CN105419868B - RFCC method and apparatus - Google Patents
RFCC method and apparatus Download PDFInfo
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- CN105419868B CN105419868B CN201510850362.4A CN201510850362A CN105419868B CN 105419868 B CN105419868 B CN 105419868B CN 201510850362 A CN201510850362 A CN 201510850362A CN 105419868 B CN105419868 B CN 105419868B
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
-
- 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
-
- 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
- C10G2400/04—Diesel oil
Abstract
The present invention provides a kind of RFCC method and apparatus.The RFCC method that the present invention is provided connects fast bed as reactor using lifting bottom of the tube, including：Heavy oil feedstock is entered riser from bottom, catalyst enters fast bed from bottom, be above advanced into riser and contacted with heavy oil feedstock and common up, while occurring the first catalytic cracking reaction；Reaction oil gas fractionation is obtained into cracked gas, gasoline, diesel oil, recycle oil and slurry oil；Recycle oil is subjected to catalytic hydrogenation reaction, condition is 340 380 DEG C of reaction temperature, the 2.0h of volume space velocity 0.5‑1, hydrogen to oil volume ratio 300 800, the 12MPa of reaction pressure 7, the oil gas fractionation that reaction is generated, acquisition cracked gas, gasoline, diesel oil and catalytic hydrogenation heavy oil；Catalytic hydrogenation heavy oil is led back into fast bed and carries out the second catalytic cracking reaction, the reaction oil gas of generation enters riser, carries out the first catalytic cracking reaction.The present invention produces light-end products and the industrial chemicals of high added value with can realizing maximum, while improving the utilization rate of heavy oil feedstock.
Description
Technical field
Heavy oil feedstock Grading And Zoning is entered the present invention relates to a kind of RFCC method and apparatus, more particularly to one kind
The method and apparatus of row catalytic cracking, belong to Petroleum Processing Technology field.
Background technology
With making constant progress for petroleum refining industry, the catalyzed cracking processing of heavy oil requires the production of increase high value added product
Amount, while the low value-added product yield such as reduction dry gas, liquefied gas and coke as far as possible.In Future Refineries, catalytic unit will
No longer it is the device of direct production final products.The petrol and diesel oil that catalytic cracking is produced must refine to lift production by subsequent product
Quality, to meet newest environmental requirement.Although facing lot of challenges, catalytic cracking technology still in development of constantly bringing forth new ideas,
Group technology particularly is taken with other processing of heavy oil techniques, catalytic unit will be made to wave core in Future Refineries relaying supervention and made
With.
Therefore, some new technologies are continued to bring out, it is such as fast from outside heat removing, leg outlet in optimizing raw material atomization, regenerator
A series of RFCC complete set technologys are developed in terms of speed separation, heavy metal passivation and catalyst pre-lift.However, existing
Some RFCC processing technologys are mostly to feed various heavy oil feedstocks as one " entirety ", are not taken into full account
In the heavy oil feedstock of wide boiling range there is larger difference in different component cracking performance.
ZL200910242917.1、ZL200910242920.3、ZL200910242921.8、ZL200910242922.2、
The patents and patent applicationss such as ZL200910242918.6, ZL200910242919.0 propose a variety of heavy oil Grading And Zoning catalysis and split
The method of change, divides into high-quality fcc raw material and fcc raw material inferior, so by catalytically cracked material according to the difference of response characteristic
Afterwards respectively enter it to be converted in differential responses area of catalytic cracking unit reactor assembly.But by high carbon residue, Gao Jin
The inferior raw material part for belonging to content enters after single reactor, and the more conventional riser reactor of green coke amount is big, catalyst activity
Fall is also increased, and causes material reactor subsequent reactions activity inferior very low, selective very poor, has a strong impact on the yield of product
And conversion ratio.
