device is stopped work because of hot spot and/or the pressure drop of hydrogenation protecting catalyst bed, device rear portion (downstream) although the desulphurization catalyst and denitrification catalyst that use also have inactivated, deactivation cause is more because of catalysis Caused by the deposited metal blocking in the aperture in agent duct, and the metal deposited inside catalyst duct is really and few.Concrete analysis Its reason, applicant think: in the middle and later periods of residual hydrogenation equipment operating, the metal in feedstock oil " has penetrated " hydrogenation protecting and has urged Agent and catalyst for demetalation bed, and it has been directly entered the desulphurization catalyst and denitrification catalyst bed at rear portion.Due to desulfurization The aperture of catalyst and/or denitrification catalyst is smaller, and the metal of removing cannot be introduced into inside duct so being deposited on catalysis Near agent aperture, so as to cause the inactivation of desulphurization catalyst and denitrification catalyst.In this condition, Hydrobon catalyst And/or the inactivation of hydrodenitrogenation catalyst be not because catalyst itself carbon distribution and caused by, but because feedstock oil wear After saturating hydrogenation protecting catalyst bed and Hydrodemetalation catalyst bed so that should undertake more hydrodesulfurizations and/or The desulfurization of denitrification functions and/or denitrification catalyst undertake caused by the function of hydrodemetallization.Meanwhile originally designed for de- After the catalyst of sulphur, denitrogenation and/or de- carbon residue undertakes partial hydrogenation demetalization function, due to the limitation of its catalyst pore structure, Also demetalization function cannot be realized well, while also creating desulfurization, denitrogenation and/or the reduction of de- carbon residue ability, and is caused The waste of catalyst function, so that the activity of hydrodesulfurization and/or hydrodenitrogenation catalyst cannot be fully utilized.
A whole set of residual hydrogenation equipment can be divided into weighted BMO spaces reaction by numerous studies discovery by the present inventor Area and hydrotreating reaction area, wherein weighted BMO spaces reaction zone operates under relatively high reaction temperature, and hydrotreating is anti- Area is answered to operate under relatively low reaction temperature.The gold of weighted BMO spaces reaction zone outlet material is controlled in technical solution first Belong to content, i.e. most of metal impurities in weighted BMO spaces reaction zone removing feedstock oil, remaining a small amount of more difficult removing Metal impurities, while realizing partial hydro-desulfurization.And the hydrotreating reaction that the reaction stream of weighted BMO spaces reaction zone enters Area is to operate at relatively low temperature, i.e., carries out hydrodesulfurization at relatively low temperature and add hydrogen saturated reaction, this Sample metal impurities can directly pass through desulphurization catalyst and/or denitrification catalyst in the case where being not involved in reaction, so as to avoid Catalyst is because of permanent deactivation caused by metal deposit.Product is made to meet the feed needs of downstream unit by scheme optimization. Compared with prior art, method of the invention changes existing residual hydrogenation equipment catalyst system and operation mode, i.e., will show It is low early and high after to have the tendency that technology is presented according to logistics orienting response temperature, changes into before being presented according to logistics orienting response temperature Low trend after height, method of the invention can make full use of the activity of all catalyst of residual hydrogenation equipment, to increase residual oil The operational efficiency of hydrogenation plant improves its economy.The present inventor completes the present invention on this basis.
In the prior art, has the technical solution that catalytic cracking recycle oil is recycled to residual hydrogenation equipment.But this hair Bright people passes through the study found that the viscosity of resid feed can be reduced by mixing a small amount of catalytic cracking recycle oil in resid feed, promotees The impurity removal of slag input oil reacts.But with the raising of catalytic cracking recycle oil mixed ratio, when residual hydrogenation equipment charging After viscosity reduces to a certain extent, the mixed ratio of catalytic cracking recycle oil is continued growing, to residual hydrogenation removing impurities qualitative response Facilitation will not further increase.Simultaneously because containing the heavy metals such as a large amount of Ni, V, carbon residue height, asphalitine in residual oil Height, can seriously affect catalytic cracking recycle oil adds hydrogen effect.Therefore catalytic cracking recycle oil is divided into two parts by the present invention, and one Flux oil of the part as residual oil raw material, another part are recycled to hydrotreating zone and mix with weighted BMO spaces area reaction effluent Hydrotreating is carried out under higher hydrogen partial pressure and lower reaction temperature afterwards.Both can achieve in this way, which reduces residual oil raw material, glues Degree, promotes the purpose of residual hydrogenation removing impurities qualitative response, while the hydrofinishing of catalytic cracking recycle oil also may be implemented, and improvement is urged Change the effect that cracking recycle oil adds hydrogen.In addition, the catalytic cracking recycle oil of low temperature position is recycled to hydrotreating zone, be conducive to adjust The temperature of weighted BMO spaces area high-temperature position reaction effluent is conducive to the reaction temperature for controlling hydrotreating zone, can save and change The equipment investments such as hot device.
By contrast with distillate hydrogenation device, the general rear portion catalyst bed carbon deposit of residual hydrocracking device is serious, And it is more closer to reactor outlet carbon deposit.This is primarily due to colloid and oil adds hydrogen saturated velocity fast, and asphalitine adds Hydrogen saturated velocity is slow, and is easy broken side chain, only the high aromatic core of surplus aromaticity, thus the environment higher and higher in saturation degree Solubility is smaller and smaller in solvent, is finally very easy to deposition and forms carbon deposit on a catalyst.After catalytic cracking recycle oil is added, Surrounding solvent will can be improved to the peptizing power of asphalitine, reduce its deposition on the catalyst of rear portion, extend making for catalyst Use the service life.In addition the partial hydrogenation product of polycyclic aromatic hydrocarbon is very strong hydrogen supply agent in catalytic cracking recycle oil, can reduce residual oil heat Free radical condensation, inhibits the generation of coke precursor.These can all greatly reduce the carbon deposit of catalyst, reduce deactivation rate, Extend the operation cycle.
