CN102311767A - Gasoline olefin reducing catalytic cracking method and device - Google Patents
Gasoline olefin reducing catalytic cracking method and device Download PDFInfo
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- CN102311767A CN102311767A CN201010219944XA CN201010219944A CN102311767A CN 102311767 A CN102311767 A CN 102311767A CN 201010219944X A CN201010219944X A CN 201010219944XA CN 201010219944 A CN201010219944 A CN 201010219944A CN 102311767 A CN102311767 A CN 102311767A
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Abstract
The invention discloses a gasoline olefin reducing catalytic cracking method and a gasoline olefin reducing catalytic cracking device. In the method and the device, a renewable catalyst is contacted with heavy oil and low-quality gasoline through conveying pipes for reactions respectively, the reaction oil gases enter a fractioning system respectively, the catalyst to be renewed is renewed in a tubular coke burning device and a catalyst dense-phase bed, and the renewed catalyst is used circularly. When the method and the device are used, the drawbacks of nonflexible control of catalyst temperature, high renewable catalyst and raw material contact temperature, long reaction time, low agent to oil ratio, low coke burning capacity of the device and the like are overcome.
Description
Technical field
The invention belongs under the situation that does not have hydrogen the catalytic cracking of hydrocarbon ils, particularly a kind of catalyst cracking method and device that reduces gasoline olefin.
Background technology
At present, there is following problem in conventional lifting tubular type CCU:
The first, regenerator temperature can't realize flexible control, and the regeneration temperature of catalyzer generally all is higher than 650 ℃; Make in the riser reactor finish moment contact temperature higher; Too high finish contact temperature can aggravate heat cracking reaction, reduce the degree of catalytic cracking reaction, and the result is that the product distribution worsens, and dry gas and coke yield rise, total liquid yield descends (total liquid yield refers to liquefied gas yield, gasoline yield and diesel yield sum); Because higher regenerated catalyst temperature; Limited by device thermal equilibrium, make the agent-oil ratio of heavy oil riser reactor less relatively, be generally 5～8.
The second, owing to promote the reaction times (generally about 4s) that the length of tubular reactor has determined raw material.The long reaction times has also been aggravated the secondary reaction of raw material cracking resultant when improving the raw material per pass conversion, make the reacted gas gain in yield, thereby has reduced the yield of vapour, diesel oil distillate.
The 3rd; Owing to being higher than the catalyzer linear speed, the oil gas linear speed in the lifting tubular reactor cause the landing of knot Pd/carbon catalyst to form back-mixing; Thus, promoting tubular type reactor feedstocks nozzle top, the catalyzer of knot charcoal landing contacts with initial stage cracking resultant with atomized feed once more; Thereby worsened the product distribution, reduced catalyzer raw material cracked product selectivity.
The 4th, catalytic cracking occupies extremely important status as the main means of oil secondary processing in China.Because the technology and the material characteristic of catalytic cracking, catalytic cracking gasoline olefine content is between 40～60v%, and its sulphur content is also in rising trend.Because the total amount of finish of China's CCU is excessive; Unreasonable products structure; Wherein the share of catalytically cracked gasoline in China's gasoline products reaches more than 70%; Cause the olefin(e) centent severe overweight in the gasoline product, the state III oil quality of carrying out now far above China requires the olefin(e) centent of gasoline to be not more than the standard of 35v%.To this; Domestic each research institution has developed various technology to reducing content of olefin in gasoline; Research Institute of Petro-Chemical Engineering of China Petrochemical Industry has developed the GOR catalyst series that reduces the catalytic gasoline olefin(e) centent (" refining of petroleum and chemical industry " 2002 7 phases the 5th～8 page); This catalyzer has very high hydrogen transfer activity and higher isomerization activity through introducing the y-type zeolite and the modification ZRP zeolite of oxide surface modification, can make the FCC gasoline olefin reduce about 10 percentage points.Refining institute of Luoyang Petrochemical engineering corporation of China Petrochemical Industry has developed the LAP series auxiliary agent (the 23rd～27 page of " oil refining design " 9 phase of calendar year 2001) that reduces the catalytic gasoline olefin(e) centent; This auxiliary agent is a main active component with the shape zeolite of selecting of poly-metal deoxide modification; Have very high gasoline olefin aromatization activity and higher cracking of olefins activity; When adding 5% LAP auxiliary agent in the catalyzer, can make the FCC gasoline olefin reduce about 10 percentage points.On process method; Research Institute of Petro-Chemical Engineering of China Petrochemical Industry has developed and has had the MGD technology that reduces the content of olefin in gasoline function (" refining of petroleum and chemical industry " 2002 2 phase the 19th～22 page), and MGD technology is divided into two sections to conventional FCC master's riser reactor, and hypomere is as the gasoline upgrading reaction zone; Epimere is as FCC master's riser reaction zone; Utilize high agent-oil ratio and high activated catalyst reformulated gasoline, this technology will be taken into account the reaction conditions of main riser tube RFCC, and the amount of gasoline upgrading is limited; It is also not ideal to fall the alkene amplitude, can make the FCC gasoline olefin reduce by 10～12 percentage points.
The 5th, because revivifier carbon-burning capacity and to burn efficient relatively low, make the size of revivifier big and catalyst inventory is higher, cause facility investment relatively large.