Numerous studies show that, because heavy oil composition and structure are extremely complex, distribution is very wide, if decompression residuum is constituted
Colloid and asphalitine are assigned to from saturation point, fragrance, composition architectural difference is very big.The heavy oil hydrocarbon or nonhydrocarbon of different structure and composition
Quasi-molecule converts suitable optimal operating condition and also differed.If using single oil Refining Technologies, according to a set of changeless
Operating condition is processed to the full fractional composition of raw material, is often attended to one thing and lose sight of another, it is difficult to realize that the hydrocarbon distribution of hydro carbons is optimized
Maximized with oil product.For example, the research for grand celebration paraffinic base RFCC shows, optimal conversion is 70% left
The right side, dry gas yied now and coke yield increasing degree increase with conversion ratio and increase smaller, i.e., dry gas and coke yield it
With in minimum, but it is unconverted now to there is more heavy oil with the ratio between conversion ratio.After conversion ratio increases and reaches certain value (such as
More than 75%), dry gas and coke yield increase and sharply increased with conversion ratio, and catalytic cracking selectively drastically declines.In addition, phase
Industrial production data is closed to show：In using Daqing Vacuum Residue as the catalytic cracking product of primary raw material (intermingled dregs ratio 85%), conversion
When rate reaches 76%, burn yield and reached 11%, dry gas, slurry oil and the total recovery burnt are more than 20%, compared to coking work
Skill, the catalytic cracking technology of high conversion has no advantage on light receive.
To sum up, also there is space to be modified in existing RFCC method, how improve heavy oil feedstock conversion ratio
Increase yield of light oil and liquid yield simultaneously, while the low value-added product yield such as reduction dry gas, liquefied gas and coke as far as possible
As urgent problem to be solved.
The content of the invention
The present invention provides a kind of RFCC method, there is the difference of response characteristic for Rfcc Feedstock
It is different, the heavy charge of composition complex is generated into various types of oil product through multiple conversion reaction, to meet city
Field demand, so as to produce light-end products and the industrial chemicals of high added value with realizing maximum, while improving the profit of heavy oil feedstock
With rate.
The present invention also provides a kind of heavy oil catalytically cracking equipment for realizing the above method.
To achieve the above object, on the one hand, the present invention provides a kind of RFCC method, using lifting bottom of the tube string
Join fast bed as reactor, the described method comprises the following steps：
Heavy oil feedstock is set to enter the riser from bottom, catalytic cracking catalyst enters the fast bed, institute from bottom
State and be advanced on catalytic cracking catalyst riser and contacted with heavy oil feedstock and common up, while occurring the first Catalytic Cracking Unit of Measure
Should；
By the reaction oil gas fractionation from riser, cracked gas, gasoline, diesel oil, recycle oil and slurry oil are obtained；
The recycle oil is subjected to catalytic hydrogenation reaction, reaction condition is 340-380 DEG C of reaction temperature, volume space velocity 0.5-
2.0h-1, hydrogen to oil volume ratio 300-800, reaction pressure 7-12MPa, the oil gas fractionation that the catalytic hydrogenation reaction is generated, acquisition
Cracked gas, gasoline, diesel oil and catalytic hydrogenation heavy oil；
The catalytic hydrogenation heavy oil is led back into the fast bed and carries out the second catalytic cracking reaction, the reaction oil gas of generation enters
Enter riser, carry out first catalytic cracking reaction.
Further, the condition of first catalytic cracking reaction is：460-520 DEG C of reaction temperature, oil ratio 7-11, instead
1.5-2.5s between seasonable.
Further, the condition of second catalytic cracking reaction is：540-600 DEG C of reaction temperature, oil ratio 10-20,
Reaction time 0.1-0.5s, the catalytic hydrogenation heavy oil enters fast bed at 200-400 DEG C, and water-oil factor is 0.03-0.30, pressure
For 130-450kPa.
Further, the catalytic hydroconversion catalyst that the recycle oil catalytic hydrogenation reaction is used is by additive, VIII
Race's metal, group vib metal and aluminum oxide and/or amorphous silicon aluminium carrier composition, wherein the additive is selected from F, P, Fe and Pt
In one or more, one or two kinds of, described group VIII metal of the group vib metal in Mo and W be selected from Co and Ni
Middle one or two.
Further, the catalytic hydroconversion catalyst by 5-15wt% additives, 5-20wt% group VIII metal,
15-50wt%VIB races metal and the aluminum oxide and/or amorphous silicon aluminium carrier of surplus are constituted.
Further, the asphalitine that methods described is also removed including the use of solvent extraction in the slurry oil obtains depitching
Oil, and the deasphalted oil is mixed into progress catalytic hydrogenation reaction with the recycle oil.
Further, the extractant that the solvent extraction is used is selected from C3-C6 alkane or its mixed fraction.
