CN105861045B - A kind of method and device of Grading And Zoning conversion catalyst cracked cycle oil - Google Patents
A kind of method and device of Grading And Zoning conversion catalyst cracked cycle oil Download PDFInfo
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- CN105861045B CN105861045B CN201610280039.2A CN201610280039A CN105861045B CN 105861045 B CN105861045 B CN 105861045B CN 201610280039 A CN201610280039 A CN 201610280039A CN 105861045 B CN105861045 B CN 105861045B
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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
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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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Abstract
The invention provides a kind of method and device of Grading And Zoning conversion catalyst cracked cycle oil.Described device includes settler (1), regenerator (2), riser reactor (3), catalytic hydrogenation device (4) and fractionating device (5), regenerator is arranged on settler bottom, oil gas vent (31) at the top of riser reactor is connected with settler, riser reactor bottom is connected by inclined tube (6) with regenerator bottoms, it is connected at the top of settler with fractionating device, fractionating device is connected with catalytic hydrogenation device to enable the light cycle oil and heavy-cycle oil that are come out from fractionating device to be entered after merging in catalytic hydrogenation device；Riser reactor from top to bottom sets feedstock oil reaction zone (32) and recycle oil reaction zone (33) respectively, in feedstock oil reaction zone and recycle oil reaction zone join domain, raw material oil-in (34) are set, circulation oil-in (35) is set in recycle oil reaction zone bottom, and is connected with the circulation oil export (41) of catalytic hydrogenation device.
Description
Technical field
The present invention relates to oil product manufacture field, specifically, is related to a kind of Grading And Zoning conversion catalyst cracking circulation
The method and device of 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,
Belong to cut inferior, wherein light cycle oil was mainly used as the blend component of diesel oil originally, and heavy-cycle oil is being catalyzed as recycle oil
Conversion and cycle in cracking unit.
But China will implement state's IV discharge standards from January, 2015, it is desirable to polycyclic aromatic hydrocarbon quality in derv fuel
Fraction is not more than 11%, and catalytic cracking light cycle oil is as diesel oil blending component by larger limitation.Although skill is refined oil in recent years
Art tool is greatly improved and innovated, but the oil plant pair that this has special nature for catalytic cracking light cycle oil (LCO)
The processing technology of product does not break through preferably also.The Efficient Conversion of catalytic cracking light cycle oil how is realized, becomes height
Value-added product is the problem of oil refining enterprise.
For catalytic cracking light cycle oil, conventional processing method is to carry out aromatic hydrocarbons saturation, hetero atom using hydrogenation technique
Removing, to realize the refined of catalytic cracking light cycle oil, produce ultra-low-sulphur diesel.Such as CN201110325356,
CN201110325408 proposes a kind of light cycle oil selective hydrogenation refining method, and naphthalene system is bicyclic in oil product after this method reaction
Aromatic hydrocarbons and condensed-nuclei aromatics fractional saturation or open loop, only up to more than 30.0%, the total aromatic hydrocarbons of product retains polycyclic aromatic hydrocarbon conversion ratio
Rate is more than 96.0%, and hydrogen consumption is high and Cetane number increase rate is little.
Some researcher (the LCO hydrogenation new technology Wang De meetings of production high value added product, Xu Xingang, Liu Ruiping, Miao Xi
Flat oil Refining Technologies and engineering, 2014,44 (7)：11-14) summarize new catalytic cracking light cycle oil hydrogen addition technology, such as LCO
Unicracking techniques, RLG technologies, LCO-X techniques etc. are using hydrofinishing the characteristics of these technologies and are hydrocracked phase
With reference to method catalytic cracking light cycle oil is converted into fine-quality diesel oil, mononuclear aromatics (component such as benzene,toluene,xylene) retains
As high-quality antiknock component or conduct light aromatics product in gasoline fraction.Although such technology makes diesel fuel cetane
The increase rate of value is larger, but still can not meet state IV diesel oil regulation requirements, is additionally present of the low and chemical hydrogen of total liquid yield
Consume the shortcomings that high.
For heavy catalytic cycle oil, conventional processing method is that conversion and cycle is carried out inside catalytic cracking unit,
I.e. fractionating column, which is drawn, splits recycle oil and fresh feed and is mixed into the conversion of catalysisization riser reactor, wherein freshening amount by
To the restriction of handicraft product structure and machining load.And recycle oil conversion ratio is low, catalytic slurry high income is caused, have impact on dress
The light hydrocarbon yield put.