Compared with prior art, the method have the advantages that:
1, by the way that heavy oil hydroprocessing units are divided into weighted BMO spaces reaction zone and hydrotreating reaction area, in weighted BMO spaces Reaction zone remove material in most of metal impurities so that into hydrotreating zone material to hydrotreating zone catalyst Murder by poisoning is greatly lowered, thus can make full use of the activity of all catalyst in hydrotreating zone.Compared with prior art, device The overall operation period can extend 30~100%, to increase the operational efficiency of device, improve economy.
2, reactor is protected using switchable type in weighted BMO spaces reaction zone, substantially increases the demetalization energy of device Power has widened raw material sources so as to process the higher raw material of tenor.
3, since weighted BMO spaces reaction zone is stripped of most of metal impurities in material, so that hydrotreating reaction area The deactivation cause of middle desulphurization catalyst and/or denitrification catalyst becomes only carbon deposit mistake from previous metal deposit and coking deactivation It is living, so that desulphurization catalyst and denitrification catalyst can carry out regeneration treatment after using a cycle, it is greatly saved and urges Agent buying expenses.
4, package unit uses liquid-phase hydrogenatin, on the one hand solves the purpose for reducing catalyst bed temperature rise, can effectively keep away Exempt from the generation of hot spot, at the same also significantly reduce between bed and/or between reactor quenching hydrogen injection rate, on the other hand by plus The recycle oil of hydrogen is saturated part aromatic hydrocarbons, has the function of hydrogen supply, can inhibit coke formation, and catalyst carbon deposit is avoided to lose It is living, and then extend the service life of catalyst.
5, the activity for making full use of the catalyst in hydrotreating reaction area, improves the treating capacity of device, or reduces Equipment investment.The catalytic cracking recycle oil of low temperature position is recycled to hydrotreating zone, is conducive to adjust weighted BMO spaces area high-temperature position The temperature of reaction effluent is conducive to the reaction temperature for controlling hydrotreating zone, can save the equipment investments such as heat exchanger.
6, catalytic cracking recycle oil and catalytic cracked oil pulp are recycled to weighted BMO spaces area and hydrotreating zone respectively, it can The imurity-removal in hydrogenation process, aromatic hydrocarbons saturation become better catalytically cracked material composition, further improve catalytic cracking High addition product yield.
7, in the method for the present invention, catalytic cracked oil pulp and partially catalyzed cracking recycle oil are recycled to as flux oil and add hydrogen pre- Entrance of the treatment zone can reduce the viscosity of residual oil raw material, improve the flow distribution and mass transfer of raw material in the reactor, and reduction is diffused in Influence during residual hydrocracking improves the deposition distributions of the metals in reaction system such as nickel, vanadium, extends making for catalyst Use the service life.Catalytic cracking recycle oil is recycled to weighted BMO spaces area and hydrotreating zone, and surrounding solvent will can be improved to asphalitine Peptizing power, reduce its deposition on the catalyst of rear portion, extend the service life of catalyst.In addition catalytic cracking recycle oil The partial hydrogenation product of middle polycyclic aromatic hydrocarbon is very strong hydrogen supply agent, can reduce the condensation of residual oil hot radical, inhibit coke precursor Generation.These can all greatly reduce the carbon deposit of catalyst, reduce deactivation rate, extend the operation cycle.
8, in the method for the present invention, catalytic cracking diesel oil is recycled to the mixed hydrogen before the last one reactor of hydrotreating reaction area Tank, the lower reaction temperature in hydrotreating reaction area are conducive to the aromatic hydrocarbons saturation in catalytic cracking diesel oil；It can be catalyzed by adjusting The internal circulating load of cracked diesel oil controls the hydrogenation depth of the last one reactor of hydrotreating reaction area.
Detailed description of the invention
Fig. 1 is a kind of process flow diagram of the method for the present invention.
Fig. 2 is another process flow diagram of the method for the present invention.
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Attached drawing is a kind of methodological principle flow diagram of group technology processing poor residuum provided by the present invention, in figure Many necessaries (heating furnace, heat exchanger, pump and valve etc.) is omitted.
A kind of process of the method for group technology processing poor residuum provided by the present invention is as follows:
It first comes from fresh feed residual oil, the catalytic cracking recycle oil from pipeline 42 and the catalytic cracked oil pulp of pipeline 8, come from The new hydrogen of pipeline 23 and the hydrotreatment products recycle oil being recycled back to through pipeline 21 enter mixer 5 together and form the molten hydrogen object of saturation Stream.It is saturated molten hydrogen stream passes via line 24 and pipeline 10 enters in the reactor 1 of the first weighted BMO spaces reaction zone, deposited in catalyst It is reacted in lower progress hydrodesulfurization and hydrodemetallization.Hydrogenation products are at the top of the reactor 1 of the first weighted BMO spaces reaction zone Outflow enters mixed hydrogen tank 6, the hydrogen introduced with pipeline 15 after pipeline 9 is mixed with the catalytic cracking recycle oil from pipeline 41 It carries out mixing molten hydrogen, the exess of H2 gas is discharged through pipeline 14, and the miscella after being saturated molten hydrogen enters liquid-phase hydrogenatin through pipeline 16 and reacts Device 3 carries out hydrotreating reaction.Reaction effluent enters mixed hydrogen tank 7 through pipeline 17, and the hydrogen introduced with pipeline 19 is mixed Molten hydrogen, the exess of H2 gas are discharged through pipeline 18, and the miscella after being saturated molten hydrogen is added through pipeline 20 into liquid phase hydrogenation reactor 4 Hydrogen processing reaction.Gained reaction effluent a part is recycled back to weighted BMO spaces area through pipeline 21, another part through pipeline 22 into Enter separator 25 and carry out gas-liquid separation, separating obtained hydrogen-rich gas is extracted out through pipeline 26, the first isolated liquid through line 27 extractions enter fractionating column 28 and are separated, and gas, naphtha, hydrogenated diesel oil and residual hydrogenation tail oil are obtained, respectively through pipeline 29, pipeline 30, pipeline 31 and pipeline 32 are extracted out.