On the other hand, the present invention also provides a kind of heavy oil catalytically cracking equipment for being used to implement the above method, described device
At least include：
Riser, the lifting bottom of the tube sets heavy oil entrance and lifting tube inlet, and top sets leg outlet；
Provided with fast bed outlet at the top of fast bed, the fast bed, bottom sets catalyst inlet and catalytic hydrogenation heavy oil
Entrance；
Oil and gas separating system, the oil and gas separating system set oil gas and catalyst mixture material entrance, oil gas vent and
Catalyst outlet；
Main fractionating tower, the main fractionating tower sets main fractionating tower entrance, and top is provided with multiple light fraction outlets, and bottom is then set
There are freshening oil export and slurry oil outlet；
Catalytic hydroconversion device, catalytic hydroconversion device sets catalytic hydroconversion device portal and catalytic hydrogenation to turn
Outlet is put in makeup；
Secondary fractionating column, the secondary fractionating column sets secondary fractionating column entrance, the outlet of catalytic hydrogenation heavy oil and multiple light components
Outlet；
Tube inlet is lifted described in the fast bed outlet makes the two series connection conducting, and the leg outlet connection is described
The oil gas and catalyst mixture material entrance of oil and gas separating system, the catalyst outlet connection of the oil and gas separating system are described fast
The catalyst inlet of fast bed, oil gas vent connects the main fractionating tower entrance, and the recycle oil outlet of the main fractionating tower is urged
Change hydroconversion unit entrance, catalytic hydroconversion device outlet pair fractionating column entrance, the catalytic hydrogenation weight of secondary fractionating column
Oil export connects the catalytic hydrogenation heavy oil entrance of the fast bed.
Further, also including extraction tower, the extraction tower has extraction tower entrance, de-oiled asphalt outlet and deasphalted oil
Outlet, the extraction tower entrance connects the slurry oil outlet of the main fractionating tower, and catalysis described in the deasphalted oil outlet adds
Hydrogen reforming unit entrance.
Further, the catalytic hydroconversion device is fixed bed reactors.
The implementation of the present invention program, at least has the advantage that：
1st, the RFCC method that the present invention is provided, is carried out heavy oil feedstock progressively by its component reaction characteristic difficulty or ease
Conversion, meanwhile, hydro-upgrading is carried out to being difficult conversion component, the different component of heavy oil is turned in its optimal conversion is interval
Change, improve the total conversion of heavy oil feedstock, while improving the yield of light oil and liquid yield of high added value, reduce dry gas and coke
Generation, to meet the market demand.
2nd, the heavy oil catalytically cracking equipment that the present invention is provided is implemented for above-mentioned catalyst cracking method, simple in construction,
Operation facility.
Brief description of the drawings
Fig. 1 is the heavy oil catalytically cracking equipment schematic diagram that provides in one embodiment of the invention；
Fig. 2 is the heavy oil catalytically cracking equipment schematic diagram that provides in another embodiment of the present invention.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, to the embodiment of the present invention
In technical scheme be clearly and completely described, it is clear that described embodiment is a part of embodiment of the invention, without
It is whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not before creative work is made
The every other embodiment obtained is put, the scope of protection of the invention is belonged to.
In the RFCC method that the present invention is provided, fast bed is arranged in series using lifting bottom of the tube and split as catalysis
Disguise the reactor put.This method comprises the following steps：
Heavy oil feedstock is set to enter the riser from bottom, catalytic cracking catalyst enters the fast bed, institute from bottom
State and be advanced on catalytic cracking catalyst riser and contacted with heavy oil feedstock and common up, while occurring the first Catalytic Cracking Unit of Measure
Should；By the reaction oil gas fractionation from riser, cracked gas, gasoline, diesel oil, recycle oil and slurry oil are obtained；By the recycle oil
Catalytic hydrogenation reaction is carried out, reaction condition is 340-380 DEG C of reaction temperature, volume space velocity 0.5-2.0h-1, hydrogen to oil volume ratio 300-
800, reaction pressure 7-12MPa, the oil gas that the catalytic hydrogenation reaction is generated are fractionated, and are obtained cracked gas, gasoline, diesel oil and are urged
Change hydrogenation heavy oil；The catalytic hydrogenation heavy oil is led back into the fast bed and carries out the second catalytic cracking reaction, the reaction oil of generation
Gas enters riser, carries out first catalytic cracking reaction.
In the above method, heavy oil feedstock enters the bottom of the riser reactive moieties of reaction system, with being reacted from fast bed
The up catalytic cracking catalyst contact in area carries out the first catalytic cracking reaction, and the process conditions of first catalytic cracking reaction are led to
Can be often：460-520 DEG C of reaction temperature, oil ratio 7-11, reaction time 1.5-2.5s.Generally, need to be former by heavy oil
Material is preheated to 100-300 DEG C and enters back into lifting tube reaction.
