CN105802663A - Method and device for converting catalytic cracking cycle oil in classified and divisional manner - Google Patents
Method and device for converting catalytic cracking cycle oil in classified and divisional manner Download PDFInfo
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- CN105802663A CN105802663A CN201610280035.4A CN201610280035A CN105802663A CN 105802663 A CN105802663 A CN 105802663A CN 201610280035 A CN201610280035 A CN 201610280035A CN 105802663 A CN105802663 A CN 105802663A
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a method and a device for converting catalytic cracking cycle oil in a classified and divisional manner, wherein the device comprises a settler (1), a regenerator (2), a first riser reactor (31), a second riser reactor (32), a catalytic hydrogenation device (4) and a fractionation device (5); the regenerator is arranged at the bottom of the settler; the first riser reactor and the second riser reactor are arranged in a way of parallel connection; the tops of the two riser reactors are respectively connected with a gas-solid separation device (11) in the settler; the bottoms of the two riser reactors are respectively connected with the bottom of the regenerator by a first inclined tube (61) and a second inclined tube (62); the top of the settler is connected with the fractionation device; the fractionation device is connected with the catalytic hydrogenation device; a raw oil inlet (34) is formed in the first riser reactor (31); a cycle oil inlet (35) is formed in the second riser reactor (32) and is connected with a cycle oil outlet (41) of the catalytic hydrogenation device.
Description
Technical field
The present invention relates to oil product manufacture field, specifically, relate to method and the device of a kind of Grading And Zoning conversion catalyst cracked cycle oil.
Background technology
Catalytic cracking recycle oil is the important by-products of catalytic cracking, and quantity is big, rich in aromatic hydrocarbons, especially polycyclic aromatic hydrocarbon, belonging to fraction inferior, wherein light cycle oil was mainly used as the blend component of diesel oil originally, and heavy-cycle oil converts at catalytic cracking unit internal recycle as recycle oil.
But, from January, 2015, China will implement state's IV discharge standard, it is desirable in derv fuel, polycyclic aromatic hydrocarbon mass fraction is not more than 11%, and catalytic cracking light cycle oil is subject to bigger restriction as diesel oil blending component.Although oil Refining Technologies tool has greatly improved and innovates in recent years, but this has the processing technique of petroleum refinery byproduct of special nature but without breaking through better for catalytic cracking light cycle oil (LCO).How to realize the Efficient Conversion of catalytic cracking light cycle oil so that it is become the difficult problem that high value added product is oil refining enterprise.
For catalytic cracking light cycle oil, conventional processing method be utilize hydrogenation technique to carry out aromatic hydrocarbons is saturated, hetero atom elimination, to realize the refining of catalytic cracking light cycle oil, produce ultra-low-sulphur diesel.Such as CN201110325356, CN201110325408 propose a kind of light cycle oil selective hydrogenation refining method, naphthalene system double ring arene and condensed-nuclei aromatics fractional saturation or open loop in oil product after the method reaction, polycyclic aromatic hydrocarbon conversion ratio is only up to more than 30.0%, the total aromatic hydrocarbons retention rate of product more than 96.0%, hydrogen consumption is high and Cetane number increase rate is little.
Some researcheres (LCO producing high value added product is hydrogenated with new technique. Wang Dehui, Xu Xingang, Liu Ruiping, Miao Xiping. oil Refining Technologies and engineering, 2014, 44 (7): 11-14) new catalytic cracking light cycle oil hydrogen addition technology is summarized, such as LCOUnicracking technique, RLG technology, LCO-X technique etc., the feature of these technology is to utilize the method that hydrofinishing and hydrogenation cracking combine that catalytic cracking light cycle oil is converted into fine-quality diesel oil, mononuclear aromatics (benzene, toluene, the components such as dimethylbenzene) it is retained in gasoline fraction and becomes the antiknock component of high-quality or as light aromatics product.Although the increase rate that this type of technology makes diesel cetane-number is relatively big, but still can not meet state IV diesel oil regulation requirement, it is additionally present of the shortcoming that total liquid yield is low and chemical hydrogen consumption is high.
For heavy catalytic cycle oil, conventional processing method is to be circulated conversion inside catalytic cracking unit, namely fractionating column is drawn and is split recycle oil and the fresh feed entrance catalysis riser reactor that is mixed and convert, and wherein freshening amount is subject to the restriction of handicraft product structure and machining load.And recycle oil low conversion rate, causes catalytic slurry yield high, have impact on the light hydrocarbon yield of device.
Hydrocarbon composition in catalytic cracking recycle oil includes alkane, cycloalkane (containing a small amount of alkene) and aromatic hydrocarbons, different different with operating severity with catalytically cracked stock, the hydrocarbon composition of recycle oil differs greatly, but aromatic hydrocarbons is its key component, run-of-the-mill mark is more than 70%, sometimes up to about 90%.In aromatic hydrocarbons, mononuclear aromatics includes alkylbenzene, indane class, tetrahydronaphthalene and indenes class, accounts for the 33% of aromatic hydrocarbons total amount；Polycyclic aromatic hydrocarbon includes naphthalene class, acenaphthene class, acenaphthylene class, luxuriant and rich with fragrance class and anthracene class etc., account for the 67% of aromatic hydrocarbons total amount, due to aromatic ring structure can not again catalytic cracking reaction when there is open loop cracking reaction, therefore to be again introduced into catalyst cracker transformation efficiency very low for this part recycle oil.