Hydro carbons composition in catalytic cracking recycle oil includes alkane, cycloalkane (containing a small amount of alkene) and aromatic hydrocarbons, with catalysis
Cracked stock oil is different different with operating severity, and the hydro carbons composition of recycle oil differs greatly, but aromatic hydrocarbons is its key component,
Run-of-the-mill fraction is more than 70%, sometimes up to 90% or so.Mononuclear aromatics includes alkylbenzene, indane class, tetrahydrochysene in aromatic hydrocarbons
Naphthalenes and indene, account for the 33% of aromatic hydrocarbons total amount；Polycyclic aromatic hydrocarbon includes naphthalenes, acenaphthene class, acenaphthylene class, luxuriant and rich with fragrance class and anthracene class etc., accounts for
The 67% of aromatic hydrocarbons total amount, because open loop cracking reaction, therefore this portion can not occur under the conditions of catalytic cracking reaction again for aromatic ring structure
Recycle oil is divided to be again introduced into catalyst cracker transformation efficiency very low.
It is polycyclic although polycyclic aromatic hydrocarbon is difficult to open loop cracking, and under the conditions of hydro-upgrading under the conditions of catalytic cracking reaction
It is alkylaromatic hydrocarbon and cyclic hydrocarbon radical aromatic hydrocarbons (indane class, tetrahydronaphthalene and indene) etc. that aromatic hydrocarbons, which is easier saturation, the virtue of this class formation
Hydrocarbon can be high-knock rating gasoline cut and lighter hydrocarbons in cracking under catalytic cracking condition.Meanwhile in order to reduce cyclic hydrocarbon radical aromatic hydrocarbons hair
Raw side reaction (such as hydrogen transfer reaction) is changed into polycyclic aromatic hydrocarbon, causes the effect after hydrogenation link not play, catalytic cracking
Reaction needs suitable reaction condition and needs to use the catalyst with notable cycloalkanes ring structure open loop cracking capability, such as rich
The Y zeolite catalyst of the basket structure containing β.
And the hydro-upgrading reaction for catalytic cracking recycle oil using the hydrogenation with high arene saturating activity, it is necessary to be urged
Agent, and control suitable reaction condition to avoid the open loop cracking of polycyclic aromatic hydrocarbon, reduce hydrogen consumption and gaseous product generation.Appropriateness
Mononuclear aromatics mass fraction is before hydrotreating than increasing substantially in catalytic cracking recycle oil after hydrogenation, wherein cyclic hydrocarbon radical benzene matter
Measure fraction increase significantly, this reenters catalytic cracking unit cracking for catalytic cracking recycle oil and provided the foundation.Due to cyclic hydrocarbon
The cracking reaction of base aromatic hydrocarbons is undertaken by catalytic cracking unit, so as to effectively realize the low hydrogen of hydrogenation plant consumption and high product liquid
Yield.
The heavy charge of catalytic cracking recycle oil and catalytic cracking unit processing after contrast hydrogenation, both molecular structures
Also there is relatively big difference with cracking performance.There is largely without the molecular group of a cracking, the molecule in heavy charge
There is the long alkyl chain structure of more easily cracking in group, belong to the raw material of easy cracking.Catalytic cracking recycle oil after hydrogenation is rich in alkane
Base aromatic hydrocarbons and cyclic hydrocarbon radical aromatic hydrocarbons, compared with heavy charge, belong to the raw material of difficult cracking.Therefore, in order to avoid two kinds of nature differences
Raw material interfering in catalyst cracker, classification charging should be carried out to two kinds of raw materials, to optimize respective reaction
Environmental creation condition.
In summary, used using two reaction units of catalytic cracking and hydro-upgrading, the recycle oil of catalytic cracking unit
Hydrogenation catalyst with high arene saturating activity reenters catalytic cracking unit after hydro-upgrading and carries out cracking, passes through
Fed with classification of the heavy charge in riser reactor, there is notable cycloalkanes by matching suitable reaction condition and using
The catalyst of ring structure open loop cracking capability, catalytic cracking can be made under conditions of low hydrogen consumption, product liquid do not lose substantially
Recycle oil is converted into high-knock rating gasoline cut, and yield of gasoline increases substantially.
The content of the invention
It is an object of the present invention to provide a kind of device of Grading And Zoning conversion catalyst cracked cycle oil.
Another object of the present invention is to provide a kind of method of Grading And Zoning conversion catalyst cracked cycle oil.Pin of the present invention
, conversion difficulty big the characteristics of high to the recycle oil arene content of catalytic cracking unit, it is proposed that one kind is according to crack materials difficulty or ease
Degree carries out heavy raw oil and recycle oil classification charging and reaction on riser reactor, and is set and followed using hydrogenation plant
Ring oil modification link improves its cracking performance, abundant cracking of the recycle oil in catalytic cracking unit is realized, to increase substantially
The yield of gasoline fraction and lighter hydrocarbons.