Afterwards, from riser reaction oil gas (oil gas of i.e. described first catalytic cracking reaction generation) and catalytic cracking
Catalyst enters oil and gas separating system together.The oil and gas separating system includes settler, is arranged at below settler and connects with it
Logical stripping section and the regenerator connected with the stripping section.The settler enters provided with oil gas and catalyst mixture material
Mouth and oil gas vent, the regenerator are provided with catalyst outlet.
The oil gas and catalytic cracking catalyst of the first catalytic cracking reaction generation are first by settler, through settler
The efficient fast gas-solid separator separation of interior setting.The catalytic cracking catalyst isolated enters stripping section, after stripping
Into regenerator regeneration；Catalytic cracking catalyst after regeneration returns again to fast bed bottom and recycled into reaction system.Point
The oil gas separated out leaves settler and is fractionated into main fractionating tower bottom, so as to obtain RFCC target product cracking
Gas, gasoline and diesel oil, while obtaining recycle oil and slurry oil.
In one embodiment of the invention, can be by cracked gas, raw gasoline, diesel oil and slurry oil ejector, and recycle oil
Catalytic hydrogenation is carried out into catalytic hydroconversion device, occurs controllability in the presence of hydrogen and catalytic hydroconversion catalyst
The hydrogenation modification reaction such as fractional saturation of polycyclic aromatic ring.
Compared with existing heavy-oil hydrogenation, almost without metal impurities such as nickel, vanadium in recycle oil, nitrogen content is also very low, no
Asphaltenes.Because freshening oil nature is more excellent, generally reaction condition will relax than heavy-oil hydrogenation.Generally obtained using the above method
Hydrogen content is 8.0wt%-11.5wt%, relative density 0.88-0.99 in the recycle oil obtained.When hydrogen content is low in recycle oil, phase
, fraction distribution deviation higher boiling big to density, can use harsher reaction condition.Carried out according to the property of above-mentioned recycle oil
Selecting catalytic hydroconversion process conditions is：340-380 DEG C of reaction temperature, volume space velocity 0.5-2.0h-1, hydrogen to oil volume ratio 300-
800, reaction pressure 7-12MPa.Recycle oil after catalytic hydrogenation typically can reach hydrogen content 12wt%-13wt%, relatively close
Spend 0.80-0.87.
In another embodiment of the invention, by cracked gas, gasoline and diesel oil ejector.Removed using solvent extraction
Asphalitine in slurry oil obtains deasphalted oil, and the process is carried out in extraction tower.The temperature control of extraction tower 80-250 DEG C it
Between, pressure is between 3.5-10.0MPa, during into extraction tower, and the mass flow ratio of extractant and slurry oil is 2.0-8.0:1,
Depitching oil phase and de-oiled asphalt phase are isolated afterwards.
Obtained de-oiled asphalt ejector, and deasphalted oil is then mixed with recycle oil, together into catalytic hydroconversion
Device carries out catalytic hydrogenation, and reaction condition is identical with a upper embodiment, and here is omitted.
Afterwards, the oil gas of catalytic hydrogenation reaction generation enters secondary fractionating column and is fractionated, and obtains RFCC target
Product cracking gas, gasoline and diesel oil, while obtaining catalytic hydrogenation heavy oil.Cracked gas, gasoline and diesel oil are separated and go out dress
Put.Heavy oil is hydrogenated with after the extraction of secondary Fractionator Bottom, the fast bed reactor of heavy oil catalytically cracking equipment reaction system bottom is returned
Bottom, carries out the second catalytic cracking reaction.
The inventive method reaches extension residence time of raw material by setting extension diameter section while controlling the fast bed of gas velocity formation
Effect, and preferably in increase reactor bed density to improve the contact probability of raw material and catalytic cracking catalyst.This is fast
Second catalytic cracking reaction technology condition of fast bed reaction zone is：540-600 DEG C of reaction temperature, oil ratio 10-20, reaction time
0.1-0.5s, the catalytic hydrogenation heavy oil enters fast bed at 200-400 DEG C, and water-oil factor is 0.03-0.30, and pressure is 130-
450kPa.The oil gas of second catalytic cracking reaction generation flows up into riser reaction zone with catalytic cracking catalyst,
In riser first catalytic cracking reaction is carried out under conditions of relative mitigation.