Residual hydrogenation tail oil from pipeline 32 enters catalytic cracking reaction zone 33, in the presence of catalytic cracking catalyst into Row cracking reaction, after reaction oil gas be fractionated after obtain gas, catalytic gasoline, catalytic cracking diesel oil, catalytic cracking recycle oil and Catalytic cracked oil pulp.Dry gas, liquefied gas and catalytic gasoline go out device through pipeline 34,35 and 36 respectively.Catalytic cracking diesel oil is through pipe Line 37 is recycled back to catalytic cracking reaction zone or as desired as product outlet.Catalytic cracking recycle oil is divided into two parts, a part , as flux oil, through pipeline 42 and pipeline 8 is come from after the catalytic cracked oil pulp of pipeline 39 mixes through pipeline 38 and pipeline 40 Fresh feed residual oil, the new hydrogen from pipeline 23 and the hydrotreating zone recycle oil from pipeline 21 enter mixer 5 together It is formed and is saturated molten hydrogen logistics, another part is recycled to hydrotreating reaction area through pipeline 38 and pipeline 41 and mixes hydrogen tank 6.
Fig. 2 is another flow diagram for the method that a kind of group technology of the present invention handles poor residuum, not with Fig. 1 It is with place, catalytic cracking diesel oil is recycled to the mixed hydrogen tank 7 before hydrotreating zone reactor 4 through pipeline 37.
When the reactor 1 of the first weighted BMO spaces reaction zone is unable to satisfy feed needs or the reaction of downstream hydrogenation treatment region The pressure drop of at least one catalyst bed reaches in device 1 when there is hot spot in the pressure drop upper limit or catalyst bed, is cut out, and The reactor 2 of the second weighted BMO spaces reaction zone is cut through pipeline 12 to continue to complete hydroprocessing processes, while replacing first Catalyst in weighted BMO spaces reaction zone reactor 1, it is stand-by to reload fresh catalyst.When the second weighted BMO spaces react The reactor 2 in area is unable to satisfy at least one catalyst bed in the feed needs or reactor 2 of downstream hydrogenation processing reaction zone Pressure drop reach in the pressure drop upper limit or catalyst bed when there is not continuing the hot spot of operation, cut out, while cutting the The reactor 1 of one weighted BMO spaces reaction zone continues to complete hydroprocessing processes, while replacing the reaction of the second weighted BMO spaces Catalyst in the reactor 2 in area, it is stand-by to reload fresh catalyst.So circulation, until reaching urging for hydrotreating zone The service life of agent.
It is limited below in conjunction with specific embodiment is further to method of the invention.Original used in Examples and Comparative Examples The property of material oil is listed in table 1, and the property of used catalyst is listed in table 2.In table 2, A is hydrogenation protecting catalyst, and B is plus hydrogen is de- golden Metal catalyst, C are Hydrobon catalyst, and D is hydrodenitrogeneration (carbon residue conversion) catalyst.Used in embodiment and comparative example Catalytic cracking catalyst is identical, 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 Auxiliary agent.
1 raw material oil nature of table
2 catalyst property of table
Embodiment 1
According to process flow described in Fig. 1, weighted BMO spaces reaction zone includes the first weighted BMO spaces reaction of changeable operation A reactor 1 is arranged in area and the second weighted BMO spaces reaction zone, the first weighted BMO spaces reaction zone, and the second weighted BMO spaces are anti- Answer area that one reactor 2 is set, hydrotreating reaction area includes the mixed hydrogen tank 6 being arranged in series, reactor 3, mixed hydrogen tank 7 and reaction Device 4.According to Flow of Goods and Materials direction, weighted BMO spaces reaction zone (it is online to only have a weighted BMO spaces reaction zone) in operation process Catalyst A, catalyst B and catalyst C are filled in reactor, the admission space ratio of each catalyst is 2: 7: 1.Hydrotreating is anti- It answers equipped with catalyst B and catalyst C in area's reactor 3, the admission space ratio of two kinds of catalyst is 1: 9, and is only filled in reactor 4 Fill out catalyst D.