For the above-mentioned purpose, on the one hand, the invention provides a kind of device of Grading And Zoning conversion catalyst cracked cycle oil,
Wherein, described device includes settler 1, regenerator 2, riser reactor 3, catalytic hydrogenation device 4 and fractionating device 5, wherein,
Regenerator is arranged on settler bottom, and the oil gas vent 31 at the top of riser reactor is connected with settler, riser reactor
Bottom is connected by inclined tube 6 with regenerator bottoms, is connected at the top of settler with fractionating device, fractionating device and catalytic hydrogenation device
Connect to enable the light cycle oil and heavy-cycle oil that are come out from fractionating device to be entered after merging in catalytic hydrogenation device；Carry
Riser reactors from top to bottom set feedstock oil reaction zone 32 and recycle oil reaction zone 33 respectively, in feedstock oil reaction zone and circulation
Oily reaction zone join domain sets raw material oil-in 34, sets circulation oil-in 35 in recycle oil reaction zone bottom, and with catalysis
The circulation oil export 41 of hydrogenation plant connects.
The present invention sets a recycle oil reaction zone in heavy oil catalytically cracking equipment riser reactor bottom, is carried with top
Riser reactors are connected, and form the reaction system of catalytic cracking unit.
The position that heavy raw oil enters riser reactor is located at recycle oil cracking reaction area top, with being split from recycle oil
Change the up catalyst of reaction zone, hydrocarbons contact carries out catalytic cracking reaction.
Wherein it is understood that described set feedstock oil in feedstock oil reaction zone and recycle oil reaction zone join domain
Entrance 34, raw material oil-in therein set location is without excessively accurate, generally in feedstock oil reaction zone and recycle oil reaction
Area's join domain, it can for example be arranged on the junction of feedstock oil reaction zone and recycle oil reaction zone, it might even be possible to be to follow
The position of close feedstock oil reaction zone and recycle oil the reaction zone junction of ring oil reaction zone；And some are specific real according to the present invention
Scheme is applied, the raw material oil-in is provided in feedstock oil reaction zone bottom, i.e., feedstock oil reaction zone is close to feedstock oil reaction zone
With the position of recycle oil reaction zone junction.
According to some specific embodiments of the invention, wherein, the length of recycle oil reaction zone 33 accounts for recycle oil reaction zone 33
With the 1/4-1/10 of the total length of feedstock oil reaction zone 32.
Described fractionating device can use the conventional fractionating device of prior art, and according to some specific implementations of the present invention
Scheme, wherein, the fractionating device includes fractionating column 51, catch pot 52, the first stripping tower 53, the second stripping tower 54 and returns
Rendering tank 55, the top of settler 1 are connected with fractionation column base, and catch pot is connected with fractionating column top, the first stripping tower, the
Two stripping towers and freshening oil tank are connected with fractionating column respectively according to order from top to bottom.
According to some specific embodiments of the invention, wherein, Fractionator Bottom sets slurry oil to export 511, and slurry oil outlet is passed through
First heat-exchanger rig 561 is connected with the Single port of four-way pipe 57, and its excess-three port of four-way pipe is changed with fractionating column, second respectively
Thermal 562 and slurry oil outlet 58 are connected, and the second heat-exchanger rig 562 is connected with fractionating column again.
According to some specific embodiments of the invention, wherein, catch pot 52 sets cracking gas exit 521 and knockout drum
Liquid distillate outlet 522.
According to some specific embodiments of the invention, wherein, the setting three-way pipe 523 of knockout drum liquid distillate outlet 522, three
The one of outlet of siphunculus is connected with fractionating column 51, will be partially separated tank liquid distillate and be led back in fractionating column.
According to some specific embodiments of the invention, wherein, the three-way pipe 523 that knockout drum liquid distillate outlet 522 is set
Another outlet be floss hole.
Wherein it is understood that in three outlets of three-way pipe 523 described here, there are one outlet and knockout drum liquid
Body fraction outlets 522 are connected, and one outlet is connected with fractionating column 51, and the 3rd outlet is floss hole.
According to some specific embodiments of the invention, wherein, the first stripping tower 53 sets the first stripping tower oil gas entrance 531
To be connected with fractionating column 51, and set the first stripping tower liquid distillate to export 532, and the first stripping tower gas is set at top
Outlet 533 is simultaneously connected with fractionating column；Second stripping tower 54 sets the second stripping tower oil gas entrance 541 to be connected with fractionating column, and
Set the second stripping tower liquid distillate to export 542, and the second stripping tower gas vent 543 is set at top and connected with fractionating column
Connect.
According to some of the invention specific embodiments, wherein, freshening oil tank 55 set freshening oil tank oil gas entrance 551 with
Fractionating column 51 connects, and sets freshening oil tank liquid distillate outlet 552.
According to some specific embodiments of the invention, wherein, freshening oil tank liquid distillate outlet 552 sets freshening oil tank three
Siphunculus 553, the one of outlet of freshening oil tank three-way pipe are connected with fractionating column, the liquid distillate of part freshening oil tank are drawn
Return in fractionating column, another outlet and the second stripping tower liquid distillate outlet 542 of freshening oil tank three-way pipe are converged by pipeline
It is connected afterwards with catalytic hydrogenation device 4.