When catalytic cracking reaction, although polycyclic aromatic hydrocarbon is difficult to open loop cracking, and when hydro-upgrading, polycyclic aromatic hydrocarbon is easier saturated for alkylaromatic hydrocarbon and cyclic hydrocarbon radical aromatic hydrocarbons (indane class, tetrahydronaphthalene and indenes class) etc., and the aromatic hydrocarbons of this class formation can be high-knock rating gasoline fraction and lighter hydrocarbons in cracking under catalytic cracking condition.Simultaneously, it is changed into polycyclic aromatic hydrocarbon to reduce cyclic hydrocarbon radical aromatic hydrocarbons generation side reaction (such as hydrogen transfer reaction), the effect after hydrogenation link is caused not play, Catalytic Cracking Unit of Measure is in requisition for suitable reaction condition and needs to use the catalyst with notable naphthenic ring structure open loop cracking capability, for instance rich in the Y zeolite catalyst of β basket structure.
And the hydro-upgrading for catalytic cracking recycle oil reacts, it is necessary to use the hydrogenation catalyst with high arene saturating activity, and the reaction condition controlling to be suitable for avoids the open loop cracking of polycyclic aromatic hydrocarbon, reduces hydrogen consumption and gaseous product generates.In catalytic cracking recycle oil after appropriateness hydrogenation, mononuclear aromatics mass fraction increases substantially than before hydrotreatment, and wherein cyclic hydrocarbon radical benzene mass fraction increases notable, and this reenters catalytic cracking unit cracking for catalytic cracking recycle oil and provides the foundation.Owing to the cracking reaction of cyclic hydrocarbon radical aromatic hydrocarbons is undertaken by catalytic cracking unit, thus effectively achieving the low hydrogen consumption of hydrogenation plant and high liquid product yield.
Contrasting the catalytic cracking recycle oil after hydrogenation and the heavy charge of catalytic cracking unit processing, both molecular structures and cracking performance there is also relatively big difference.Heavy charge also exists a large amount of molecular group without a cracking, this molecular group has the long alkyl chain structure of more easy cracking, belongs to the raw material of easy cracking.Catalytic cracking recycle oil after hydrogenation is rich in alkylaromatic hydrocarbon and cyclic hydrocarbon radical aromatic hydrocarbons, compared with heavy charge, belongs to the raw material of difficult cracking.Therefore, in order to avoid raw material the interfering in catalyst cracker of two kinds of nature differences, tackle two kinds of raw materials and carry out classification charging, create conditions for optimizing respective reaction environment.
In sum, utilize catalytic cracking and two reaction units of hydro-upgrading, the recycle oil of catalytic cracking unit uses the hydrogenation catalyst with high arene saturating activity to reenter catalytic cracking unit after hydro-upgrading to carry out cracking, by with heavy charge classification charging in riser reactor, by mating suitable reaction condition and use has the catalyst of notable naphthenic ring structure open loop cracking capability, can consume at low hydrogen, when product liquid does not lose substantially, catalytic cracking recycle oil is made to be converted into high-knock rating gasoline fraction, yield of gasoline increases substantially.
Summary of the invention
It is an object of the present invention to provide the device of a kind of Grading And Zoning conversion catalyst cracked cycle oil.
The method that another object of the present invention is to provide a kind of Grading And Zoning conversion catalyst cracked cycle oil.The present invention is directed to the feature that the recycle oil arene content of catalytic cracking unit is high, conversion difficulty is big, propose one and on riser reactor, carry out heavy raw oil and recycle oil classification charging and reaction according to crack materials complexity, and use hydrogenation plant to arrange recycle oil upgrading link to improve its cracking performance, realize the recycle oil abundant cracking in catalytic cracking unit, to increase substantially the yield of gasoline fraction and lighter hydrocarbons.
nullFor reaching above-mentioned purpose，On the one hand，The invention provides the device of a kind of Grading And Zoning conversion catalyst cracked cycle oil，Wherein，Described device includes settler 1、Regenerator 2、First riser reactor 31、Second riser reactor 32、Catalytic hydrogenation device 4 and fractionating device 5，Wherein，Regenerator 2 is arranged on bottom settler 1，First riser reactor 31 and the second riser reactor 32 are for being arranged in parallel，Two riser reactor 31 tops are connected with the gas-solid separating device 11 in settler respectively，It is connected with bottom regenerator 2 respectively through the first inclined tube 61 and the second inclined tube 62 bottom two riser reactors，Settler 1 top is connected with fractionating device 5，Fractionating device 5 is connected with catalytic hydrogenation device 4 so that can enter into after merging catalytic hydrogenation device 4 from fractionating device 5 light cycle oil out and heavy-cycle oil；Arranging raw oil entrance 34 at the first riser reactor 31, arrange recycle oil entrance 35 at the second riser reactor 32, recycle oil entrance 35 exports 41 with the recycle oil of catalytic hydrogenation device and is connected.