The related FDFCC Technology of Chinese patent ZL200510017751.5 is to utilize the technical superiority of catalytic cracking double lifting leg; The spent agent that remains with high remaining activity (being equivalent to regenerator active 90%), low temperature (about 500 ℃) after the lighter hydrocarbons riser tube reaction is partly or entirely returned the mixing tank that heavy oil riser tube bottom is provided with, in mixing tank with entering heavy oil riser tube and heavy oil contact reacts after regenerated catalyst from revivifier mixes.Because the heat exchange action of two strands of catalyzer effectively drops to about 630 ℃ the temperature of mixed catalyst in the mixing tank; Get into heavy oil riser tube and heavy feed stock contact reacts; Agent-oil ratio is significantly improved; And effectively reduce dry gas, the coke yield of device, and liquid yield improves, and product distributes and improves.Catalytic gasoline is through lighter hydrocarbons riser tube upgrading, and content of olefin in gasoline is reduced to 10～25v% behind the upgrading, 25～50 percentage points of the ranges of decrease; Gasoline octane rating (RON) improves 0.1～2 unit; Content of sulfur in gasoline reduces by 20～40%.But should technology have following some deficiency: 1. regenerator temperature can't realize flexible control, and this technical superiority only is embodied in the CCU of two above riser tubes.2. because this technology is traditional lifting tubular type catalytic cracking, shown still that long reaction time, dry gas and coke yield are high relatively, product distribution relative mistake, the revivifier carbon-burning capacity is low and the high deficiency of plant energy consumption.3. contact temperature during the catalytic gasoline upgrading with regenerated catalyst high, and long reaction time causes the dry gas of device and coke yield further to increase, the reduction of reformulated gasoline yield.
The related high efficiency regenerating technology for molecular sieve catalyst technology of Chinese patent ZL97106088.6 mainly comprises: 1. reclaimable catalyst gets into the external cyclone water-separator group in first root regeneration pipe regeneration back, gets into the second root regeneration pipe through dipleg.2. the second root regeneration pipe external cyclone water-separator group dipleg directly gets into external warmer, and inclined tube gets into riser reactor through the bottom.Technology was burnt the time in 10 seconds, burnt intensity (per hour, the burning carbon amount of catalyzer per ton) and be about 10 times of prior art.But should technology also have following 2 deficiencies: 1. employing promotes tubular reactor and can't realize the raw material short reaction time.2. technological process and complicated operation are difficult to carry out on the engineering.3. should technology not relate to the catalytic gasoline upgrading.
The related a kind of catalytic cracking riser coke burning regeneration device technical characterstic of Chinese patent ZL93242428.7 is: riser regenerator is provided with the multistage air inlet and carries out reclaimable catalyst regeneration; Strengthened the coke burning regeneration process of reclaimable catalyst; It is simple in structure, and is easy to operate.But should technology have the lifting tubular reactor and can't realize the operation of raw material short reaction time.This technology does not relate to the catalytic gasoline upgrading yet.
The related technology features of U.S. Pat P:5462652 is: 1. reacting-settler top is provided with the catalyst mix jar, and mixing tank adopts water vapor to carry out the uniform mixing of catalyzer; The reacting-settler top is provided with the mixed catalyst chamber, and catalyzer gets into reacting-settler by mixed catalyst chamber central opening.2. the stripping of the reaction of catalyzer and raw material and reclaimable catalyst all carries out in reacting-settler, and catalyzer flows and is directed downwards, and the raw material injection direction of nozzle becomes 90 ° of angles, the plug-in cyclonic separator of reacting-settler with the mobile direction of catalyzer.3. a part of reclaimable catalyst is promoted to revivifier by first air-lift tube and carries out coke burning regeneration; Another part reclaimable catalyst is promoted to the catalyst mix jar by second air-lift tube, and the catalyzer after the regeneration is promoted to the catalyst mix jar by the 3rd air-lift tube and mixes the mixed catalyst temperature that reduces the entering reacting-settler with reclaimable catalyst.Because above characteristic, U.S. Pat P:5462652 technology realize the raw material short reaction time in reacting-settler, low finish contact temperature, the high agent-oil ratio operation descends the dry gas of device, coke yield, and liquid yield improves, and product distributes and improves.But should technology still have following some deficiency: 1. adopt conventional catalytic cracking regenerator, its carbon-burning capacity is low.2. participate in catalyzer and the mixture of reclaimable catalyst of catalyst for reaction after for regeneration, this mixed catalyst must be affected to the cracking activity of raw material, also certainly will be to the product deleterious impact that distributes.3. technological process and complicated operation.4. this technology does not relate to the catalytic gasoline modification technology.
Therefore; Reduce and control the agent-oil ratio of temperature, raising heavy oil catalytic cracking reaction and the catalytic gasoline upgrading of regenerated catalyst; Shorten its reaction times and adopt tubular type to burn to improve and regenerate carbon-burning capacity and burn efficient; Reduce total dry gas (even comprising liquefied gas) and coke yield and improve the reformulated gasoline yield and the product that improves catalytic cracking reaction is distributed and product property reduction plant energy consumption, the catalyst inventory of reduction revivifier; Dwindle the revivifier size, reduce facility investment and have important effect.
Summary of the invention
Technical problem to be solved by this invention be the catalyst temperature control flexibly that is in revivifier of existing catalytic cracking process, regenerated catalyst with raw material contact temperature height, long reaction time, agent-oil ratio is low and the device carbon-burning capacity is low etc.
The purpose of this invention is to provide a kind of catalyst cracking method and device that reduces gasoline olefin; Implement reclaimable catalyst tubular type coke burning regeneration on the CCU and controlling the regenerated catalyst temperature (between 580～650 ℃) of revivifier; RFCC and catalytic gasoline upgrading are separate and all adopt under short reaction time between low finish contact temperature, the 0.1～1.0s, the high agent-oil ratio condition and operate; Reach the olefin(e) centent that reduces reacted gas and coke yield, raising gasoline and diesel oil distillate yield, reduces catalytic gasoline, improve the purpose of gasoline product quality.