Wherein it is understood that in three of freshening oil tank three-way pipe 553 described here outlets, have one outlet with
The connection of freshening oil tank liquid distillate outlet 552, one outlet are connected with fractionating column 51, the 3rd outlet and the second stripping tower liquid
Fraction outlets 542 are connected after being converged by pipeline with catalytic hydrogenation device 4.
According to some specific embodiments of the invention, wherein, the catalytic hydrogenation device 4 includes catalytic hydrogenation reaction device
42 and separator 43, fractionating device 5 at the top of catalytic hydrogenation reaction device with being connected, and catalytic hydrogenation reaction bottom of device is with separating
Device is connected, and separator is connected with the circulation oil-in 35 of riser reactor 3.
On the other hand, present invention also offers a kind of method of Grading And Zoning conversion catalyst cracked cycle oil, wherein, it is described
Method includes heavy raw oil in riser reactor in the presence of a catalyst after catalytic cracking reaction, obtained reaction
Oil gas obtains light cycle oil and heavy-cycle oil by fractionation, and it is anti-to carry out catalytic hydrogenation after light cycle oil and heavy-cycle oil are merged
Should, obtained recycle oil carries out preliminary catalytic after being mixed with the catalyst of the foregoing catalytic cracking reaction by regeneration and split
Change reaction, reactant mixture carries out Catalytic Cracking Unit of Measure after being mixed again with heavy raw oil in foregoing riser reactor
Should.
Wherein described catalyst can use the conventional catalyst in this area, and those skilled in the art are in existing catalyst
More creative works need not be paid by carrying out selection；And according to some specific embodiments of the invention, the catalyst activity group
It is divided into the combination of two or three of metal in tungsten, nickel, molybdenum, wherein with overall catalyst weight gauge, tungsten 1-5%, molybdenum 1-5%, nickel
5-20%；Surplus is the carrier of aluminum oxide and silica.
According to some specific embodiments of the invention, wherein, recycle oil and the heavy for carrying out preliminary catalytic cracking reaction are former
Expect that weight of oil ratio is 0.1-0.35：1.
The present invention is had found by many experiments, and recycle oil and the control of heavy raw oil ratio are advantageous to control in this scope
Catalytic cracking conversion processed, after making the molecular structure (aromatic hydrocarbons) of difficult conversion in catalytic cracking enter the modification of hydrogenation plant saturation as far as possible
Catalytic cracking conversion is returned, so as to improve yield of light oil.
According to other specific embodiments of the invention, wherein, the recycle oil and heavy of progress preliminary catalytic cracking reaction
Raw material weight of oil ratio is 0.3：1.
According to some specific embodiments of the invention, wherein, the catalytic cracking reaction condition is：Reaction temperature 470~
550 DEG C, oil ratio 5~9,1.5~3.5s of reaction time, 150~300 DEG C of raw material preheating temperature, water-oil factor is 0.03~0.10.
According to some specific embodiments of the invention, wherein, the catalytic hydrogenation reaction condition is：Hydrogen dividing potential drop 6.0~
12.0MPa, 300~400 DEG C of reaction temperature, 300~1000v/v of hydrogen to oil volume ratio, 0.5~3.0h of volume space velocity-1。
According to some specific embodiments of the invention, wherein, the preliminary catalytic cracking reaction condition is：Reaction temperature
540~600 DEG C, oil ratio 10~20,0.1~0.6s of reaction time, water-oil factor is 0.01~0.06.
According to some specific embodiments of the invention, wherein, the preliminary catalytic cracking reaction condition also includes：Raw material is pre-
Hot 150~350 DEG C of temperature.
According to some specific embodiments of the invention, wherein, carry out catalytic hydrogenation after light cycle oil and heavy-cycle oil merging
Hydrogen weight content is 11.5-14.5% in distillate obtained by reaction.
According to some specific embodiments of the invention, wherein, methods described is using described in any one before the present invention
Device carry out.
According to some specific embodiments of the invention, wherein, methods described includes, by heavy raw oil by raw material oil-in
It is sent into riser reactor and is reacted under catalyst existence condition, reactant mixture separates in settler, catalyst
It is settled down in regenerator and is regenerated, and the inclined tube set by regenerator bottoms is returned in riser reactor, oil gas is by sinking
Drop and enter at the top of device in fractionating device, enter catalytic hydrogenation device after the light cycle oil and heavy-cycle oil that fractionation obtains merge
Catalytic hydrogenation reaction is carried out, obtained recycle oil is transmitted back to riser reactor, and anti-into recycle oil by circulating oil-in
Area is answered, the catalyst obtained after being regenerated with regenerator carries out preliminary catalytic cracking reaction after mixing, and reactant mixture enters back into
Feedstock oil reaction zone, catalytic cracking reaction is carried out after being mixed with the heavy raw oil come in through raw material oil-in.