Wherein the settler of the present invention, regenerator, riser reactor and gas-solid separating device are existing equipment, and the present invention is piece second riser reactor arranged side by side with former riser reactor of increase on the basis of existing equipment.
Raw oil entrance 34, namely the position of heavy raw oil entrance riser reactor is consistent with the raw oil entrance of conventional riser reactor, such as the bottom of the first riser reactor 31 it is in, and on the top of the first inclined tube 61 and the first riser reactor 31 junction.
So enter the first riser reactor 31 raw oil can with enter in the first riser reactor from the first inclined tube and up catalyst contacts and carries out catalytic cracking reaction.
And recycle oil entrance 35, namely to enter the position of the second riser reactor 32 consistent with the raw oil entrance of conventional riser reactor for recycle oil, such as the bottom of the second riser reactor 32 it is in, and on the top of the second inclined tube 62 and the second riser reactor 32 junction.
Wherein it is understood that the first riser reactor and second this body structure of riser reactor do not improve, namely the riser reactor of existing routine be can be used for the present invention.
Wherein it is understood that the gas-solid separating device 11 being connected with riser reactor can be one, it is also possible to be two；
It is to say, two riser reactor 31 tops are connected with the same gas-solid separating device 11 in settler respectively, or it is connected with two gas-solid separating devices being set up in parallel 11 respectively.
When gas-solid separating device 11 is one, represent that the first riser reactor and the second riser reactor share a gas-solid separating device 11；
When gas-solid separating device 11 is two, then it represents that the first riser reactor and the second riser reactor are each connected with separate gas-solid separating device respectively；
For convenient mark, two gas-solid separating devices can represent by same drawing reference numeral 11.
According to some specific embodiments of the present invention, wherein, described gas-solid separating device 11 includes the first gas-solid separating device 11 ' and the second gas-solid separating device 11 "; wherein the first riser reactor 31 top is connected with the first gas-solid separating device 11 ', the second riser reactor 32 top and the second gas-solid separating device 11 " be connected.
Described fractionating device can adopt the fractionating device that prior art is conventional, and according to some specific embodiments of the present invention, wherein, described fractionating device includes fractionating column 51, catch pot the 52, first stripping tower the 53, second stripping tower 54 and freshening oil tank 55, settler 1 top is connected with fractionation column base, and catch pot is connected with fractionating column top, and the first stripping tower, the second stripping tower and freshening oil tank are connected with fractionating column respectively according to order from top to bottom.
According to some specific embodiments of the present invention, wherein, Fractionator Bottom arranges slurry oil outlet 511, slurry oil outlet is connected with the Single port of four-way pipe 57 through the first heat-exchanger rig 561, its excess-three port of four-way pipe is connected with fractionating column, the second heat-exchanger rig 562 and slurry oil outlet 58 respectively, and the second heat-exchanger rig 562 is connected with fractionating column again.
According to some specific embodiments of the present invention, wherein, catch pot 52 arranges cracking gas exit 521 and knockout drum liquid distillate outlet 522.
According to some specific embodiments of the present invention, wherein, the outlet of knockout drum liquid distillate 522 arranges tee T 523, and one of them outlet of tee T is connected with fractionating column 51, leads back in fractionating column will be partially separated tank liquid distillate.
According to some specific embodiments of the present invention, wherein, another outlet of the tee T 523 of knockout drum liquid distillate outlet 522 setting is floss hole.
Wherein it is understood that in three outlets of tee T 523 described here, have an outlet to export 522 with knockout drum liquid distillate and be connected, an outlet is connected with fractionating column 51, and the 3rd outlet is floss hole.
According to some specific embodiments of the present invention, wherein, first stripping tower 53 arranges the first stripping tower oil gas entrance 531 to be connected with fractionating column 51, and arranges the first stripping tower liquid distillate outlet 532, and arranges the first stripping tower gas outlet 533 at top and be connected with fractionating column；Second stripping tower 54 arranges the second stripping tower oil gas entrance 541 to be connected with fractionating column, and arranges the second stripping tower liquid distillate outlet 542, and arranges the second stripping tower gas outlet 543 at top and be connected with fractionating column.
According to some specific embodiments of the present invention, wherein, freshening oil tank 55 arranges freshening oil tank oil gas entrance 551 to be connected with fractionating column 51, and arranges freshening oil tank liquid distillate outlet 552.
According to some specific embodiments of the present invention, wherein, freshening oil tank liquid distillate outlet 552 arranges freshening oil tank tee T 553, one of them outlet of freshening oil tank tee T is connected with fractionating column, leading back in fractionating column with the liquid distillate by part freshening oil tank, another outlet of freshening oil tank tee T is connected with catalytic hydrogenation device 4 after being converged by pipeline with the second stripping tower liquid distillate outlet 542.
Wherein it is understandable that, in three outlets of freshening oil tank tee T 553 described here, have an outlet to export 552 with freshening oil tank liquid distillate to be connected, one outlet is connected with fractionating column 51, and the 3rd outlet is connected with catalytic hydrogenation device 4 after being converged by pipeline with the second stripping tower liquid distillate outlet 542.