In operation process, the reaction temperature of weighted BMO spaces reaction zone is compared with hydrotreating zone height, specific reaction condition and slag Oily hydrogenation reaction the results are shown in Table 3, and Hydrocarbon Content by Catalytic Cracking Operation condition is shown in Table 5, and catalytic cracking product is distributed and catalytically cracked gasoline property It is shown in Table 6.Feedstock oil A is followed by mixer 5, reactor 1, mixed hydrogen tank 6, reactor 3, mixed hydrogen tank 7 and reactor 4, a part Reaction effluent is recycled to mixer 5(recycle ratio 0.3:1), another part reaction effluent enters after gas-liquid separation and fractionation Catalytic cracking reaction zone is followed the 40% of the catalytic cracked oil pulp of catalytic cracking reaction zone whole and whole catalytic cracking recycle oils Ring is recycled to hydrotreating reaction area for the 40% of catalytic cracking reaction zone whole catalytic cracking recycle oil and mixes hydrogen tank to mixer 5 6, the straight connecting device of catalytic cracking diesel oil, and metal (Ni+V) content for controlling weighted BMO spaces reaction zone outlet effluent is not high In 12 μ g/g.Sulfur content is 0.21 weight % in hydrogenated back end hydrogenation processing reaction zone effluent, nitrogen content is 2016 μ g/g, residual Charcoal value is 4.54 weight %, metal (Ni+V) content is 7.37 μ g/g.Operating 6 months after, the first weighted BMO spaces reaction zone it is anti- Answer device 1 export effluent metal (Ni+V) content be more than at least one catalyst bed in 12 μ g/g or reactor 1 pressure drop Reach in the pressure drop upper limit or catalyst bed and hot spot occur, cut out, and cuts the reaction of the second weighted BMO spaces reaction zone Device 2 come continue to complete hydroprocessing processes (at this time feedstock oil A followed by mixer 5, reactor 2, mixed hydrogen tank 6, reactor 3, Mixed hydrogen tank 7 and reactor 4), device still even running, generating oil quality can satisfy downstream RFCC feed needs.When second The reactor 2 of weighted BMO spaces reaction zone export effluent metal (Ni+V) content be more than in 12 μ g/g or reactor 2 at least The pressure drop of one catalyst bed reaches in the pressure drop upper limit or catalyst bed when there is not continuing the hot spot of operation, is cut Out, while the reactor 1 of the first weighted BMO spaces reaction zone is cut to continue to complete hydroprocessing processes, while replacing second and adding Catalyst in the reactor 2 of hydrogen pretreatment reaction zone, it is stand-by to reload fresh catalyst.So circulation, the final residual oil Hydrogenation plant has operated 24 months, since product quality variation is stopped work, operates present invention device 1 and reactor 2 is distinguished Handling agent 2 times.
Comparative example 1
According to process flow described in Fig. 1, weighted BMO spaces reaction zone includes the first weighted BMO spaces reaction of changeable operation A reactor 1 is arranged in area and the second weighted BMO spaces reaction zone, the first weighted BMO spaces reaction zone, and the second weighted BMO spaces are anti- Answer area that one reactor 2 is set, hydrotreating reaction area includes the mixed hydrogen tank 6 being arranged in series, reactor 3, mixed hydrogen tank 7 and reaction Device 4.According to Flow of Goods and Materials direction, weighted BMO spaces reaction zone (it is online to only have a weighted BMO spaces reaction zone) in operation process Catalyst A, catalyst B and catalyst C are filled in reactor, the admission space ratio of each catalyst is 2: 7: 1.Hydrotreating is anti- It answers equipped with catalyst B and catalyst C in area's reactor 3, the admission space ratio of two kinds of catalyst is 1: 9, and is only filled in reactor 4 Fill out catalyst D.
In operation process, the reaction temperature of weighted BMO spaces reaction zone is lower than hydrotreating zone, specific reaction condition and slag Oily hydrogenation reaction the results are shown in Table 3, and Hydrocarbon Content by Catalytic Cracking Operation condition is shown in Table 5, and catalytic cracking product is distributed and catalytically cracked gasoline property It is shown in Table 6.Feedstock oil A is followed by mixer 5, reactor 1, mixed hydrogen tank 6, reactor 3, mixed hydrogen tank 7 and reactor 4, a part Reaction effluent is recycled to mixer 5(recycle ratio 0.3:1), another part reaction effluent enters after gas-liquid separation and fractionation Catalytic cracking reaction zone is followed the 40% of the catalytic cracked oil pulp of catalytic cracking reaction zone whole and whole catalytic cracking recycle oils Ring is recycled to hydrotreating reaction area for the 40% of catalytic cracking reaction zone whole catalytic cracking recycle oil and mixes hydrogen tank to mixer 5 6, the straight connecting device of catalytic cracking diesel oil, and metal (Ni+V) content of weighted BMO spaces reaction zone outlet effluent is not controlled. Sulfur content is 0.22 weight % in hydrogenated back end hydrogenation processing reaction zone effluent, nitrogen content is 2164 μ g/g, carbon residue 4.74 Weight %, metal (Ni+V) content are 9.55 μ g/g.After operating 10 months, in the reactor 1 of the first weighted BMO spaces reaction zone extremely The pressure drop of a few catalyst bed, which reaches in the pressure drop upper limit or catalyst bed, there is hot spot, is cut out, and cut second (feedstock oil A is at this time followed by mixer 5, anti-to continue to complete hydroprocessing processes for the reactor 2 of weighted BMO spaces reaction zone Answer device 2, mixed hydrogen tank 6, reactor 3, mixed hydrogen tank 7 and reactor 4), device still even running, generating oil quality can satisfy down Swim RFCC feed needs.After switching reactor 2, which has operated 7.5 months again, since product quality becomes Difference is stopped work, and the final device has operated 17.5 months.
Embodiment 2
According to process flow described in Fig. 1, weighted BMO spaces reaction zone includes the first weighted BMO spaces reaction of changeable operation A reactor 1 is arranged in area and the second weighted BMO spaces reaction zone, the first weighted BMO spaces reaction zone, and the second weighted BMO spaces are anti- Answer area that one reactor 2 is set, hydrotreating reaction area includes the mixed hydrogen tank 6 being arranged in series, reactor 3, mixed hydrogen tank 7 and reaction Device 4.According to Flow of Goods and Materials direction, weighted BMO spaces reaction zone (it is online to only have a weighted BMO spaces reaction zone) in operation process Catalyst A, catalyst B and catalyst C are filled in reactor, the admission space ratio of each catalyst is 3: 6: 1.Hydrotreating is anti- It answers equipped with catalyst B and catalyst C in area's reactor 3, the admission space ratio of two kinds of catalyst is 3: 7, and filling is urged in reactor 4 Agent C and catalyst D, the admission space ratio of two kinds of catalyst are 2: 8.