Each specific equipment suitable for the heavy oil catalytically cracking equipment of the above method, such as riser, fast bed, again
Raw device, settler, gs-oil separator and catalytic hydroconversion device etc. are the common equipment in PETROLEUM PROCESSING field, according to this
Invented technology requires that carrying out appropriate reconstruction and assembling can come into operation.Specific structure of reactor can be found in Chinese patent or special
Profit application ZL200910242917.1, ZL200910242920.3, ZL200910242921.8, ZL200910242922.2,
Related suitable reactor configuration in ZL200910242918.6 and ZL200910242919.0.
Catalyst cracking method in the present invention is applicable all types of catalytic cracking catalysts.
Wherein, heavy oil feedstock can be oil decompression residuum (VR), reduced crude (AR), hydrogenated residue, coker gas oil, de-
The mixture of one or more arbitrary proportions in coal tar, crude oil with high acid value and high metal crude oil.
The catalytic hydroconversion catalyst that catalytic hydrogenation reaction is used can have high polycyclic aromatic hydrocarbon to satisfy to be all types of
With the hydrotreating catalyst of activity；For example can be aluminum oxide and/or amorphous silicon aluminium supported on carriers group vib metal and/
Or the loaded catalyst of group VIII metal.
The catalytic hydroconversion catalyst used in a particular embodiment can be by 5-15wt% additives, 5-
The aluminum oxide of the one or more group vib metals of 20wt% one or more group VIII metals, 15-50wt% and surplus and/or
Amorphous silicon aluminium carrier is constituted.Wherein additive is selected from nonmetalloid and the metallic elements such as fluorine, phosphorus, iron, platinum.Group vib metal
Co or/and Ni is selected from selected from Mo or/and W, group VIII metal.Fixed bed reactors can be selected to realize the catalytic hydroconversion mistake
Journey.
In above-mentioned steps, catalytic hydrogenation heavy oil can also enter in other catalytic cracking units, under conditions of its is suitable
Carry out efficient catalytic cracking reaction.
With reference to specific embodiments and the drawings, the present invention will be described in detail.
Embodiment 1
The RFCC method provided in the present embodiment uses device as shown in Figure 1.Described device at least includes：
Riser 101, the bottom of riser 101 sets heavy oil entrance and lifting tube inlet, and top sets riser
Outlet；Fast bed 001, the top of fast bed 001 is provided with fast bed outlet, and bottom sets catalyst inlet and catalytic hydrogenation weight
Oil-in；Oil and gas separating system, the oil and gas separating system includes settler 102, is arranged at the lower section of settler 102 and connects with it
Logical stripping section 104 and the regenerator 105 connected with the stripping section 104, the settler 102 set oil gas and catalyst
Oil gas vent is additionally provided with the top of mixed material entrance, the oil and gas separating system, the regenerator 105 sets catalyst outlet；
Main fractionating tower 106, the main fractionating tower 106 sets main fractionating tower entrance, and top is provided with multiple light fraction outlets, under
Portion is then exported provided with freshening oil export and slurry oil；
Catalytic hydroconversion device 201, catalytic hydroconversion device 201 sets catalytic hydroconversion device portal and catalysis
Hydroconversion unit is exported；
Secondary fractionating column 202, the secondary fractionating column 202 sets secondary fractionating column entrance, catalytic hydrogenation heavy oil to export and multiple
Light fraction outlet；
Tube inlet is lifted described in the fast bed outlet makes the two series connection conducting, and the leg outlet connection is described
The oil gas and catalyst mixture material entrance of settler 102, the catalyst outlet of regenerator 105 connect the fast bed 001
Catalyst inlet, oil gas vent connects the entrance of the main fractionating tower 106, the recycle oil outlet of the main fractionating tower 106
The entrance of catalytic hydroconversion device 201, the catalytic hydroconversion device outlet pair entrance of fractionating column 202, secondary fractionating column 202
Catalytic hydrogenation heavy oil outlet described in fast bed catalytic hydrogenation heavy oil entrance.
Wherein, fixed bed reactors can be used in catalytic hydroconversion device 201.Main fractionating tower 106 and secondary fractionating column 202
Light fraction outlet includes the oil gas product exit located at tower top and the diesel oil outlet on top, and oil gas product exit connection oil gas point
From tank 107, the catch pot 107 further respectively has cracking gas exit and fuel dispensing outlet.