According to some specific embodiments of the present invention, wherein, described catalytic hydrogenation device 4 includes catalytic hydrogenation reaction device 42 and segregation apparatus 43, fractionating device 5 is connected with catalytic hydrogenation reaction device top, catalytic hydrogenation reaction bottom of device is connected with segregation apparatus, and segregation apparatus is connected with the recycle oil entrance 35 of riser reactor 3.
On the other hand, the method that present invention also offers a kind of Grading And Zoning conversion catalyst cracked cycle oil, wherein, described method includes heavy raw oil in riser reactor in the presence of a catalyst after raw oil catalytic cracking reaction, the reaction oil gas obtained enters fractionating device and obtains light cycle oil and heavy-cycle oil through fractional distillation, catalytic hydrogenation reaction is carried out after light cycle oil and heavy-cycle oil being merged, the recycle oil obtained carries out recycle oil catalytic cracking reaction with after the catalyst mix of the foregoing catalytic cracking reaction of regeneration, wherein recycle oil catalytic cracking reaction and raw oil catalytic cracking reaction are to carry out in two respective independent riser reactors being arranged in parallel respectively；The reaction oil gas that recycle oil catalytic cracking reaction and raw oil catalytic cracking reaction obtain is re-circulated into fractionating device to carry out fractional distillation and obtains light cycle oil and heavy-cycle oil.
Wherein said catalyst can use the catalyst that this area is conventional, and those skilled in the art carry out selecting without paying more creative work in existing catalyst；And according to some specific embodiments of the present invention, described catalyst activity component is the combination of two or three metal in tungsten, nickel, molybdenum, wherein with overall catalyst weight gauge, tungsten 10-30%, molybdenum 1-10%, nickel 5-15%；Surplus is the carrier of aluminium oxide and silicon oxide.
According to some specific embodiments of the present invention, wherein, described raw oil catalytic cracking reaction condition is: reaction temperature 470～550 DEG C, oil ratio 5～9, response time 1.5～3.5s, water-oil factor is 0.03～0.10；
According to some specific embodiments of the present invention, wherein, described raw oil catalytic cracking reaction condition also includes: raw material preheating temperature 150～300 DEG C.
According to some specific embodiments of the present invention, wherein, described catalytic hydrogenation reaction condition is: at hydrogen dividing potential drop 6.0～12.0MPa, reaction temperature 300～400 DEG C, hydrogen to oil volume ratio 300～1000v/v, volume space velocity 0.5～3.0h-1。
According to some specific embodiments of the present invention, wherein, described recycle oil catalytic cracking reaction condition is: reaction temperature 520～600 DEG C, oil ratio 7～20, response time 0.6～3.0s, water-oil factor is 0.01～0.06.
According to some specific embodiments of the present invention, wherein, described recycle oil catalytic cracking reaction condition also includes: raw material preheating temperature 150～300 DEG C.
According to some specific embodiments of the present invention, wherein, light cycle oil and heavy-cycle oil carry out hydrogen weight content in the distillate that catalytic hydrogenation reaction is obtained after merging is 11.5-14.5%.
According to some specific embodiments of the present invention, wherein, described method is to use before the present invention device described in any one to carry out.
nullAccording to some specific embodiments of the present invention，Wherein，Described method includes，Heavy raw oil is sent in the first riser reactor 31 by raw oil entrance 34 and reacts under catalyst existence condition，Reactant mixture separates in settler 1，Catalyst sedimentation regenerates to regenerator 2，And the first inclined tube 61 arranged by regenerator bottoms is returned in the first riser reactor，Oil gas is entered in fractionating device 5 by settler top，The light cycle oil obtained through fractional distillation and heavy-cycle oil enter catalytic hydrogenation device 4 after merging and carry out catalytic hydrogenation reaction，The recycle oil obtained is transported to the second riser reactor 32，With carry out recycle oil catalytic cracking reaction after catalyst mix，The reaction oil gas that recycle oil catalytic cracking reaction and raw oil catalytic cracking reaction obtain is re-circulated into fractionating device to carry out fractional distillation and obtains light cycle oil and heavy-cycle oil.
According to some specific embodiments of the present invention, wherein, oil gas is to be entered fractionation column base by settler top, through fractionating column fractional distillation, obtain fractional distillation oil gas at fractionating column top, in the middle part of fractionating column, obtain light diesel fuel fraction through the first stripping tower, obtain light cycle oil through the second stripping tower, obtain heavy-cycle oil through freshening oil tank, obtain slurry oil at fractionation column base；Wherein fractional distillation oil gas obtains through catch pot entering catalytic hydrogenation device after cracked gas and gasoline fraction, heavy-cycle oil and light cycle oil merge.
According to some specific embodiments of the present invention, wherein, after fractional distillation oil gas obtains cracked gas and gasoline fraction through catch pot, part of gasoline fraction sends fractionating column, another part ejector back to.
Wherein gasoline fraction is sent the ratio of the part of fractionating column and the part of ejector back to and according to this area routine operation, or can be arranged according to producing needs, and the present invention is to this and has no special requirements.
According to some specific embodiments of the present invention, wherein, the heavy-cycle oil part obtained through freshening oil tank merges with light cycle oil, and another part returns to fractionating column.
According to some specific embodiments of the present invention, wherein, the weight ratio of the heavy-cycle oil returning to fractionating column and the heavy-cycle oil merged with light cycle oil is 0-10:1.