According to some specific embodiments of the invention, wherein, oil gas is by entering fractionation column base at the top of settler, passing through
Fractionating column is fractionated, and obtains being fractionated oil gas at the top of fractionating column, light diesel fuel cut is obtained by the first stripping tower in the middle part of fractionating column,
Light cycle oil is obtained by the second stripping tower, heavy-cycle oil is obtained by freshening oil tank, slurry oil is obtained in fractionation column base；Wherein
Fractionation oil gas obtains cracked gas and gasoline fraction by catch pot, and heavy-cycle oil and light cycle oil enter catalysis after merging and added
Hydrogen production device.
According to some specific embodiments of the invention, wherein, fractionation oil gas obtains cracked gas and vapour by catch pot
After oil distillate, part of gasoline cut sends fractionating column, another part ejector back to.
Wherein gasoline fraction sends the part of fractionating column back to and the ratio of the part of ejector can be conventional according to this area
Operation, or needed according to production to set, the present invention is to this and has no special requirements.
According to some specific embodiments of the invention, wherein, the heavy-cycle oil obtained by freshening oil tank is a part of and light
Recycle oil merges, and another part returns to fractionating column.
According to some specific embodiments of the invention, wherein, return to the heavy-cycle oil of fractionating column and merge with light cycle oil
The weight ratio of heavy-cycle oil be 0-10：1.
Wherein it is understood that when aforementioned proportion is 0：When 1, the heavy-cycle oil whole obtained by freshening oil tank is represented
Merge with light cycle oil, without returning to fractionating column.
In summary, the invention provides a kind of method and device of Grading And Zoning conversion catalyst cracked cycle oil.This hair
Bright method has the following advantages that：
By setting recycle oil cracking reaction area, cracking heavy feedstocks reaction zone respectively in riser bottom, to avoid turning
Change the big raw material of performance difference to interfere in the reactor；Set recycle oil to modify conversion zone using hydrogenation plant, will follow
Ring oil draws catalytic cracking unit and carries out hydro-upgrading, improves its hydrogen content and reduces the aromatic hydrocarbons building stone in cut, then returns
The recycle oil cracking reaction area for returning catalytic cracking unit is converted, effectively reduce in Conventional catalytic cracking technique recycle oil with again
The oil gas molecule the Effect of Competitive Adsorption occurred between matter feedstock oil in catalyst active center, improve the cracking effect of recycle oil
Rate, produce gasoline fraction and lighter hydrocarbons to maximum.
Brief description of the drawings
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.
Embodiment
The implementation process of the present invention and caused beneficial effect are described in detail below by way of specific embodiment, it is intended to which help is read
Reader more fully understand the present invention essence and feature, not as to this case can practical range restriction.
Embodiment 1
Device and flow visible Fig. 1, Fig. 2 of the present invention, is summarized as follows：In heavy oil catalytically cracking equipment riser reactor
3 bottoms set a recycle oil reaction zone 33, are connected with the feedstock oil reaction zone 32 on top, the length of recycle oil reaction zone 33 accounts for
The 3/20 of recycle oil reaction zone 33 and the total length of feedstock oil reaction zone 32, form the reaction system of catalytic cracking unit.Heavy is former
Material oil enters the bottom of the feedstock oil reaction zone 32 of reaction system, and progress is contacted with from the up catalyst of recycle oil reaction zone 33
Catalytic cracking reaction, the process conditions of riser reaction zone are：500 DEG C of reaction temperature, oil ratio 6.5, reaction time 3.0s are former
Expect 240 DEG C of preheating temperature, water-oil factor 0.06.
Settled in the oil gas that recycle oil reaction zone 33 and feedstock oil reaction zone 32 generate together with catalyst by being arranged on
The efficient fast gas-solid separator 11 of leg outlet in device 1 separates, and catalyst enters stripping section 12, warp by settler 1
Regenerated after crossing stripping into regenerator 2；The bottom cycle that regenerated catalyst returns again to the recycle oil reaction zone 33 of reaction system makes
With.From the top of settler 1, reaction oil gas out enters the separation that the bottom of fractionating column 51 carries out each component.Tower top oil gas is condensed
Enter catch pot 52 after cooling, cracked gas is drawn on top, and gasoline is drawn in bottom, and a part goes back to fractionating column backflow, another portion
It is divided into gasoline fraction and goes out device；Light diesel fuel cut is drawn after being stripped by the first stripping tower 53；Light cycle oil passes through the second air lift
Tower 54 is drawn after stripping；Heavy-cycle oil cut (recycle oil) passes through the rear portion refluxed fractionation tower of freshening oil tank 55, part weight
Recycle oil is drawn enters catalytic hydrogenation reaction device 42 together with after light cycle oil mixing, and wherein heavy-cycle oil goes back to the portion of fractionating column
The ratio for the part divided and mixed with light cycle oil is 1：1；The slurry oil that fractionation column bottom obtains is flowed back by the rear portion that exchanges heat
Fractionating column, a part of slurry oil ejector.