A kind of catalyst cracking method that reduces gasoline olefin of the present invention is characterised in that:
1) regenerated catalyst in the revivifier 2 gets into regenerated catalyst 4 and regenerated catalyst 21 respectively; The catalyzer contact reacts of heavy oil feed 10 and regenerated catalyst 4 bottoms; Reacted reclaimable catalyst separates with the cyclonic separator 12 that generation oil gas gets in the settling vessel 13; The heavy oil reaction generates oil gas 7 and gets into separation column, and isolated reclaimable catalyst gets into 3 regeneration; The catalyzer contact reacts of inferior patrol charging 26 and regenerated catalyst 21 bottoms; Reclaimable catalyst behind the upgrading separates with cyclonic separator 29 with the cyclonic separator 30 that generation oil gas gets in the settling vessel 13; Isolated oil gas 24 gets into the gasoline fractionating system through oil gas collection chamber 25 and carries out fractionation, and isolated reclaimable catalyst gets into step 2);
2) behind stripped vapor 31 strippings, getting into tubular type from the reclaimable catalyst of step 1) at the stripping stage 15 of settling vessel 13 burns device 20 and carries out coke burning regeneration; Cyclonic separator 19 in the half regenerated catalyzer entering revivifier 2 carries out catalyzer with cyclonic separator 1 to be separated with flue gas; Flue gas 17 after the separation is discharged; Half regenerated catalyst entering regenerated catalyst dense bed 3 after the separation is regenerated and is cooled off, and the regeneration cooled regenerated catalyst turns back to 1).
A kind of catalyst cracking method that reduces gasoline olefin of the present invention; Be characterised in that: the regenerated catalyst temperature that gets into regenerated catalyst 4 and regenerated catalyst 21 is 580～650 ℃, and the reaction times that heavy raw oil 10 contacts with regenerated catalyst is 0.1～1.0s; Temperature of reaction is 480～580 ℃, and agent-oil ratio is 5～30, and the reaction absolute pressure is 0.15～0.40MPa; The reaction times that inferior patrol contacts with regenerated catalyst is 0.1～1.0s; Temperature of reaction is 400～550 ℃, and agent-oil ratio is 5～30, and the reaction absolute pressure is 0.15～0.40MPa;
A kind of catalyst cracking method that reduces gasoline olefin of the present invention is characterised in that: the temperature of burning that tubular type is burnt in the device is 600～720 ℃, and the air linear speed is 1.0～5m/s, and burning intensity is 300～1000kg/ (t.h), burns time 8～40s,
Catalytic cracking process of the present invention is further characterized in that: revivifier catalyzer dense bed temperature is 580～650 ℃.
The present invention also provides a kind of CCU that reduces gasoline olefin; Be characterised in that: comprise that the regenerated catalyst 4 of revivifier 2, heavy oil cracking, regenerated catalyst 21, settling vessel 13 and the tubular type of catalytic gasoline upgrading burn device 20; Revivifier 2 is communicated with settling vessel 13 through the regenerated catalyst 4 of heavy oil cracking and the regenerated catalyst 21 of catalytic gasoline upgrading; Metal partion (metp) 28 is isolated oil gas collection chamber 8 and oil gas collection chamber 25; Settling vessel stripping stage 15 burns device 20 with tubular type and is communicated with, and tubular type is burnt device 20 outlets and is communicated with the cyclonic separator 19 of revivifier 2.
Said a kind of CCU that reduces gasoline olefin is characterised in that: cyclonic separator 19, cyclonic separator 1 and distributor pipe of cardinal wind 5 are set in the revivifier 2.
Said a kind of CCU that reduces gasoline olefin is characterised in that: settling vessel 13 is provided with metal partion (metp) 28, collection chamber 8, collection chamber 25, cyclonic separator 9, cyclonic separator 12, cyclonic separator 29, cyclonic separator 30 and settling vessel stripping stage 15.
Said a kind of CCU that reduces gasoline olefin is characterised in that: tubular type is burnt device 20 and is comprised and burn wind distribution pipe 34.
Said a kind of CCU that reduces gasoline olefin is characterised in that: on the regenerated catalyst 4 of heavy oil cracking and the regenerated catalyst 21 of catalytic gasoline upgrading valve 6 and valve 23 are set respectively.
Said a kind of CCU that reduces gasoline olefin is characterised in that: revivifier is positioned at the reacting-settler top.
Said a kind of CCU that reduces gasoline olefin is characterised in that: the regenerated catalyst 4 of heavy oil cracking and regenerated catalyst 21 xsects of catalytic gasoline upgrading are for circular.
Said a kind of CCU that reduces gasoline olefin is characterised in that: heavy feedstocks nozzle 11 is identical or different with the distance of settling vessel 13 walls with inferior patrol feed nozzle 27, is generally 2～5 meters.
The regenerated catalyst 4 of heavy oil cracking and the regenerated catalyst 21 liner insulated linings of inferior gasoline upgrading, Φ 200～3000mm.
The catalyst cracking method that the present invention is a kind of to reduce gasoline olefin compared with prior art has following beneficial effect:
1. burn in the device in tubular type; Burning air flow quantity can adjust flexibly; And the reclaimable catalyst amount of unit time gets into tubular type and burns the device bottom and contact and strengthened the carbon-burning capacity that tubular type is burnt device with the oxygen containing fresh air that burns capacity, rich all the time; Make tubular type burn device and burn the intensity increase, improved the efficient of burning that tubular type is burnt device.But tubular type is burnt on the device burning-off reclaimable catalyst 70～80% coke.Tubular type is burnt device, and to burn temperature be that 600～720 ℃, air linear speed are 1.0～5m/s, burn time 8～40s; Tubular type is burnt device, and to burn the intensity burning carbon amount of catalyzer per ton (per hour) be 300～1000kg/ (t.h), and tubular type is burnt device and compared with conventional CCU regeneration and have stronger carbon-burning capacity and turndown ratio more flexibly.
2. the finish of RFCC and catalytic gasoline upgrading contact temperature is high can aggravate the heat cracking reaction of raw material, the degree of reduction catalytic cracking reaction; The result is that the product distribution worsens, and dry gas and coke yield rise, total liquid yield descends (total liquid yield refers to liquefied gas yield, gasoline yield and diesel yield sum).Adopt revivifier main air cooling regenerated catalyst technology; Can effectively control regenerated catalyst temperature between 580～650 ℃; Thereby reduce the temperature that contacts of regenerated catalyst and raw material, reach the dry gas, the coke yield that reduce device, the raising liquid yield; Improve product and distribute, improve the purpose of the economic benefit of refinery.