Wherein it is understood that when aforementioned proportion is 0:1, represent that the heavy-cycle oil obtained through freshening oil tank all merges with light cycle oil, without returning to fractionating column.
In sum, the invention provides the method for a kind of Grading And Zoning conversion catalyst cracked cycle oil and device.The method of the present invention has the advantage that
The present invention is directed to the feature that the recycle oil arene content of catalytic cracking unit is high, conversion difficulty is big, propose a kind of heavy raw oil that carries out on each independent riser reactor according to crack materials complexity and distinguish charging and reaction with recycle oil, to avoid the raw material that conversion performance difference is big to interfere in same reactor；Use hydrogenation plant that recycle oil upgrading conversion zone is set, recycle oil is drawn catalytic cracking unit and carries out hydro-upgrading, the aromatic hydrocarbons building stone improving its hydrogen content and reduce in fraction, the recycle oil cracking reaction district returning again to catalytic cracking unit converts, effectively reduce the oil gas molecule the Effect of Competitive Adsorption occurred in catalyst active center between recycle oil and heavy raw oil in Conventional catalytic cracking technique, improving the cracking efficiency of recycle oil, maximum ground produces gasoline fraction and lighter hydrocarbons.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the device of embodiment 1；
Fig. 2 is the schematic diagram of the fractionating device of embodiment 1.
Detailed description of the invention
The beneficial effect of the implementation process of the present invention and generation is described in detail, it is intended to help reader to be more fully understood that essence and the feature of the present invention, not as can the restriction of practical range to this case below by way of specific embodiment.
Embodiment 1
Assembly of the invention and visible Fig. 1 and the Fig. 2 of flow process, it is summarized as follows: device includes settler 1, regenerator 2, first riser reactor 31, second riser reactor 32, catalytic hydrogenation device 4 and fractionating device 5, wherein, regenerator is arranged on bottom settler, first riser reactor and the second riser reactor are for being arranged in parallel, two riser reactor tops respectively with two gas-solid separating devices 11 ' and 11 in settler " be connected, it is connected with regenerator bottoms respectively through the first inclined tube 61 and the second inclined tube 62 bottom two riser reactors, settler top is connected with fractionating device, fractionating device is connected with catalytic hydrogenation device so that can enter into after merging catalytic hydrogenation device from fractionating device light cycle oil out and heavy-cycle oil；At the first riser reactor 31, raw oil entrance 34 is set, at the second riser reactor 32, recycle oil entrance 35 is set, and be connected with the recycle oil outlet 41 of catalytic hydrogenation device, wherein raw oil entrance and recycle oil entrance are separately positioned on the bottom of first, second riser reactor, and be positioned at the first inclined tube and the second inclined tube respectively with the top of the first riser reactor and the second riser reactor junction.The process conditions (raw oil catalytic cracking) of the first riser reaction zone are: reaction temperature 500 DEG C, oil ratio 6.5, response time 3.0s, raw material preheating temperature 240 DEG C, water-oil factor is 0.06.
The oil gas generated at the first riser reactor is separated by the first gas-solid separating device 11 ' being arranged in settler 1 together with catalyst, and catalyst enters stripping section 12 through settler 1, enters regenerator 2 and regenerate after stripping；The bottom cycle that regeneration catalyzing agent returns the first riser reactor 31 and the second riser reactor 32 again through the first inclined tube 61 and the second inclined tube 62 uses.The separation carrying out each component bottom fractionating column 51 is entered from settler 1 top reaction oil gas out.Entering catch pot 52 after the condensed cooling of tower top oil gas, cracked gas is drawn on top, and gasoline is drawn in bottom, and a part returns fractionating column backflow, and another part is that gasoline fraction goes out device；Light diesel fuel fraction is by drawing after the first stripping tower 53 stripping；Light cycle oil is by drawing after the second stripping tower 54 stripping；Heavy-cycle oil fraction (recycle oil) is by freshening oil tank 55 rear portion refluxed fractionation tower, a part of heavy-cycle oil enters catalytic hydrogenation reaction device 42 together with drawing after mixing with light cycle oil, and part that wherein heavy-cycle oil returns fractionating column and the ratio of part mixed with light cycle oil are 1:1；The slurry oil obtained at the bottom of fractionation column passes through heat exchange rear portion refluxed fractionation tower, a part of slurry oil ejector.