Light cycle oil and heavy-cycle oil enter catalytic hydrogenation reaction device 42 after drawing mixing respectively, in hydrogen and catalyst
In the presence of, the modification reactions such as the polycyclic aromatic ring hydrogenation saturation of controllability occur.Catalytic hydrogenation modifying process condition is：In hydrogen point
Press 8.0MPa, 360 DEG C of reaction temperature, hydrogen to oil volume ratio 600v/v, volume space velocity 1.2h-1.Wherein, light cycle oil and heavy-cycle oil
Hydrogen weight content is 12.33% in distillate after merging obtained by progress catalytic hydrogenation reaction.Afterwards, reaction oil gas, which enters, divides
From device 43, gas component and gasoline fraction ejector are isolated.Catalytic hydrogenation Posterior circle oil is then after heat-exchanger rig 563
The recycle oil reaction zone 33 of riser reactor bottom is returned, is contacted with the regenerated catalyst from regenerator 2, is carried out catalysis and split
Change reaction.Reaction oil gas and catalyst flow up into feedstock oil reaction zone 32, then with heavy raw oil haptoreaction.Circulation
The process conditions of oily reaction zone 33 are：550 DEG C of reaction temperature, oil ratio 20, reaction time 0.2s, water-oil factor 0.01, raw material
260 DEG C of preheating temperature.Wherein, it is 0.3 to carry out the recycle oil of preliminary catalytic cracking reaction and heavy charge weight of oil ratio：1.
For the effect of the checking present invention, using above-mentioned technological process, filled in the catalytic cracking of certain refinery and hydro-upgrading
Put and tested, result of the test is as shown in the table.
A certain heavy crude oil and its catalytic cycle oil (property is shown in Table 1), after the invention, catalytic cycle oil, which enters, urges
Change hydro-upgrading unit conversion, the catalysis of the catalytic hydrogenation recycle oil Returning catalyticing cracking device reaction system bottom after modification follows
Huan You cracking reactions area is reacted, and following reaction oil gas flows up into riser reaction zone with catalyst, former with heavy
It is oily further to be reacted in riser reactor.For the catalyst property that each device each uses as shown in table 2 and table 3, optimization is anti-
Answer condition as shown in table 4.Compared with conventional RFCC, it can improve yield of gasoline using the patented technology
21.67 percentage points, light hydrocarbon yield increases by 5.4 percentage points, increasing gasoline yield and lighter hydrocarbons significant effect.Detailed product distribution is visible
Table 5.
The heavy raw oil of table 1 and catalytic cycle oil nature
The catalytic cracking catalyst property of table 2
| Project | Data |
| Micro-activity/% | 63 |
| Specific surface area/(m2/g) | 110 |
| Matrix 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 |
| Sieve volume composition/% | |
| 0~40 μm | 21 |
| 0~80 μm | 70 |
| 0~149 μm | 98 |
| Average grain diameter/μm | 62 |
The catalyst for hydro-upgrading property of table 3
| Project | Data |
| Diameter/mm | 1.6 |
| Specific surface area/(m2/g) | 140 |
| Shape | Clover |
| Pore volume/(mL/g) | 0.3 |
| Major metal active component | Tungsten and nickel |
The technological condition of table 4
The major product of table 5 is distributed
| Product is distributed and property | Prior art | The present invention program |
| Dry gas | 3.52 | 3.01 |
| Liquefied gas | 17.85 | 22.45 |
| Gasoline | 43.02 | 64.69 |
| Light diesel fuel | 22.02 | 1.15 |
| Slurry oil | 4.8 | 1.05 |
| Coke | 8.79 | 7.65 |
| It is total | 100.0 | 100.0 |
Embodiment 2
Other conditions are constant, using the process conditions of table 6, can obtain the effect shown in table 7.
The technological condition of table 6
The major product of table 7 is distributed
| Product is distributed and property | Prior art | The present invention program |
| Dry gas | 3.52 | 2.89 |
| Liquefied gas | 17.85 | 21.17 |
| Gasoline | 43.02 | 65.02 |
| Light diesel fuel | 22.02 | 2.29 |
| Slurry oil | 4.8 | 1.65 |
| Coke | 8.79 | 6.98 |
| It is total | 100.0 | 100.0 |
Embodiment 3
Other conditions are constant, using the process conditions of table 8, can obtain the effect shown in table 9.