3. in the heavy feed stock catalytic cracking process, the long reaction times has also been aggravated the secondary reaction of raw material cracking resultant when improving the raw material per pass conversion, make the reacted gas gain in yield, thereby has reduced the yield of vapour, diesel oil distillate; The high agent-oil ratio operation can remedy the raw material per pass conversion dampening factor that is brought owing to the short reaction time.Adopt short reaction time (reaction times is between 0.1～1.0s), high agent-oil ratio 5～30 operations of regenerated catalyst and raw material; Can reduce reacted gas (comprising dry gas and the liquefied gas) productive rate of device; Make the yield of vapour, diesel oil distillate obtain increasing, improved the utilization ratio of petroleum resources.
4. when catalytic gasoline carried out upgrading under the condition of short reaction time, low finish contact temperature, high agent-oil ratio, reacted gas (liquefied gas+dry gas) and coke yield were low, and the reformulated gasoline yield is high.The present invention is because RFCC and catalytic gasoline upgrading and fractionation are separate; Catalytic gasoline through upgrading; Content of olefin in gasoline can be reduced to 10～25v%; Can dispatch from the factory as gasoline products separately, the blend component that also can be used as gasoline products is used to be in harmonious proportion and satisfies state's III oil quality that China carries out now and require the olefin(e) centent of gasoline to be not more than the gasoline products of 35v%.Gasoline octane rating behind the upgrading (RON) improves 0.1～1.5 unit; Content of sulfur in gasoline reduces by 15～35%.
5. device dry gas, coke yield descend, and the energy consumption of device is reduced.Tubular type is burnt device and is burnt the catalyst inventory that the intensity burning carbon amount of catalyzer per ton (per hour) can reduce revivifier greatly, makes the dimension shrinks of revivifier, and plant investment descends.
Heavy oil reactive system of the present invention is applicable to the catalyzed cracking processing of long residuum, vacuum residuum, straight-run gas oil, wax tailings, deasphalted oil, hydrogenation wax oil, recycle stock, slurry oil, crude oil, shale oil, synthetic oil and the various hydro carbons heavy oil of coal tar wet goods.
The inferior gasoline upgrading reactive system mainly is applicable to the catalytic gasoline of self or other devices, but also inferior patrols such as upgrading coker gasoline, straight-run spirit.
Below in conjunction with accompanying drawing, embodiment and embodiment the present invention is done further detailed explanation.But do not limit the present invention and require the scope protected.
Description of drawings
Accompanying drawing 1 is a kind of CCU synoptic diagram that reduces gasoline olefin of the present invention.
1. cyclonic separator, 2. revivifier, 3. regenerated catalyst dense bed, the 4. regenerated catalyst of heavy oil cracking, 5. distributor pipe of cardinal wind; 6. the regenerated catalyst flowrate control valve of heavy oil cracking, 7. the heavy oil cracking reaction generates oil gas, and 8. the heavy oil cracking reaction generates oil gas collection chamber, 9. cyclonic separator, 10. heavy raw oil; 11. the heavy feed stock oil burner nozzle, 13. settling vessels, 14. reclaimable catalyst dense beds, 15. settling vessel stripping stages, 16. inclined tubes to be generated; 17. flue gas, 18. regenerated flue gas collection chambers, 19. cyclonic separators, 20. tubular types are burnt device, the regenerated catalyst of 21. catalytic gasoline upgradings; 22. main air, 23. catalytic gasoline upgradings the regenerated catalyst flowrate control valve, the reaction of 24. catalytic gasoline upgradings generates oil gas, the reaction of 25. catalytic gasoline upgradings generates the oil gas collection chamber; 26. the catalytic gasoline charging, 27. catalytic gasoline feed nozzles, 28. metal partion (metp)s, 29. cyclonic separators; 31. water stripping steam, 32. reclaimable catalyst flowrate control valves, 33. burn wind, and 34. burn the wind distribution pipe.
Embodiment
A kind of CCU of producing low-alkene gasoline of the present invention shown in accompanying drawing, this device comprise that revivifier 2, settling vessel 13, tubular type burn device 20 three parts and form.Press the flow process of device inner catalyst; Be provided with the regenerated catalyst 4 of revivifier 2, heavy oil cracking, the regenerated catalyst 21 of catalytic gasoline upgrading successively; The regenerated catalyst flowrate control valve 6 of heavy oil cracking; The regenerated catalyst flowrate control valve 23 of catalytic gasoline upgrading, settling vessel 13, stripping stage 15 and tubular type are burnt device 20.Revivifier 2 is connected with settling vessel 13 through the regenerated catalyst 4 of heavy oil cracking and the regenerated catalyst 21 of catalytic gasoline upgrading; On the regenerated catalyst 4 of the heavy oil cracking between revivifier 2 and the settling vessel 13, the regenerated catalyst 21 of catalytic gasoline upgrading regenerated catalyst flowrate control valve 6 and 23 are set respectively; The bottom of settling vessel 13 is a reclaimable catalyst stripping stage 15, and the stripping stage 15 below standpipes of settling vessel 13 are connected with inclined tube 16 to be generated.Inclined tube to be generated 16 middle parts are provided with reclaimable catalyst flowrate control valve 32, and inclined tube 16 to be generated burns device 20 bottoms with tubular type and is connected; Tubular type is burnt device 20 outlets and is connected with revivifier 2 interior cyclonic separators 19.The dipleg of cyclonic separator 19 gets in the regenerated catalyst dense bed 3.
Described revivifier 2 comprises cyclonic separator 1, cyclonic separator 19, and its size and structure confirm to meet the conventional general feature that promotes tubular type CCU revivifier.It is circular metal tube that the pipeline of the regenerated catalyst 4 of heavy oil cracking, the regenerated catalyst 21 of catalytic gasoline upgrading adopts xsect; The liner insulating and wearing-resistant lining; Internal diameter is Φ 200～2000mm, and its diameter is confirmed according to the stream pipe method of calculation of flooding in routine list or the double lifting leg formula CCU revivifier.