Light cycle oil and heavy-cycle oil enter catalytic hydrogenation reaction device 42 after drawing mixing respectively, and under the effect of hydrogen and catalyst, the multi-ring aromatic ring hydrogenation of generation controllability is saturated waits upgrading reaction.Catalytic hydrogenation modifying process condition is: at hydrogen dividing potential drop 8.0MPa, reaction temperature 360 DEG C, hydrogen to oil volume ratio 600v/v, volume space velocity 1.2h-1.Wherein, light cycle oil and heavy-cycle oil carry out hydrogen weight content in the distillate that catalytic hydrogenation reaction is obtained after merging is 12.4%.Afterwards, reaction oil gas enters segregation apparatus 43, isolates gas component and gasoline fraction ejector.Catalytic hydrogenation Posterior circle oil then enters the second riser reactor by recycle oil entrance 35 after heat-exchanger rig 563, contacts with the regeneration catalyzing agent from regenerator 2, carries out catalytic cracking reaction.Reaction oil gas and catalyst flow up in settler 1, and by connected second gas-solid separating device 11 " separation oil and gas and catalyst.Second riser reactor oil gas (oil gas of recycle oil catalytic cracking reaction) out and the first riser reactor oil gas (oil gas of raw oil catalytic cracking reaction) out are entered into by settler 1 top to enter back into after carrying out fractional distillation in fractionating device 5 and carry out catalytic hydrogenation reaction in catalytic hydrogenation device 4.Wherein the process conditions of recycle oil catalytic cracking reaction are: reaction temperature 550 DEG C, oil ratio 10, response time 2.0s, and water-oil factor is 0.04, raw material preheating temperature 260 DEG C.
For verifying the effect of the present invention, adopting above-mentioned technological process, test in the catalytic cracking and hydro-upgrading unit of certain refinery, result of the test is as shown in the table.
A certain heavy crude and catalytic cycle oil (character is in Table 1) thereof, after adopting this invention, catalytic cycle oil enters catalytic hydrogenation modifying apparatus and converts, catalytic hydrogenation recycle oil after upgrading enters in the second riser reactor and reacts with catalyst, and the oil gas that the raw oil catalytic cracking reaction in the oil gas obtained and the first riser reactor obtains is entered in fractionating device 5 by the outlet at settler top in the lump.Shown in the catalyst property that each device each adopts such as table 2 and table 3, optimize reaction condition as shown in table 4.Comparing with conventional RFCC, adopt this patented technology that yield of gasoline can be made to improve 21.67 percentage points, light hydrocarbon yield increases by 5.4 percentage points, and increasing gasoline yield and lighter hydrocarbons effect are notable.Detailed product is distributed visible table 5.
Table 1 heavy raw oil and catalytic cycle oil nature
| Project | Heavy raw oil | Catalytic cycle oil |
| Density (20 DEG C) kg/m3 | 928.1 | 970.0 |
| Hydrogen content, wt% | 12.29 | 8.9 |
| Carbon content, wt% | 86.30 | 91.0 |
| Sulfur content, wt% | 1.0 | 1.21 |
| Nitrogen content, wt% | 0.20 | 0.07 |
| Hydrocarbon group composition analysis | ||
| Saturated hydrocarbons, wt% | 59.0 | 8.7 |
| Aromatic hydrocarbons, wt% | 31.5 | 91.3 |
| Colloid, wt% | 8.9 | 0.0 |
| Asphalitine, wt% | 0.6 | 0.0 |
| Carbon residue, wt% | 4.02 | |
| Ni content, wt% | 8.4 | |
| V content, wt% | 6.1 |
Table 2 catalytic cracking catalyst character
| Project | Data |
| Micro-activity/% | 63 |
| Specific surface area/(m2/g) | 110 |
| Substrate specific surface area/(m2/g) | 47 |
| Micropore specific area/(m2/g) | 65 |
| Pore volume/(mL/g) | 0.20 |
| Micro pore volume/(mL/g) | 0.03 |
| Screening volume composition/% | |
| 0～40 μm | 21 |
| 0～80 μm | 70 |
| 0～149 μm | 98 |
| Mean diameter/μm | 62 |
Table 3 catalyst for hydro-upgrading character
| Project | Data |
| Diameter/mm | 1.6 |
| Specific surface area/(m2/g) | 140 |
| Shape | Herba Trifolii Pratentis |
| Pore volume/(mL/g) | 0.3 |
| Major metal active component | Tungsten and nickel |
Table 4 technological condition
Table 5 major product is distributed
| Product slates and character | Prior art | The present invention program |
| Dry gas | 3.52 | 4.21 |
| Liquefied gas | 17.85 | 22.92 |
| Gasoline | 43.02 | 64.01 |
| Light diesel fuel | 22.02 | 1.21 |
| Slurry oil | 4.8 | 1.07 |
| Coke | 8.79 | 6.58 |
| Add up to | 100.0 | 100.0 |
Remarks: the prior art in table 5 can referring to being permitted friendly " catalytic cracking chemistry and technique ", Science Press, 2013, p1162-1184.
Embodiment 2
Other conditions are constant, use the process conditions of table 6, it is possible to obtain the effect shown in table 7.
Table 6 technological condition
Table 7 major product is distributed
| Product slates and character | Prior art | The present invention program |
| Dry gas | 3.52 | 3.25 |
| Liquefied gas | 17.85 | 21.47 |
| Gasoline | 43.02 | 65.11 |
| Light diesel fuel | 22.02 | 2.67 |
| Slurry oil | 4.8 | 1.49 |
| Coke | 8.79 | 6.01 |
| Add up to | 100.0 | 100.0 |
Embodiment 3
Other conditions are constant, use the process conditions of table 8, it is possible to obtain the effect shown in table 9.