In operation process, the reaction temperature of weighted BMO spaces reaction zone is compared with hydrotreating zone height, specific reaction condition and slag Oily hydrogenation reaction the results are shown in Table 4, and Hydrocarbon Content by Catalytic Cracking Operation condition is shown in Table 5, and catalytic cracking product is distributed and catalytically cracked gasoline property It is shown in Table 6.Feedstock oil B is followed by mixer 5, reactor 1, mixed hydrogen tank 6, reactor 3, mixed hydrogen tank 7 and reactor 4, a part Reaction effluent is recycled to mixer 5(recycle ratio 0.4:1), another part reaction effluent enters after gas-liquid separation and fractionation Catalytic cracking reaction zone is followed the 25% of the catalytic cracked oil pulp of catalytic cracking reaction zone whole and whole catalytic cracking recycle oils Ring is recycled to hydrotreating reaction area for the 25% of catalytic cracking reaction zone whole catalytic cracking recycle oil and mixes hydrogen tank to mixer 5 6, the straight connecting device of catalytic cracking diesel oil, and metal (Ni+V) content for controlling weighted BMO spaces reaction zone outlet effluent is not high In 20 μ g/g.Sulfur content is 0.23 weight % in hydrogenated back end hydrogenation processing reaction zone effluent, nitrogen content is 1556 μ g/g, residual Charcoal value is 3.90 weight %, metal (Ni+V) content is 9.82 μ g/g.Operating 3 months after, the first weighted BMO spaces reaction zone it is anti- Answer device 1 export effluent metal (Ni+V) content be more than at least one catalyst bed in 20 μ g/g or reactor 1 pressure drop Reach in the pressure drop upper limit or catalyst bed and hot spot occur, cut out, and cuts the reaction of the second weighted BMO spaces reaction zone Device 2 come continue to complete hydroprocessing processes (at this time feedstock oil B followed by mixer 5, reactor 2, mixed hydrogen tank 6, reactor 3, Mixed hydrogen tank 7 and reactor 4), device still even running, generating oil quality can satisfy downstream RFCC feed needs.When second The reactor 2 of weighted BMO spaces reaction zone export effluent metal (Ni+V) content be more than in 20 μ g/g or reactor 2 at least The pressure drop of one catalyst bed reaches in the pressure drop upper limit or catalyst bed when there is not continuing the hot spot of operation, is cut Out, while the reactor 1 of the first weighted BMO spaces reaction zone is cut to continue to complete hydroprocessing processes, while replacing second and adding Catalyst in the reactor 2 of hydrogen pretreatment reaction zone, it is stand-by to reload fresh catalyst.So circulation, the final residual oil Hydrogenation plant has operated 12 months, since product quality variation is stopped work, operates present invention device 1 and reactor 2 is distinguished Handling agent 2 times.
Embodiment 3
According to process flow described in Fig. 1, weighted BMO spaces reaction zone includes the first weighted BMO spaces reaction of changeable operation A reactor 1 is arranged in area and the second weighted BMO spaces reaction zone, the first weighted BMO spaces reaction zone, and the second weighted BMO spaces are anti- Answer area that one reactor 2 is set, hydrotreating reaction area includes the mixed hydrogen tank 6 being arranged in series, reactor 3, mixed hydrogen tank 7 and reaction Device 4.According to Flow of Goods and Materials direction, weighted BMO spaces reaction zone (it is online to only have a weighted BMO spaces reaction zone) in operation process Catalyst A, catalyst B and catalyst C are filled in reactor, the admission space ratio of each catalyst is 4: 5: 1.Hydrotreating is anti- It answers equipped with catalyst B and catalyst C in area's reactor 3, the admission space ratio of two kinds of catalyst is 1: 9, is only loaded in reactor 4 Catalyst D.
In operation process, the reaction temperature of weighted BMO spaces reaction zone is compared with hydrotreating zone height, specific reaction condition and slag Oily hydrogenation reaction the results are shown in Table 4, and Hydrocarbon Content by Catalytic Cracking Operation condition is shown in Table 5, and catalytic cracking product is distributed and catalytically cracked gasoline property It is shown in Table 6.Feedstock oil C is followed by mixer 5, reactor 1, mixed hydrogen tank 6, reactor 3, mixed hydrogen tank 7 and reactor 4, a part Reaction effluent is recycled to mixer 5(recycle ratio 0.5:1), another part reaction effluent enters after gas-liquid separation and fractionation Catalytic cracking reaction zone, by the 80% of catalytic cracking reaction zone whole catalytic cracked oil pulp and the 20% of whole catalytic cracking recycle oils It is recycled to mixer 5, hydrotreating reaction area is recycled to by the 20% of catalytic cracking reaction zone whole catalytic cracking recycle oil and mixes hydrogen Tank 6, the straight connecting device of catalytic cracking diesel oil, and control the metal (Ni+V+Fe+Ca) of weighted BMO spaces reaction zone outlet effluent Content is not higher than 10 μ g/g.Sulfur content is 0.18 weight %, nitrogen content 2615 in hydrogenated back end hydrogenation processing reaction zone effluent μ g/g, carbon residue are 3.62 weight %, metal (Ni+V) content is 5.67 μ g/g, and metal Ca content is 0.68 μ g/g, and metal Fe contains Amount is 0.30 μ g/g.After operating 4 months, the reactor 1 of the first weighted BMO spaces reaction zone exports the metal (Ni+V+ of effluent Fe+Ca) content is more than that the pressure drop of at least one catalyst bed in 10 μ g/g or reactor 1 reaches the pressure drop upper limit or catalyst bed There is hot spot in layer, cut out, and cuts the reactor 2 of the second weighted BMO spaces reaction zone to continue to complete hydrotreating Journey (feedstock oil B is at this time followed by mixer 5, reactor 2, mixed hydrogen tank 6, reactor 3, mixed hydrogen tank 7 and reactor 4), device Still even running, generating oil quality can satisfy downstream RFCC feed needs.When the reaction of the second weighted BMO spaces reaction zone Metal (Ni+V+Fe+Ca) content that device 2 exports effluent is more than at least one catalyst bed in 10mg/g or reactor 2 Pressure drop reaches in the pressure drop upper limit or catalyst bed when there is not continuing the hot spot of operation, is cut out, while cutting first The reactor 1 of weighted BMO spaces reaction zone continues to complete hydroprocessing processes, while replacing the second weighted BMO spaces reaction zone Reactor 2 in catalyst, it is stand-by to reload fresh catalyst.So circulation, the final residual hydrogenation equipment operate It 16 months, since product quality variation is stopped work, operates present invention device 1 and reactor 2 loads and unloads agent 2 times respectively.