Described regenerated catalyst flowrate control valve 6 and 23 is located at respectively on the regenerated catalyst 21 of regenerated catalyst 4, catalytic gasoline upgrading of the heavy oil cracking that links to each other between revivifier 2 and the settling vessel 13; Can adopt various flowrate control valves commonly used (as adopting guiding valve); To regulate the regenerated catalyst flow, realize temperature of reaction is controlled.
The inlet of the regenerated catalyst 4 of described heavy oil cracking, the regenerated catalyst 21 of catalytic gasoline upgrading is arranged on regenerated catalyst dense bed 3 tops; Below, regenerated catalyst dense bed 3 interfaces, its set-up mode can be confirmed with reference to the stream pipe that floods in the conventional CCU revivifier.The outlet of the regenerated catalyst 4 of heavy oil cracking, the regenerated catalyst 21 of catalytic gasoline upgrading is connected with settling vessel 13 by the side wall entering of settling vessel 13, above reclaimable catalyst dense bed 14 interfaces of outlet position in settling vessel 13.
Described settling vessel 13 comprises cyclonic separator and stripping stage, and its size and structure confirm to meet the conventional general calculated characteristics that promotes tubular type CCU settling vessel.
The oil gas collection chamber at described settling vessel 13 tops is isolated into two independently oil gas collection chambers 8 and 25 by metal partion (metp) 28 on settling vessel 13 diameters.
Heavy feedstocks nozzle 11 in the described settling vessel 13 points to the regenerated catalyst Way out of entering settling vessel with catalytic gasoline feed nozzle 27 Way outs and is provided with in the same way with the mobile direction of regenerated catalyst; Its position is arranged on the medullary ray of regenerated catalyst outlet separately; Heavy feedstocks nozzle (11) is identical with the distance of settling vessel 13 walls with catalytic gasoline feed nozzle 27, and L and 1 is 2～5M.Heavy feedstocks nozzle 11 and catalytic gasoline feed nozzle 27 meet the general feature of conventional CCU feed nozzle.
It is circular metal tube that described inclined tube to be generated 16, pipeline adopt xsect, and liner insulating and wearing-resistant lining, internal diameter are Φ 300～2000mm, and its diameter promotes tubular type CCU inclined tube method of calculation to be generated according to routine and confirms.Reclaimable catalyst flowrate control valve 32 is located on the inclined tube 16 to be generated, can adopt various flowrate control valves commonly used (as adopting guiding valve), to regulate the reclaimable catalyst flow.
Described tubular type is burnt device 20 and is adopted xsect to be circular metal tube, the liner insulating and wearing-resistant lining, and length is 20～40M, Φ 400～2500mm; Tubular type is burnt the setting of device 20 bottoms and is burnt wind distribution pipe 34, and its size is confirmed according to the distribution pipe method of calculation that routine promotes the tubular type CCU.The concrete diameter that tubular type is burnt device 20 confirms according to burning the operating linear velocity that wind 33 burns device 20 in tubular type, and tubular type is burnt device 20 length and confirmed according to the total height of revivifier 2 and reacting-settler 13.
A kind of catalyst cracking method of producing low-alkene gasoline of the present invention is following shown in accompanying drawing: the regenerated catalysts in the revivifier 2 divide two-way to get into regenerated catalyst 4 and 21 downwards, regenerated catalyst 4 and 21 bottoms with through heavy oil feed 10 and catalytic gasoline charging 26 contact reactss of heavy oil feed nozzle 11 with 27 entering of catalytic gasoline feed nozzle.Heavy oil feed 10 reacted reclaimable catalysts separate with 9 with the cyclonic separator 12 that generation oil gas gets in the settling vessel; Reclaimable catalyst behind catalytic gasoline charging 26 upgradings separates with 29 with the cyclonic separator 30 that generation oil gas gets in the settling vessel.Separating heavy oil reaction behind the stripping generates oil gas 7 and stripped vapor and gets into independently fractionating system through oil gas collection chamber 8 and carry out fractionation.The catalytic gasoline upgrading generates oil gas 24 and carries out fractionation through the fractionating system that oil gas collection chamber 25 gets into self.Isolated reclaimable catalyst gets into tubular types through inclined tube 16 to be generated and reclaimable catalyst flowrate control valve 32 at the stripping stage 15 of settling vessel 13 and burns device 20 bottoms and burn from distribution pipe 34 that wind 33 contacts and burn the device 20 up reclaimable catalyst coke burning regenerations that carry out along tubular type behind water vapor 31 strippings.Burning half regenerated catalyst after device 20 regeneration through tubular type gets into cyclonic separator 19 and 1 in the revivifier 2 and carries out catalyzer and separate with flue gas.The dipleg of half regenerated catalyst after the separation through cyclonic separator 19 and 1 gets in the catalyzer dense bed 3 of revivifier 2; Main air 22 contacts the residual coke on burning-off half regenerated catalyst and cools off regenerated catalyst through the bottom that distribution pipe 5 gets into revivifier 2 with half regenerated catalyst, the regeneration rear catalyst gets into two root regeneration catalyst transports and recycles.The flue gas 17 that generates is discharged revivifier 2 through cyclonic separator 1 through regenerated flue gas collection chamber 18.Above-mentioned operating process circulation is continuously carried out.
The present invention adopts tubular type to burn and the cooling of revivifier main air; Can effectively control regenerated catalyst temperature; Thereby reduce the temperature that contacts of regenerated catalyst and heavy feed stock and catalytic gasoline raw material, reach the dry gas, the coke yield that reduce cracking heavy feedstocks and the generation of catalytic gasoline upgrading, the raising liquid yield; Improve product and distribute and quality product, improve the economic benefit of refinery; Adopt the short reaction time, the high agent-oil ratio operation has reduced the secondary reaction in raw material cracking and the catalytic gasoline upgrading process, and reacted gas (comprising dry gas and liquefied gas) productive rate is descended, and the yield of vapour, diesel oil distillate obtains increasing; Adopt tubular type to burn device and improved the carbon-burning capacity of device and burnt efficient, reduced the catalyst inventory of revivifier, dwindled the size of revivifier, the appliance arrangement investment is descended.Device dry gas, coke yield descend, and the energy consumption of device is reduced.