Table 8 technological condition
Table 9 major product is distributed
| Product slates and character | Prior art | The present invention program |
| Dry gas | 3.52 | 4.27 |
| Liquefied gas | 17.85 | 30.74 |
| Gasoline | 43.02 | 55.73 |
| Light diesel fuel | 22.02 | 1.03 |
| Slurry oil | 4.80 | 1 |
| Coke | 8.79 | 7.23 |
| Add up to | 100.0 | 100.0 |
Claims (10)
- null1. the device of a Grading And Zoning conversion catalyst cracked cycle oil，Wherein，Described device includes settler (1)、Regenerator (2)、First riser reactor (31)、Second riser reactor (32)、Catalytic hydrogenation device (4) and fractionating device (5)，Wherein，Regenerator (2) is arranged on settler (1) bottom，First riser reactor (31) and the second riser reactor (32) are for being arranged in parallel，Two riser reactor (31) tops are connected with the gas-solid separating device (11) in settler respectively，It is connected with regenerator (2) bottom respectively through the first inclined tube (61) and the second inclined tube (62) bottom two riser reactors，Settler (1) top is connected with fractionating device (5)，Fractionating device (5) is connected with catalytic hydrogenation device (4) so that can enter into after merging catalytic hydrogenation device (4) from fractionating device (5) light cycle oil out and heavy-cycle oil；At the first riser reactor (31), raw oil entrance (34) is set, arranging recycle oil entrance (35) at the second riser reactor (32), recycle oil entrance (35) exports (41) with the recycle oil of catalytic hydrogenation device and is connected；Preferred described gas-solid separating device (11) includes the first gas-solid separating device (11 ') and the second gas-solid separating device (11 "); wherein the first riser reactor (31) top is connected with the first gas-solid separating device (11 '), and the second riser reactor (32) top and the second gas-solid separating device (11 ") it is connected.
- 2. device according to claim 1, wherein, described fractionating device includes fractionating column (51), catch pot (52), the first stripping tower (53), the second stripping tower (54) and freshening oil tank (55), settler (1) top is connected with fractionation column base, catch pot is connected with fractionating column top, and the first stripping tower, the second stripping tower and freshening oil tank are connected with fractionating column respectively according to order from top to bottom.
- 3. device according to claim 2, wherein, Fractionator Bottom arranges slurry oil outlet (511), slurry oil outlet is connected through the Single port of the first heat-exchanger rig (561) with four-way pipe (57), its excess-three port of four-way pipe is connected with fractionating column, the second heat-exchanger rig (562) and slurry oil outlet (58) respectively, and the second heat-exchanger rig (562) is connected with fractionating column again.
- 4. device according to claim 2, wherein, catch pot (52) arranges cracking gas exit (521) and knockout drum liquid distillate outlet (522)；Wherein preferable separate tank liquid distillate outlet (522) arranges tee T (523), and one of them outlet of tee T is connected with fractionating column (51), leads back in fractionating column will be partially separated tank liquid distillate.
- 5. device according to claim 2, wherein, first stripping tower (53) arranges the first stripping tower oil gas entrance (531) to be connected with fractionating column (51), and the first stripping tower liquid distillate outlet (532) is set, and the first stripping tower gas outlet (533) is set at top and is connected with fractionating column；Second stripping tower (54) arranges the second stripping tower oil gas entrance (541) to be connected with fractionating column, and the second stripping tower liquid distillate outlet (542) is set, and the second stripping tower gas outlet (543) is set at top and is connected with fractionating column.
- 6. device according to claim 2, wherein, freshening oil tank (55) arranges freshening oil tank oil gas entrance (551) to be connected with fractionating column (51), and arranges freshening oil tank liquid distillate outlet (552)；Wherein preferably freshening oil tank liquid distillate outlet (552) arranges freshening oil tank tee T (553), one of them outlet of freshening oil tank tee T is connected with fractionating column, leading back in fractionating column with the liquid distillate by part freshening oil tank, another outlet of freshening oil tank tee T exports after (542) are converged by pipeline with the second stripping tower liquid distillate and is connected with catalytic hydrogenation device (4).
- 7. device according to claim 1, wherein, described catalytic hydrogenation device (4) includes catalytic hydrogenation reaction device (42) and segregation apparatus (43), fractionating device (5) is connected with catalytic hydrogenation reaction device top, catalytic hydrogenation reaction bottom of device is connected with segregation apparatus, and segregation apparatus is connected with the recycle oil entrance (35) of riser reactor (3).
- 8. the method for a Grading And Zoning conversion catalyst cracked cycle oil, wherein, described method includes heavy raw oil in riser reactor in the presence of a catalyst after raw oil catalytic cracking reaction, the reaction oil gas obtained enters fractionating device and obtains light cycle oil and heavy-cycle oil through fractional distillation, catalytic hydrogenation reaction is carried out after light cycle oil and heavy-cycle oil being merged, the recycle oil obtained carries out recycle oil catalytic cracking reaction with after the catalyst mix of the foregoing catalytic cracking reaction of regeneration, wherein recycle oil catalytic cracking reaction and raw oil catalytic cracking reaction are to carry out in two respective independent riser reactors being arranged in parallel respectively；The reaction oil gas that recycle oil catalytic cracking reaction and raw oil catalytic cracking reaction obtain is re-circulated into fractionating device to carry out fractional distillation and obtains light cycle oil and heavy-cycle oil；Preferred described raw oil catalytic cracking reaction condition is: reaction temperature 470～550 DEG C, oil ratio 5～9, response time 1.5～3.5s, water-oil factor is 0.03～0.10；Wherein more preferably raw material preheating temperature 150～300 DEG C；Preferred described catalytic hydrogenation reaction condition is: at hydrogen dividing potential drop 6.0～12.0MPa, reaction temperature 300～400 DEG C, hydrogen to oil volume ratio 300～1000v/v, volume space velocity 0.5～3.0h-1；Preferred described recycle oil catalytic cracking reaction condition is: reaction temperature 520～600 DEG C, oil ratio 7～20, response time 0.6～3.0s, water-oil factor is 0.01～0.06；Wherein more preferably raw material preheating temperature 150～300 DEG C；It is 11.5-14.5% that preferred light cycle oil and heavy-cycle oil carry out hydrogen weight content in the distillate that catalytic hydrogenation reaction is obtained after merging.