The method that the device provided using the present embodiment carries out RFCC is summarized as follows：
A fast bed 001 is arranged in series in the bottom of riser 101, the reaction system of catalytic cracking unit is formed.Heavy oil
Raw material 1 enter riser 101 bottom, catalyst simultaneously from the bottom of fast bed 001 enter, and along fast bed 001 it is up with again
The oily contact of raw material 1 carries out the first catalytic cracking reaction, and the process conditions of the reaction zone of riser 101 (carry out the first catalytic cracking
The condition of reaction) be：460-520 DEG C of reaction temperature, oil ratio 7-11, reaction time 1.5-2.5s, raw material preheating temperature 100-
300℃.The oil gas of generation enters settler 102 together with catalytic cracking catalyst, real through efficient fast gas-solid separator 103
Existing efficient gas solid separation, catalytic cracking catalyst regenerates after stripping section 104 into regenerator 105；Regenerated catalyst 2 is through oblique
The bottom cycle that pipe returns to fast bed 001 is used.
The oil gas 3 isolated is from the top of settler 102 out and from the bottom of main fractionating tower 106 into being fractionated.Fractionation
Enter catch pot 107 after the condensed cooling of tower top oil gas 4 gone out, cracked gas 5 is drawn from the top of knockout drum 107, and gasoline evaporates
6 are divided to be drawn from the bottom of knockout drum 107, a part is overhead reflux, another part ejector；Diesel oil 7 passes through the vapour of stripper 108
Drawn after carrying, slurry oil 9 is while bottom of towe circulation is carried out, a part of ejector.Cracked gas 5, gasoline 6 and diesel oil 7 are made respectively
Corresponding storage tank is sent into for the target product of the present invention.
Main fractionating tower bottom separates polycyclic aromatic ring component that recycle oil 8 enters in freshening oil tank 109, heavy oil feedstock 1 at this
It is enriched with, can be modified by further catalytic hydrogenation in recycle oil.Refer to the attached drawing 1, what freshening oil tank 109 came out returns
Oil refining 8 enters catalytic hydroconversion device 201, modification occurs in the presence of hydrogen 16 and catalytic hydroconversion catalyst anti-
Should.Catalytic hydroconversion process conditions are：In hydrogen dividing potential drop 6.0-20.0MPa, 300-450 DEG C of reaction temperature, hydrogen to oil volume ratio
300-2000, volume space velocity 0.1-3.0h-l.Afterwards, reaction oil gas 10 enters the secondary middle and lower part of fractionating column 202, carries out each component
Separation.Enter catch pot 107 after the condensed cooling of tower top oil gas 11, cracked gas 5 is drawn on the top of catch pot 107, under
Draw gasoline 6 in portion；Diesel oil 7 is drawn after being stripped by stripper 108, and catalytic hydrogenation heavy oil 15 is drawn from the secondary bottom of towe of fractionating column 202.
Cracked gas 5, gasoline 6, diesel oil 7 are separated and go out device.Catalytic hydrogenation heavy oil 15 then returns to heavy-oil catalytic and split
The bottom of fast bed 001 of reaction system bottom is put in makeup, is contacted with the regenerated catalyst 2 from regenerator 105, is carried out second and is urged
Change cracking reaction.Reaction oil gas flows up into riser 101 with catalytic cracking catalyst, then is contacted instead with heavy oil feedstock 1
Should.The process conditions (condition for carrying out the second catalytic cracking reaction) of the reaction zone of fast bed 001 are：Reaction temperature 540-
600 DEG C, oil ratio 10-20, reaction time 0.1-0.5s, 200-400 DEG C of raw material preheating temperature, water-oil factor is 0.03-0.30, pressure
Power is 130-450kPa.
For the effect of the checking present invention, using the device shown in Fig. 1 and technological process, the RFCC in laboratory
Tested on pilot-plant.
Table 1 show the property of heavy oil feedstock 1, recycle oil 8 and catalytic hydrogenation heavy oil 15.Using the side in the present embodiment
Method, recycle oil 8 enters catalytic hydroconversion device 201 and converted, and the catalytic hydrogenation heavy oil 15 after conversion returns to fast bed 001 and carried out
Second catalytic cracking reaction, reaction oil gas flows up into riser 101 with catalytic cracking catalyst, enters with heavy oil feedstock 1
One step carries out the first catalytic cracking reaction in riser 101.The reaction condition of optimization as shown in table 2, splits with routine heavy-oil catalytic
Chemical industry skill is compared, and can improve yield of light oil using the method in the present embodiment, and liquid yield is improved, dry gas and Jiao
Charcoal yield is substantially reduced, and detailed product distribution can be shown in Table 3.