Regenerated catalyst temperature is 580～650 ℃ in the said revivifier 2, and absolute regeneration pressure is 0.15～0.40MPa, the catalyzer residence time 3～6min.Other operating parameterss meet the general feature of conventional CCU revivifier.
The main air 22 of described revivifier 2 is a pressurized air; The main effect of this main air 22 is residual coke on burning-off half regenerated catalyst and the temperature of cooling off the catalyzer dense bed 3 of revivifier 2, and catalyzer dense bed 3 temperature that reach control revivifier 2 are 580～650 ℃ purpose.The air quantity of main air 22 is confirmed through heat calculation according to the catalyst inventory and the control target temperature of revivifier 2.
Described heavy raw oil 10 cracking operational conditions are: temperature of reaction is 480～580 ℃, is preferably 500～560 ℃, is preferably 530～550 ℃; Heavy raw oil 10 is 0.1～1.0s through the reaction times that contacts of feed nozzle 11 and regenerated catalyst, is preferably 0.05～0.5s, is preferably 0.1～0.3s; Agent-oil ratio is 5～30, and agent-oil ratio is confirmed by the heat calculation in when reaction; The reaction absolute pressure is 0.15～0.40MPa;
Described catalytic gasoline 26 upgrading operational conditions are: temperature of reaction is 400～550 ℃, is preferably 420～530 ℃, is preferably 450～500 ℃; Catalytic gasoline raw material 26 is 0.01～1.0s through the reaction times that contacts of catalytic gasoline feed nozzle 27 and regenerated catalyst, is preferably 0.05～0.5s, is preferably 0.1～0.3s; Agent-oil ratio is 5～30, and agent-oil ratio is confirmed by the heat calculation in when reaction; The reaction absolute pressure is 0.15～0.40MPa;
The stripping condition of the stripping stage 15 of described settling vessel 13 also is conventional, and the stripping medium is a water vapor, and the stripping temperature is 480～520 ℃.
Described reclaimable catalyst burns device 20 bottoms and burns that wind 33 contacts and burn on the device 20 up burning-off reclaimable catalysts 70～80% coke along tubular type in tubular type.Tubular type is burnt device 20, and to burn temperature be 600～720 ℃, and the air linear speed that tubular type is burnt device 20 is 1.0～5m/s, and tubular type is burnt device, and to burn the intensity burning carbon amount of catalyzer per ton (per hour) be 300～1000kg/ (t.h), burns time 8～40s.Burn wind 33 and be pressurized air, this pressurized air meets the compressed-air actuated general feature of conventional CCU, and its flow can multiply by unit weight coke required air quantity when burning according to total green coke amount of raw material unit time and calculate to confirm.
Described heavy raw oil 10 meets the conventional ingredient requirement that promotes the tubular type CCU with catalytic gasoline raw material 26.
What a kind of catalyst cracking method of producing low-alkene gasoline of the present invention adopted is the conventional tubular type catalytic cracking catalyst that promotes.
The concrete operations of catalytic cracking of the present invention and control process, the those of ordinary skill in catalytic cracking field can be selected for use according to the concrete operations situation.
Comparative Examples and embodiment
Comparative Examples 1
Test raw material adopts the grand celebration long residuum, and catalyzer adopts commercially available CC-20 catalytic cracking industry equilibrium catalyst, and micro-activity is 65.Catalytic cracking heavy oil makes an experiment on the catalytic cracking riser pilot plant.The pilot plant riser reactor is simulated full freshening operation, and the regeneration temperature of revivifier inner catalyst is 700 ℃, and the carbon content of regenerated catalyst is 0.03w%, and micro-activity is 65.The stripping medium of reacting-settler stripping stage is a water vapor, and the stripping temperature is 500 ℃.
Catalytic cracking heavy feedstocks character is seen table 1, and the operational condition of catalytic cracking reaction, product distribute and see table 3.Comparative Examples 2
Test raw material adopts the generation gasoline of grand celebration long residuum catalytic cracking.Catalyzer adopts commercially available CC-20 catalytic cracking industry equilibrium catalyst, and micro-activity is 65.The catalytic gasoline upgrading makes an experiment on the catalytic cracking riser pilot plant, and the regeneration temperature of revivifier inner catalyst is 700 ℃, and the carbon content of regenerated catalyst is 0.03w%, and micro-activity is 65.The stripping medium of reacting-settler stripping stage is a water vapor, and the stripping temperature is 500 ℃.Catalytic gasoline upgrading feedstock property is seen table 2, and catalytic gasoline upgraded condition, product distribute and part character is seen table 4.
Embodiment 1
Test raw material adopts the grand celebration long residuum, and catalyzer adopts commercially available CC-20 catalytic cracking industry equilibrium catalyst, and micro-activity is 65.
The catalytic cracking scheme is carried out on the scale fluidized bed equipment of laboratory, and reclaimable catalyst adopts tubular type to burn the back and gets in the revivifier, and micro-activity is 65.The stripping medium of settling vessel stripping stage is a water vapor, and the stripping temperature is 500 ℃.The present embodiment CCU adopts full freshening operating operation condition, product to distribute and portioned product character is seen table 5.
Embodiment 2
Press embodiment 1, different is the temperature from the regenerated catalyst of revivifier, temperature of reaction, agent-oil ratio and the reaction times of raw material.The operational condition of present embodiment CCU, product distribute and portioned product character is seen table 6.
Embodiment 3
Press embodiment 1, different is temperature, agent-oil ratio and the reaction times of raw material when reaction from the regenerated catalyst of revivifier.The operational condition of present embodiment CCU, product distribute and portioned product character is seen table 7.
Embodiment 4
Press embodiment 1, different is temperature, agent-oil ratio and the reaction times of raw material when reaction from the regenerated catalyst of revivifier.The operational condition of present embodiment CCU, product distribute and portioned product character is seen table 8.
Embodiment 5
Press embodiment 1, different is temperature, temperature of reaction, agent-oil ratio and the reaction times of raw material when reaction from the regenerated catalyst of revivifier.The operational condition of present embodiment CCU, product distribute and portioned product character is seen table 9.