- 9. method according to claim 8, wherein, described method is to use the device described in claim 1～7 any one to carry out；nullPreferred described method includes，Heavy raw oil is sent in the first riser reactor (31) by raw oil entrance (34) and reacts under catalyst existence condition，Reactant mixture separates in settler (1)，Catalyst sedimentation regenerates to regenerator (2)，And the first inclined tube (61) arranged by regenerator bottoms is returned in the first riser reactor，Oil gas is entered in fractionating device (5) by settler top，The light cycle oil obtained through fractional distillation and heavy-cycle oil enter catalytic hydrogenation device (4) after merging and carry out catalytic hydrogenation reaction，The recycle oil obtained is transported to the second riser reactor (32)，With carry out recycle oil catalytic cracking reaction after catalyst mix，The reaction oil gas that recycle oil catalytic cracking reaction and raw oil catalytic cracking reaction obtain is re-circulated into fractionating device to carry out fractional distillation and obtains light cycle oil and heavy-cycle oil.
- 10. method according to claim 9, wherein, oil gas is to be entered fractionation column base by settler top, through fractionating column fractional distillation, obtain fractional distillation oil gas at fractionating column top, in the middle part of fractionating column, obtain light diesel fuel fraction through the first stripping tower, obtain light cycle oil through the second stripping tower, obtain heavy-cycle oil through freshening oil tank, obtain slurry oil at fractionation column base；Wherein fractional distillation oil gas obtains through catch pot entering catalytic hydrogenation device after cracked gas and gasoline fraction, heavy-cycle oil and light cycle oil merge；After preferred fractional distillation oil gas obtains cracked gas and gasoline fraction through catch pot, part of gasoline fraction sends fractionating column, another part ejector back to；The heavy-cycle oil part obtained preferably through freshening oil tank merges with light cycle oil, and another part returns to fractionating column.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109722307A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method and system of processing of heavy oil |
| CN109722309A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The process and process system for adding hydrogen to combine with catalytic cracking |
| CN110305694A (en) * | 2018-03-20 | 2019-10-08 | 中国石油化工股份有限公司 | A kind of method of low-carbon olefines high-output and light aromatic hydrocarbons |
| US10961471B2 (en) | 2017-10-25 | 2021-03-30 | China Petroleum & Chemical Corporation | Process for producing catalytic cracking gasoline with a high octane number |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4422925A (en) * | 1981-12-28 | 1983-12-27 | Texaco Inc. | Catalytic cracking |
| CN105505459A (en) * | 2015-11-27 | 2016-04-20 | 中国石油大学(北京) | Catalytic cracking method of heavy oil and device thereof |
| CN105505462A (en) * | 2015-11-27 | 2016-04-20 | 中国石油大学(北京) | Catalytic cracking method of heavy oil and device thereof |
-
2016
- 2016-04-29 CN CN201610280035.4A patent/CN105802663B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4422925A (en) * | 1981-12-28 | 1983-12-27 | Texaco Inc. | Catalytic cracking |
| CN105505459A (en) * | 2015-11-27 | 2016-04-20 | 中国石油大学(北京) | Catalytic cracking method of heavy oil and device thereof |
| CN105505462A (en) * | 2015-11-27 | 2016-04-20 | 中国石油大学(北京) | Catalytic cracking method of heavy oil and device thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10961471B2 (en) | 2017-10-25 | 2021-03-30 | China Petroleum & Chemical Corporation | Process for producing catalytic cracking gasoline with a high octane number |
| CN109722307A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The method and system of processing of heavy oil |
| CN109722309A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | The process and process system for adding hydrogen to combine with catalytic cracking |
| CN109722307B (en) * | 2017-10-31 | 2021-05-14 | 中国石油化工股份有限公司 | Method and system for heavy oil processing |
| CN109722309B (en) * | 2017-10-31 | 2021-05-14 | 中国石油化工股份有限公司 | Hydrogenation and catalytic cracking combined process method and process system |
| CN110305694A (en) * | 2018-03-20 | 2019-10-08 | 中国石油化工股份有限公司 | A kind of method of low-carbon olefines high-output and light aromatic hydrocarbons |
| CN110305694B (en) * | 2018-03-20 | 2021-07-09 | 中国石油化工股份有限公司 | Method for increasing yield of low-carbon olefin and light aromatic hydrocarbon |
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