The technological condition of table 8
The major product of table 9 is distributed
| Product is distributed and property | Prior art | The present invention program |
| Dry gas | 3.52 | 3.00 |
| Liquefied gas | 17.85 | 29.28 |
| Gasoline | 43.02 | 57.46 |
| Light diesel fuel | 22.02 | 1.11 |
| Slurry oil | 4.80 | 1.00 |
| Coke | 8.79 | 8.15 |
| It is total | 100.0 | 100.0 |
Claims (18)
1. a kind of device of Grading And Zoning conversion catalyst cracked cycle oil, wherein, described device includes settler (1), regenerator
(2), riser reactor (3), catalytic hydrogenation device (4) and fractionating device (5), wherein, regenerator is arranged on settler bottom,
Oil gas vent (31) at the top of riser reactor is connected with settler, and riser reactor bottom passes through inclined tube (6) and regeneration
Device bottom is connected, and is connected at the top of settler with fractionating device, and fractionating device is connected with catalytic hydrogenation device to fill from fractionation
The light cycle oil and heavy-cycle oil for putting out are entered in catalytic hydrogenation device after can merging；Riser reactor is from top to bottom
Feedstock oil reaction zone (32) and recycle oil reaction zone (33) are set respectively, in feedstock oil reaction zone and recycle oil reaction zone bonding pad
Domain set raw material oil-in (34), recycle oil reaction zone bottom set circulation oil-in (35), and with catalytic hydrogenation device
Circulate oil export (41) connection；The length of recycle oil reaction zone (33) accounts for recycle oil reaction zone (33) and feedstock oil reaction zone (32)
The 1/4-1/10 of total length；The fractionating device includes fractionating column (51), catch pot (52), the first stripping tower (53),
Two stripping towers (54) and freshening oil tank (55), settler (1) top are connected with fractionation column base, catch pot and fractionation tower top
Portion is connected, 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, is fractionated
Bottom of towe sets slurry oil to export (511), and slurry oil outlet is connected by the first heat-exchanger rig (561) with the Single port of 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 second
Heat-exchanger rig (562) is connected with fractionating column again.
2. device according to claim 1, wherein, catch pot (52) sets cracking gas exit (521) and knockout drum
Liquid distillate exports (522).
3. device according to claim 2, wherein, knockout drum liquid distillate outlet (522) setting three-way pipe (523), three
The one of outlet of siphunculus is connected with fractionating column (51), will be partially separated tank liquid distillate and be led back in fractionating column.
4. device according to claim 1, wherein, the first stripping tower (53) sets the first stripping tower oil gas entrance (531)
To be connected with fractionating column (51), and set the first stripping tower liquid distillate to export (532), and the first stripping tower is set at top
Gas vent (533) is simultaneously connected with fractionating column；Second stripping tower (54) set the second stripping tower oil gas entrance (541) with fractionation
Tower connects, and sets the second stripping tower liquid distillate to export (542), and sets the second stripping tower gas vent at top
(543) and with fractionating column it is connected.
5. device according to claim 1, wherein, freshening oil tank (55) set freshening oil tank oil gas entrance (551) with
Fractionating column (51) connects, and sets freshening oil tank liquid distillate outlet (552).
6. device according to claim 1, wherein, freshening oil tank liquid distillate outlet (552) sets freshening oil tank threeway
Manage (553), the one of outlet of freshening oil tank three-way pipe is connected with fractionating column, and the liquid distillate of part freshening oil tank is drawn
Return in fractionating column, another outlet and the second stripping tower liquid distillate outlet (542) of freshening oil tank three-way pipe are converged by pipeline
It is connected after poly- with catalytic hydrogenation device (4).
7. device according to claim 1, wherein, the catalytic hydrogenation device (4) includes catalytic hydrogenation reaction device
(42) it is connected with separator (43), fractionating device (5) with catalytic hydrogenation reaction device top, catalytic hydrogenation reaction bottom of device
It is connected with separator, separator is connected with the circulation oil-in (35) of riser reactor (3).
8. a kind of method of Grading And Zoning conversion catalyst cracked cycle oil, wherein, methods described is being lifted including heavy raw oil
In pipe reactor in the presence of a catalyst after catalytic cracking reaction, obtained reaction oil gas enters fractionating device by fractionation
Light cycle oil and heavy-cycle oil are obtained, carries out catalytic hydrogenation reaction after light cycle oil and heavy-cycle oil are merged, obtained circulation
Oil carries out preliminary catalytic cracking reaction after being mixed with the catalyst of the foregoing catalytic cracking reaction by regeneration, reaction is mixed
Compound carries out catalytic cracking reaction after being mixed again with heavy raw oil in foregoing riser reactor, obtained reaction
Oil gas is re-circulated into fractionating device and is fractionated to obtain light cycle oil and heavy-cycle oil；Oil gas is divided by entering at the top of settler
Tower bottom is evaporated, is fractionated by fractionating column, obtains being fractionated oil gas at the top of fractionating column, is obtained in the middle part of fractionating column by the first stripping tower
To light diesel fuel cut, light cycle oil is obtained by the second stripping tower, heavy-cycle oil is obtained by freshening oil tank, in fractionation column base
Obtain slurry oil；Wherein it is fractionated oil gas and obtains cracked gas and gasoline fraction by catch pot, heavy-cycle oil and light cycle oil closes
And enter catalytic hydrogenation device afterwards.