Embodiment 6
Press embodiment 1, different is temperature, temperature of reaction, agent-oil ratio and the reaction times of raw material when reaction from the regenerated catalyst of revivifier.The operational condition of present embodiment CCU, product distribute and portioned product character is seen table 10.
Embodiment 7
Test raw material adopts the generation gasoline of grand celebration long residuum catalytic cracking.Catalyzer adopts commercially available CC-20 catalytic cracking industry equilibrium catalyst, and micro-activity is 65.
Catalytic gasoline upgrading scheme is carried out on the scale fluidized bed equipment of laboratory, and reclaimable catalyst adopts tubular type to burn the back and gets in the revivifier, and micro-activity is 65.The stripping medium of settling vessel stripping stage is a water vapor, and the stripping temperature is 500 ℃.The operational condition of present embodiment CCU upgrading catalytic gasoline, product distribute and portioned product character is seen table 11.
Embodiment 8
Press embodiment 7, different is temperature of reaction, agent-oil ratio and the reaction times of raw material at reacting-settler.The operational condition of present embodiment CCU upgrading catalytic gasoline, product distribute and portioned product character is seen table 12.
Table 1 catalytic cracking heavy feedstocks character (Comparative Examples)
| The catalytic cracking charging | The grand celebration long residuum |
| Density (20 ℃), kgm -3 | 908.2 |
| Carbon residue, weight % | 4.2 |
| Group composition, weight % | |
| Stable hydrocarbon | 62.3 |
| Aromatic hydrocarbons | 25.6 |
| Colloid+bituminous matter | 12.1 |
| Sulphur content, μ gg -1 | 1180 |
| Ni，μg·g -1 | 4.3 |
| V，μg·g -1 | 0.2 |
Table 2 grand celebration catalytic gasoline character weight
Table 3 operational condition, product distribute and portioned product character
Table 4 operational condition, product distribute and portioned product character
Table 5 operational condition, product distribute and portioned product character
Table 6 operational condition, product distribute and portioned product character
Table 7 operational condition, product distribute and portioned product character
Table 8 operational condition, product distribute and portioned product character
| Project | Reactor drum |
| Raw material | The grand celebration long residuum |
| Temperature of reaction, ℃ | 530 |
| Reaction times, s | 0.2 |
| Catalyzer | Catalyzer (CC-20) |
| Raw material preheating temperature, ℃ | 220 |
| Agent-oil ratio | 19.0 |
| The reaction absolute pressure, MPa | 0.25 |
| The regenerator temperature, ℃ | 600 |
| Tubular type is burnt device and is burnt intensity, kg/ (t.h) | 820 |
| Tubular type is burnt device and is burnt the time, s | 15 |
| Tubular type is burnt device linear speed, m/s | 3.0 |
| Recycle ratio (weight ratio) | 0.24 |
| Product distributes, weight % | |
| Dry gas | 2.10 |
| Liquefied gas | 8.38 |
| Gasoline (＜180 ℃) | 49.60 |
| Diesel oil (＜360 ℃) | 33.35 |
| Coke | 6.18 |
| Loss | 0.39 |
| Add up to | 100 |
| Total liquid yield, weight % | 91.33 |
| Gasoline+diesel yield, weight % | 82.95 |
| Gasoline RON | 89.8 |
| Gasoline endpoint, ℃ | 198 |
| Diesel cetane-number | 32.5 |
Table 9 operational condition, product distribute and portioned product character
| Project | Reactor drum |
| Raw material | The grand celebration long residuum |
| Temperature of reaction, ℃ | 565 |
| Reaction times, s | 0.1 |
| Catalyzer | Catalyzer (CC-20) |
| Raw material preheating temperature, ℃ | 220 |
| Agent-oil ratio | 23.0 |
| The reaction absolute pressure, MPa | 0.25 |
| The regenerator temperature, ℃ | 630 |
| Tubular type is burnt device and is burnt intensity, kg/ (t.h) | 900 |
| Tubular type is burnt device and is burnt the time, s | 13 |
| Tubular type is burnt device linear speed, m/s | 3.4 |
| Recycle ratio (weight ratio) | 0.18 |
| Product distributes, weight % | |
| Dry gas | 3.35 |
| Liquefied gas | 14.81 |
| Gasoline (＜180 ℃) | 48.26 |
| Diesel oil (＜360 ℃) | 24.95 |
| Coke | 8.23 |
| Loss | 0.40 |
| Add up to | 100 |
| Total liquid yield, weight % | 88.02 |
| Gasoline+diesel yield, weight % | 73.21 |
| Gasoline RON | 90.5 |
| Gasoline endpoint, ℃ | 200 |
| Diesel cetane-number | 26.4 |
Table 10 operational condition, product distribute and portioned product character
| Project | Reactor drum |
| Raw material | The grand celebration long residuum |
| Temperature of reaction, ℃ | 520 |
| Reaction times, s | 0.50 |
| Catalyzer | Catalyzer (CC-20) |
| Raw material preheating temperature, ℃ | 220 |
| Agent-oil ratio | 18 |
| The reaction absolute pressure, MPa | 0.25 |
| The regenerator temperature, ℃ | 590 |
| Tubular type is burnt device and is burnt intensity, kg/ (t.h) | 930 |
| Tubular type is burnt device and is burnt the time, s | 10 |
| Tubular type is burnt device linear speed, m/s | 4.7 |
| Recycle ratio (weight ratio) | 0.19 |
| Product distributes, weight % | |
| Dry gas | 1.95 |
| Liquefied gas | 8.06 |
| Gasoline (＜180 ℃) | 49.98 |
| Diesel oil (＜360 ℃) | 32.02 |
| Coke | 7.61 |
| Loss | 0.38 |
| Add up to | 100 |
| Total liquid yield, weight % | 90.06 |
| Gasoline+diesel yield, weight % | 82.00 |
| Gasoline RON | 90.2 |
| Gasoline endpoint, ℃ | 199 |
| Diesel cetane-number | 32 |
Table 11 operational condition, product distribute and portioned product character
Table 12 operational condition, product distribute and portioned product character
Claims (13)
1. a catalyst cracking method that reduces gasoline olefin is characterised in that, step is:
1) regenerated catalyst in the revivifier (2) gets into regenerated catalyst (4) and regenerated catalyst (21) respectively; The catalyzer contact reacts of heavy oil feed (10) and regenerated catalyst (4) bottom; Reacted reclaimable catalyst separates with the cyclonic separator (12) that generation oil gas gets in the settling vessel (13); The heavy oil reaction generates oil gas (7) and gets into separation column, and isolated reclaimable catalyst gets into (3) regeneration; The catalyzer contact reacts of inferior patrol charging (26) and regenerated catalyst (21) bottom; Reclaimable catalyst behind the upgrading separates with cyclonic separator (29) with the cyclonic separator (30) that generation oil gas gets in the settling vessel (13); Isolated oil gas (24) gets into the gasoline fractionating system through oil gas collection chamber (25) and carries out fractionation, and isolated reclaimable catalyst gets into step 2);
2) behind stripped vapor (31) stripping, getting into tubular type from the stripping stage (15) of reclaimable catalyst in settling vessel (13) of step 1) burns device (20) and carries out coke burning regeneration; Cyclonic separator (19) in the half regenerated catalyzer entering revivifier (2) carries out catalyzer with cyclonic separator (1) to be separated with flue gas; Flue gas after the separation (17) is discharged; Half regenerated catalyst entering regenerated catalyst dense bed (3) after the separation is regenerated and is cooled off, and the regeneration cooled regenerated catalyst turns back to 1).