Table 1
Table 2
Table 3
| Product | Mass content |
| H2S | 0.4% |
| Fuel gas | 2.7% |
| Liquefied gas | 17.7% |
| Gasoline | 47.0% |
| Diesel oil | 24.4% |
| Slurry oil | 1.1% |
| Coke | 6.7% |
| It is total | 100.0% |
Embodiment 2
The RFCC method provided in the present embodiment uses device as shown in Figure 2.With the catalysis in embodiment 1
Unlike cracking unit, the device of the present embodiment also includes：Extraction tower 301, the extraction tower 301 have extraction tower entrance,
De-oiled asphalt is exported and deasphalted oil outlet, and the extraction tower entrance connects the slurry oil outlet of the main fractionating tower 106, described de-
The entrance of catalytic hydroconversion device 201 described in coal tar outlet.
The device provided using the present embodiment carries out the method and the method difference in embodiment 1 of RFCC
It is that slurry oil 9 is after the extraction of the bottom of towe of main fractionating tower 106, with for removing after the extractant 26 of slurry oil studies on asphaltene mixes, entering
Enter extraction tower 301, carry out depitching processing, the extractant 26 is selected from C3-C6 alkane or its mixed fraction.Extraction tower 301
Temperature control between 80-250 DEG C, pressure is between 3.5-10.0MPa, during into extraction tower 301, extractant 26 with oil
The mass flow ratio of slurry 9 is 2.0-8.0:1, isolate de-oiled asphalt 17 and deasphalted oil 18.
De-oiled asphalt 17 goes out device, and after deasphalted oil 18 is then mixed with the recycle oil 8 drawn from freshening oil tank 109, enters
Enter catalytic hydroconversion device 201, in the presence of hydrogen 16 and catalytic hydrogenation catalyst, occur catalytic hydroconversion reaction,
Process conditions are in the same manner as in Example 1.
To verify the effect of the present invention, using the device shown in Fig. 2 and technological process, to the heavy oil feedstock in embodiment 1
Carry out catalytic cracking processing.
Table 4 is solvent extraction removing slurry oil studies on asphaltene process conditions and slurry oil and deasphalted oil in the present embodiment
Property is contrasted.Compared with conventional RFCC, using the method in the present embodiment can improve yield of light oil and
Liquid yield, dry gas and coke yield are substantially reduced, while more effectively being utilized to heavy oil feedstock.It is detailed in the present embodiment
Product distribution can be shown in Table 5.
Table 4
Table 5
| Product | Weight content |
| H2S | 0.41% |
| Fuel gas | 2.70% |
| Liquefied gas | 17.90% |
| Gasoline | 47.30% |
| Diesel oil | 24.65% |
| Slurry oil | 0.50% |
| Coke | 6.54% |
| It is total | 100.0% |
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, or which part or all technical characteristic are entered
Row equivalent；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (8)
1. a kind of RFCC method, it is characterised in that connect fast bed as reactor using lifting bottom of the tube, described
Method comprises the following steps：
Heavy oil feedstock is set to enter the riser from bottom, catalytic cracking catalyst enters the fast bed from bottom, described to urge
It is advanced into riser on fluidized cracking catalysts to contact with heavy oil feedstock and common up, while occurring the first catalytic cracking reaction；
By the reaction oil gas fractionation from riser, cracked gas, gasoline, diesel oil, recycle oil and slurry oil are obtained；
The recycle oil is subjected to catalytic hydrogenation reaction, reaction condition is 340-380 DEG C of reaction temperature, volume space velocity 0.5-2.0h-1, hydrogen to oil volume ratio 300-800, reaction pressure 7-12MPa, the oil gas fractionation that the catalytic hydrogenation reaction is generated, acquisition cracking
Gas, gasoline, diesel oil and catalytic hydrogenation heavy oil；
The catalytic hydrogenation heavy oil is led back into the fast bed and carries out the second catalytic cracking reaction, the reaction oil gas of generation, which enters, to be carried
Riser, carries out first catalytic cracking reaction；
The condition of first catalytic cracking reaction is：460-520 DEG C of reaction temperature, oil ratio 7-11, reaction time 1.5-
2.5s；
The condition of second catalytic cracking reaction is：540-600 DEG C of reaction temperature, oil ratio 10-20, reaction time 0.1-
0.5s, the catalytic hydrogenation heavy oil enters fast bed at 200-400 DEG C, and water-oil factor is 0.03-0.30, and pressure is 130-
450kPa。
2. according to the method described in claim 1, it is characterised in that the catalytic hydrogenation that the recycle oil catalytic hydrogenation reaction is used
Reforming catalyst is made up of additive, group VIII metal, group vib metal and aluminum oxide and/or amorphous silicon aluminium carrier, wherein institute
State one or more of the additive in F, P, Fe and Pt, one or two of the group vib metal in Mo and W, institute
State group VIII metal one or two kinds of in Co and Ni.