Embodiment 4
According to process flow described in Fig. 2, weighted BMO spaces reaction zone includes the first weighted BMO spaces reaction of changeable operation A reactor 1 is arranged in area and the second weighted BMO spaces reaction zone, the first weighted BMO spaces reaction zone, and the second weighted BMO spaces are anti- Answer area that one reactor 2 is set, hydrotreating reaction area includes the mixed hydrogen tank 6 being arranged in series, reactor 3, mixed hydrogen tank 7 and reaction Device 4.According to Flow of Goods and Materials direction, weighted BMO spaces reaction zone (it is online to only have a weighted BMO spaces reaction zone) in operation process Catalyst A, catalyst B and catalyst C are filled in reactor, the admission space ratio of each catalyst is 3: 6: 1.Hydrotreating is anti- It answers equipped with catalyst B and catalyst C in area's reactor 3, the admission space ratio of two kinds of catalyst is 1: 9, and is only filled in reactor 4 Fill out catalyst D.
In operation process, the reaction temperature of weighted BMO spaces reaction zone is compared with hydrotreating zone height, specific reaction condition and slag Oily hydrogenation reaction the results are shown in Table 4, and Hydrocarbon Content by Catalytic Cracking Operation condition is shown in Table 5, and catalytic cracking product is distributed and catalytically cracked gasoline property It is shown in Table 6.Feedstock oil A is followed by mixer 5, reactor 1, mixed hydrogen tank 6, reactor 3, mixed hydrogen tank 7 and reactor 4, a part Reaction effluent is recycled to mixer 5(recycle ratio 0.3:1), another part reaction effluent enters after gas-liquid separation and fractionation Catalytic cracking reaction zone is followed the 40% of the catalytic cracked oil pulp of catalytic cracking reaction zone whole and whole catalytic cracking recycle oils Ring is recycled to hydrotreating reaction area for the 40% of catalytic cracking reaction zone whole catalytic cracking recycle oil and mixes hydrogen tank to mixer 5 6, hydrotreating reaction area is recycled to by the 40% of catalytic cracking reaction zone whole catalytic cracking diesel oil and mixes hydrogen tank 7, and is controlled and added hydrogen Metal (Ni+V) content that pretreatment reaction area exports effluent is not higher than 12 μ g/g.Hydrogenated back end hydrogenation processing reaction zone outflow Sulfur content is 0.21 weight % in object, nitrogen content is 2011 μ g/g, carbon residue is 4.52 weight %, metal (Ni+V) content is 7.19 μg/g.After operating 6 months, metal (Ni+V) content that the reactor 1 of the first weighted BMO spaces reaction zone exports effluent is more than The pressure drop of at least one catalyst bed, which reaches in the pressure drop upper limit or catalyst bed, in 12 μ g/g or reactor 1 there is hot spot, It is cut out, and cuts the reactor 2 of the second weighted BMO spaces reaction zone to continue to complete hydroprocessing processes (feedstock oil at this time A is followed by mixer 5, reactor 2, mixed hydrogen tank 6, reactor 3, mixed hydrogen tank 7 and reactor 4), device still even running, Generating oil quality can satisfy downstream RFCC feed needs.When the reactor 2 of the second weighted BMO spaces reaction zone exports effluent Metal (Ni+V) content be more than that the pressure drop of at least one catalyst bed in 12 μ g/g or reactor 2 reaches the pressure drop upper limit or urges It when occurring not continuing the hot spot of operation in agent bed, is cut out, while cutting the anti-of the first weighted BMO spaces reaction zone Device 1 is answered to continue to complete hydroprocessing processes, while replacing the catalyst in the reactor 2 of the second weighted BMO spaces reaction zone, It is stand-by to reload fresh catalyst.So circulation, the final residual hydrogenation equipment have operated 24 months, since product quality becomes Difference is stopped work, and operates present invention device 1 and reactor 2 loads and unloads agent 2 times respectively.
Embodiment 5
According to process flow described in Fig. 2, weighted BMO spaces reaction zone includes the first weighted BMO spaces reaction of changeable operation A reactor 1 is arranged in area and the second weighted BMO spaces reaction zone, the first weighted BMO spaces reaction zone, and the second weighted BMO spaces are anti- Answer area that one reactor 2 is set, hydrotreating reaction area includes the mixed hydrogen tank 6 being arranged in series, reactor 3, mixed hydrogen tank 7 and reaction Device 4.According to Flow of Goods and Materials direction, weighted BMO spaces reaction zone (it is online to only have a weighted BMO spaces reaction zone) in operation process Catalyst A, catalyst B and catalyst C are filled in reactor, the admission space ratio of each catalyst is 3: 6: 1.Hydrotreating is anti- It answers equipped with catalyst B and catalyst C in area's reactor 3, the admission space ratio of two kinds of catalyst is 1: 9, and filling is urged in reactor 4 Agent C and catalyst D, the admission space ratio of two kinds of catalyst are 2: 8.