9. the method according to claim 11, wherein, the recycle oil and heavy raw oil weight of progress preliminary catalytic cracking reaction
It is 0.1-0.35 to measure ratio：1.
10. the method according to claim 11, wherein, the recycle oil and heavy raw oil of progress preliminary catalytic cracking reaction
Weight ratio is 0.3：1.
11. according to the method for claim 8, wherein, the catalytic cracking reaction condition is：Reaction temperature 470~550
DEG C, oil ratio 5~9,1.5~3.5s of reaction time, 150~300 DEG C of raw material preheating temperature, water-oil factor is 0.03~0.10.
12. according to the method for claim 8, wherein, the catalytic hydrogenation reaction condition is：Hydrogen dividing potential drop 6.0~
12.0MPa, 300~400 DEG C of reaction temperature, 300~1000v/v of hydrogen to oil volume ratio, 0.5~3.0h of volume space velocity-1。
13. according to the method for claim 8, wherein, the preliminary catalytic cracking reaction condition is：Reaction temperature 540~
600 DEG C, oil ratio 10~20,0.1~0.6s of reaction time, water-oil factor is 0.01~0.06.
14. according to the method for claim 8, wherein, the preliminary catalytic cracking reaction condition is：Reaction temperature 540~
600 DEG C, oil ratio 10~20,0.1~0.6s of reaction time, water-oil factor is 0.01~0.06, raw material preheating temperature 150~350
℃。
15. according to the method for claim 8, wherein, catalytic hydrogenation reaction is carried out after light cycle oil and heavy-cycle oil merging
Hydrogen weight content is 11.5-14.5% in resulting distillate.
16. according to the method described in claim 8~15 any one, wherein, methods described is usage right requirement 1~8
Device described in meaning one is carried out；Methods described includes, and heavy raw oil is sent into lifting tube reaction by raw material oil-in (34)
Device is reacted in (3) under catalyst existence condition, and reactant mixture separates in settler (1), and catalyst sedimentation is to again
Regenerated in raw device (2), and the inclined tube (6) set by regenerator bottoms is returned in riser reactor, oil gas is by settling
Enter at the top of device in fractionating device (5), entering catalytic hydrogenation after the light cycle oil and heavy-cycle oil that fractionation obtains merge fills
Put (4) and carry out catalytic hydrogenation reaction, obtained recycle oil is transmitted back to riser reactor, and is entered by circulating oil-in (35)
Recycle oil reaction zone (33), the catalyst obtained after being regenerated with regenerator carry out preliminary catalytic cracking reaction after mixing, reaction is mixed
Compound enters back into feedstock oil (32) reaction zone, is catalyzed after being mixed with the heavy raw oil come in through raw material oil-in (34)
Cracking reaction.
17. according to the method for claim 8, wherein, fractionation oil gas obtains cracked gas by catch pot and gasoline evaporates
After point, part of gasoline cut sends fractionating column, another part ejector back to.
18. according to the method for claim 8, wherein, the heavy-cycle oil part obtained by freshening oil tank circulates with light
Oil merges, and another part returns to fractionating column.
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|---|---|---|---|---|
| US3489673A (en) * | 1967-11-03 | 1970-01-13 | Universal Oil Prod Co | Gasoline producing process |
| US4585545A (en) * | 1984-12-07 | 1986-04-29 | Ashland Oil, Inc. | Process for the production of aromatic fuel |
| CN1422327A (en) * | 2000-04-17 | 2003-06-04 | 埃克森美孚研究工程公司 | Cycle oil conservation process |
| CN105419868A (en) * | 2015-11-27 | 2016-03-23 | 中国石油大学(北京) | Heavy oil fluid catalytic cracking method and device |
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2016
- 2016-04-29 CN CN201610280039.2A patent/CN105861045B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3489673A (en) * | 1967-11-03 | 1970-01-13 | Universal Oil Prod Co | Gasoline producing process |
| US4585545A (en) * | 1984-12-07 | 1986-04-29 | Ashland Oil, Inc. | Process for the production of aromatic fuel |
| CN1422327A (en) * | 2000-04-17 | 2003-06-04 | 埃克森美孚研究工程公司 | Cycle oil conservation process |
| CN105419868A (en) * | 2015-11-27 | 2016-03-23 | 中国石油大学(北京) | Heavy oil fluid catalytic cracking method and device |
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Address after: 102249 18 Fu Xue Road, Changping District, Beijing Co-patentee after: Hebei Xinpeng New Materials Technology Co., Ltd. Patentee after: China University of Petroleum (Beijing) Address before: 102249 18 Fu Xue Road, Changping District, Beijing Co-patentee before: HEBEI XINPENG CHEMICAL CO., LTD. Patentee before: China University of Petroleum (Beijing) |