3. method according to claim 2, it is characterised in that the catalytic hydroconversion catalyst is added by 5-15wt%
Agent, 5-20wt% group VIII metal, the aluminum oxide and/or amorphous silicon aluminium vehicle group of 15-50wt%VIB races metal and surplus
Into.
4. the method according to claim any one of 1-3, it is characterised in that methods described is also including the use of solvent extraction
Remove the asphalitine in the slurry oil and obtain deasphalted oil, and the deasphalted oil is mixed into progress catalysis with the recycle oil and add
Hydrogen reacts.
5. method according to claim 4, it is characterised in that the extractant that the solvent extraction is used is selected from C3-
C6 alkane or its mixed fraction.
6. a kind of heavy oil catalytically cracking equipment for being used to implement the method described in claim any one of 1-5, it is characterised in that institute
Stating device at least includes：
Riser, the lifting bottom of the tube sets heavy oil entrance and lifting tube inlet, and top sets leg outlet；
Provided with fast bed outlet at the top of fast bed, the fast bed, bottom sets catalyst inlet and catalytic hydrogenation heavy oil entrance；
Oil and gas separating system, the oil and gas separating system sets oil gas and catalyst mixture material entrance, oil gas vent and catalysis
Agent is exported；
Main fractionating tower, the main fractionating tower sets main fractionating tower entrance, and top is provided with multiple light fraction outlets, and bottom is then provided with back
Oil refining outlet and slurry oil outlet；
Catalytic hydroconversion device, catalytic hydroconversion device sets catalytic hydroconversion device portal and catalytic hydroconversion dress
Put outlet；
Secondary fractionating column, the secondary fractionating column sets secondary fractionating column entrance, the outlet of catalytic hydrogenation heavy oil and multiple light fraction outlets；
Tube inlet is lifted described in the fast bed outlet makes the two series connection conducting, and the leg outlet connects the oil gas
The oil gas and catalyst mixture material entrance of piece-rate system, the catalyst outlet of the oil and gas separating system connect the fast bed
Catalyst inlet, oil gas vent connects the main fractionating tower entrance, the recycle oil outlet catalysis of the main fractionating tower plus
Hydrogen reforming unit entrance, catalytic hydroconversion device outlet pair fractionating column entrance, the catalytic hydrogenation heavy oil of secondary fractionating column goes out
The catalytic hydrogenation heavy oil entrance of the mouth connection fast bed.
7. there is device according to claim 6, it is characterised in that also including extraction tower, the extraction tower extraction tower to enter
Mouth, de-oiled asphalt outlet and deasphalted oil outlet, the extraction tower entrance connect the slurry oil outlet of the main fractionating tower, described to take off
Catalytic hydroconversion device portal described in coal tar outlet.
8. the device according to claim 6 or 7, it is characterised in that the catalytic hydroconversion device is fixed bed reaction
Device.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510850362.4A CN105419868B (en) | 2015-11-27 | 2015-11-27 | RFCC method and apparatus |
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|---|---|---|---|
| CN201510850362.4A CN105419868B (en) | 2015-11-27 | 2015-11-27 | RFCC method and apparatus |
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| CN105419868B true CN105419868B (en) | 2017-07-11 |
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| CN105861045B (en) * | 2016-04-29 | 2018-02-27 | 中国石油大学(北京) | A kind of method and device of Grading And Zoning conversion catalyst cracked cycle oil |
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| US7682501B2 (en) * | 2004-12-23 | 2010-03-23 | Abb Lummus Global, Inc. | Processing of different feeds in a fluid catalytic cracking unit |
| CN101538481B (en) * | 2008-03-20 | 2012-08-22 | 中国石油化工股份有限公司 | Improved hydrotreatment and catalytic cracking combination method for hydrocarbon oil |
| CN102102026B (en) * | 2009-12-17 | 2014-04-02 | 中国石油大学(北京) | Method and device for heavy oil tandem regional catalytic cracking |
| CN103571534B (en) * | 2013-09-17 | 2014-07-30 | 中国石油大学(华东) | Device and method for producing clean gasoline by combining catalytic cracking and hydrofining |
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