In operation process, the reaction temperature of weighted BMO spaces reaction zone is compared with hydrotreating zone height, specific reaction condition and slag Oily hydrogenation reaction the results are shown in Table 4, and Hydrocarbon Content by Catalytic Cracking Operation condition is shown in Table 5, and catalytic cracking product is distributed and catalytically cracked gasoline property It is shown in Table 6.Feedstock oil C is followed by mixer 5, reactor 1, mixed hydrogen tank 6, reactor 3, mixed hydrogen tank 7 and reactor 4, a part Reaction effluent is recycled to mixer 5(recycle ratio 0.5:1), another part reaction effluent enters after gas-liquid separation and fractionation Catalytic cracking reaction zone, by the 80% of catalytic cracking reaction zone whole catalytic cracked oil pulp and the 20% of whole catalytic cracking recycle oils It is recycled to mixer 5, hydrotreating reaction area is recycled to by the 20% of catalytic cracking reaction zone whole catalytic cracking recycle oil and mixes hydrogen Tank 6 is cut into LCO light fraction and LCO heavy distillat for the 20% of catalytic cracking reaction zone whole catalytic cracking diesel oil (LCO), cutting Point is 275 DEG C, and LCO heavy distillat is recycled to hydrotreating reaction area and mixes hydrogen tank 7, and LCO light fraction is recycled to hydrotreating reaction area 4 middle part of reactor, and metal (Ni+V+Fe+Ca) content for controlling weighted BMO spaces reaction zone outlet effluent is not higher than 10 μ g/ g.Sulfur content is 0.17 weight % in hydrogenated back end hydrogenation processing reaction zone effluent, nitrogen content is 2605 μ g/g, carbon residue is 3.58 weight %, metal (Ni+V) content are 5.40 μ g/g, and metal Ca content is 0.65 μ g/g, and metal Fe content is 0.30 μ g/g. After operating 4 months, metal (Ni+V+Fe+Ca) content that the reactor 1 of the first weighted BMO spaces reaction zone exports effluent is more than The pressure drop of at least one catalyst bed, which reaches in the pressure drop upper limit or catalyst bed, in 10 μ g/g or reactor 1 there is hot spot, It is cut out, and cuts the reactor 2 of the second weighted BMO spaces reaction zone to continue to complete hydroprocessing processes (feedstock oil at this time B is followed by mixer 5, reactor 2, mixed hydrogen tank 6, reactor 3, mixed hydrogen tank 7 and reactor 4), device still even running, Generating oil quality can satisfy downstream RFCC feed needs.When the reactor 2 of the second weighted BMO spaces reaction zone exports effluent Metal (Ni+V+Fe+Ca) content be more than that the pressure drop of at least one catalyst bed in 10mg/g or reactor 2 reaches in pressure drop It when occurring not continuing the hot spot of operation in limit or catalyst bed, is cut out, while cutting the reaction of the first weighted BMO spaces The reactor 1 in area continues to complete hydroprocessing processes, while replacing urging in the reactor 2 of the second weighted BMO spaces reaction zone It is stand-by to reload fresh catalyst for agent.So circulation, the final residual hydrogenation equipment has operated 16 months, due to product Quality variation is stopped work, and operates present invention device 1 and reactor 2 loads and unloads agent 2 times respectively.
3 hydroprocessing condition of table and result
4 hydroprocessing condition of table and result
5 Hydrocarbon Content by Catalytic Cracking Operation condition of table
The distribution of 6 catalytic cracking product of table and catalytically cracked gasoline property
In order to further investigate the influence of technology of the invention to hydrotreating reaction area catalyst, respectively to embodiment 1 Catalyst C and catalyst D after operating with comparative example 1 are dissected, and the results are shown in Table 7 and table 8.
Wherein, catalyst sample dissects analysis method used: carrying out C using Japan's production EMZA-820V elemental analyser and contains It is fixed to measure；Metal deposition capability is carried out using IRIS HR plasma emission spectrum (ICP) instrument of Thermo Fisher company, the U.S. Measurement；Catalyst pore structure property analysis uses low temperature N2Absorption method, instrument are that ASAP2420 type Full-automatic physical adsorption instrument (divides Analysis method is GB/T-19587).
7 catalyst C of table operating front and back dissects result
8 catalyst D of table dissects result
As seen from the above analysis, by changing residual hydrogenation equipment catalyst system and operation mode, i.e., by the prior art Low early and high after trend (comparative example 1) is presented according to logistics orienting response temperature, changes into and is according to logistics orienting response temperature The existing trend (embodiment 1) that the front is high and the back is low can make full use of the activity of all catalyst while guaranteeing product quality, Since weighted BMO spaces reaction zone is stripped of most of metal impurities in material, so that desulfurization catalyst in hydrotreating reaction area The deactivation cause of agent and/or denitrification catalyst is from becoming only carbon deposit using the metal deposit and coking deactivation of prior art technology Inactivation, effectively increases the utilization rate of desulphurization catalyst and/or denitrification catalyst, while urge desulphurization catalyst and denitrogenation Agent can carry out regeneration treatment after using a cycle, reuse, saved catalyst buying expenses, improved economy Property.

Claims (11)

1. a kind of method of group technology processing poor residuum, including the following contents:
(1) at least one weighted BMO spaces reaction zone, a hydrotreating reaction area and a catalytic cracking reaction zone are provided；Add Include hydrogenation protecting catalyst and Hydrodemetalation catalyst in hydrogen pretreatment reaction zone, includes adding hydrogen in hydrotreating reaction area Desulphurization catalyst and hydrodenitrogenation catalyst include catalytic cracking catalyst in catalytic cracking reaction zone；
(2) inferior feedstock oil, the recycle oil of hydrotreating zone, catalytic cracked oil pulp, partially catalyzed cracking recycle oil and hydrogen one It rises and enters the molten hydrogen logistics of mixer formation saturation；
(3) the molten hydrogen logistics of saturation from step (2) enters weighted BMO spaces reaction zone, and liquid is carried out under the conditions of weighted BMO spaces Metal impurities are removed 40wt%~90wt% by phase hydrogenation reaction, and sulphur is removed 20wt%~70wt%；
(4) reaction effluent that step (3) obtains enters mixed hydrogen tank without isolation, after mixing with partially catalyzed cracking recycle oil, Miscella after being saturated molten hydrogen enters liquid-phase hydrogenatin treatment reactor, carries out hydrogenation reaction under hydroprocessing conditions；
(5) liquid-phase hydrogenatin reaction effluent a part obtained by step (4) is recycled back to weighted BMO spaces reaction zone, and another part enters Separator carries out gas-liquid separation, obtains hydrogen-rich gas and the first liquid；
(6) the first product liquid obtained by step (5) enters fractionating column, obtains gas, naphtha, hydrogenated diesel oil and hydrogenation tail oil；
(7) hydrogenation tail oil obtained by step (6) enters catalytic cracking reaction zone, and it is anti-that cracking is carried out in the presence of catalytic cracking catalyst It answers, reaction generates after oil is fractionated and obtains dry gas, liquefied gas, catalytically cracked gasoline, catalytic cracking diesel oil, catalytic cracking recycle oil And catalytic cracked oil pulp；
(8) catalytic cracking recycle oil obtained by step (7) is divided into two parts, and a part is used as dilution after mixing with catalytic cracked oil pulp Oil, is recycled back to weighted BMO spaces reaction zone, and another part is recycled back to hydrotreating reaction area and mixes hydrogen tank；
Wherein, the average reaction temperature t1 of the weighted BMO spaces reaction zone is higher than the average response in the hydrotreating reaction area 5~40 DEG C of t2 high of temperature t2, preferably t1 ratio, 10~30 DEG C of t2 high of more preferable t1 ratio.
2. according to the method for claim 1, which is characterized in that it is anti-to provide more than two weighted BMO spaces in step (1) Area is answered, which is usually the reaction zone that is arranged in parallel, can be switched operation.
3. according to the method for claim 1, which is characterized in that the tenor of the inferior feedstock oil is greater than 30 μ g/g.
4. according to method described in claim 1 or 3, which is characterized in that the inferior feedstock oil is selected from by topped crude, stone One group of substance that the hydro carbons for the high asphalt content that dregs of fat oil, oil-sand, pitch, shale oil, liquefaction coal or reclaimed oil obtain is constituted One or more of.
5. according to the method for claim 1, which is characterized in that in weighted BMO spaces reaction zone, hydrogenation protecting catalyst Admission space ratio with Hydrodemetalation catalyst is 5:95~95:5.
6. according to the method for claim 5, which is characterized in that the weighted BMO spaces reaction zone further includes hydrodesulfurization Catalyst, the loadings of Hydrobon catalyst are 5v%~30v% of Hydrodemetalation catalyst loadings.
7. according to the method for claim 1, which is characterized in that the weighted BMO spaces condition is that reaction pressure is 5MPa~35MPa, average reaction temperature are 340 DEG C~430 DEG C, and volume space velocity is 0.1h when liquid-1~5.0h-1, liquid phase circulation matter Amount is than being 0.1:1~10:1；The hydroprocessing condition are as follows: reaction pressure is 5MPa~35MPa, and average reaction temperature is 320 DEG C~420 DEG C, volume space velocity is 0.1h when liquid-1~5.0h-1, liquid phase circulation mass ratio is 0.1:1~10:1.
8. according to the method for claim 1, which is characterized in that in the hydrotreating reaction area, hydrodesulfurization catalytic The admission space of agent and hydrodenitrogenation catalyst ratio is 20:80~80:20.
9. according to the method for claim 1, which is characterized in that the operating condition of the catalytic cracking reaction zone are as follows: reaction 470~650 DEG C of temperature, 0.5~5 second reaction time, catalyst and feedstock oil weight ratio 3~10, catalyst regeneration temperature 650 ~800 DEG C.
10. according to the method for claim 1, which is characterized in that be recycled to hydrotreating reaction area first and mix returning for hydrogen tank It refines oil and accounts for 10% or more of catalytic cracking recycle oil weight obtained by catalytic cracking reaction zone, preferably 20 ~ 50%；It is recycled to plus hydrogen is located in advance The recycle oil of reason reaction zone accounts for 10% or more of catalytic cracking recycle oil weight obtained by catalytic cracking reaction zone, preferably 20 ~ 50%；It follows The recycle oil total amount that ring to hydrotreating reaction area first mixes hydrogen tank and is recycled to weighted BMO spaces reaction zone accounts for Catalytic Cracking Unit of Measure Answer 20% or more of catalytic cracking recycle oil weight obtained by area, preferably 30 ~ 95%.
11. according to the method for claim 1, which is characterized in that be recycled to the cycle oil of weighted BMO spaces reaction zone It starches and accounts for 30% or more of catalytic cracked oil pulp weight obtained by catalytic cracking reaction zone, preferably 50 ~ 80%.
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