2. reduce the catalyst cracking method of gasoline olefin according to claim 1; Be characterised in that: the regenerated catalyst temperature that gets into regenerated catalyst (4) and regenerated catalyst (21) is 580～650 ℃, and the reaction times that heavy raw oil (10) contacts with regenerated catalyst is 0.1～1.0s; Temperature of reaction is 480～580 ℃, and agent-oil ratio is 5～30, and the reaction absolute pressure is 0.15～0.40MPa; The reaction times that inferior patrol contacts with regenerated catalyst is 0.1～1.0s; Temperature of reaction is 400～550 ℃, and agent-oil ratio is 5～30, and the reaction absolute pressure is 0.15～0.40MPa.
3. reduce the catalyst cracking method of gasoline olefin according to claim 1, be characterised in that: the temperature of burning that tubular type is burnt in the device is 600～720 ℃, and the air linear speed is 1.0～5m/s, and burning intensity is 300～1000kg/t.h, burns time 8～40s.
4. reduce the catalyst cracking method of gasoline olefin according to claim 1, be characterised in that: revivifier catalyzer dense bed temperature is 580～650 ℃.
5. CCU that reduces gasoline olefin; Be characterised in that: comprise that the regenerated catalyst (4) of revivifier (2), heavy oil cracking, regenerated catalyst (21), settling vessel (13) and the tubular type of catalytic gasoline upgrading burn device (20); Revivifier (2) is communicated with settling vessel (13) through the regenerated catalyst (4) of heavy oil cracking and the regenerated catalyst (21) of inferior gasoline upgrading; Metal partion (metp) (28) is isolated oil gas collection chamber (8) and oil gas collection chamber (25); Settling vessel stripping stage (15) burns device (20) with tubular type and is communicated with, and tubular type is burnt device (20) outlet and is communicated with the cyclonic separator (19) of revivifier (2).
6. according to the said a kind of CCU that reduces gasoline olefin of claim 5, be characterised in that: cyclonic separator (19), cyclonic separator (1) and distributor pipe of cardinal wind (5) are set in the revivifier (2).
7. according to the said a kind of CCU that reduces gasoline olefin of claim 5, be characterised in that: settling vessel (13) is provided with metal partion (metp) (28), collection chamber (8), collection chamber (25), cyclonic separator (9), cyclonic separator (12), cyclonic separator (29), cyclonic separator (30) and settling vessel stripping stage (15).
8. according to the said a kind of CCU that reduces gasoline olefin of claim 5, be characterised in that: tubular type is burnt device (20) and is comprised and burn wind distribution pipe (34).
9. according to the said a kind of CCU that reduces gasoline olefin of claim 5, be characterised in that: valve (6) and valve (23) are set respectively on the regenerated catalyst (21) of regenerated catalyst of heavy oil cracking (4) and catalytic gasoline upgrading.
10. according to the said a kind of CCU that reduces gasoline olefin of claim 5, be characterised in that: revivifier is positioned at the reacting-settler top.
11. according to the said a kind of CCU that reduces gasoline olefin of claim 5, be characterised in that: regenerated catalyst (21) xsect of regenerated catalyst of heavy oil cracking (4) and catalytic gasoline upgrading is for circular.
12. according to the said a kind of CCU that reduces gasoline olefin of claim 5, be characterised in that: heavy feedstocks nozzle (11) is 2～5 meters with inferior patrol feed nozzle (27) is identical with the distance of settling vessel (13) wall again.
13. according to the said a kind of CCU that reduces gasoline olefin of claim 5, be characterised in that: heavy feedstocks nozzle (11) and inferior patrol feed nozzle (27) are inequality with the distance of settling vessel (13) wall, are 2～5 meters.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585882A (en) * | 2012-03-06 | 2012-07-18 | 东北石油大学 | Novel fluid catalytic cracking (FCC) device and stripping coupling technology |
| CN104099129A (en) * | 2013-04-08 | 2014-10-15 | 中石化洛阳工程有限公司 | Short-reaction-time catalytic cracking method |
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| US6287522B1 (en) * | 1998-10-05 | 2001-09-11 | Uop Llc | FCC apparatus with dual riser |
| CN1710029A (en) * | 2005-07-01 | 2005-12-21 | 中国石油化工集团公司 | Catalytic cracking method and apparatus |
| CN102268291A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Catalytic cracking technology and device for reducing olefins in gasoline |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6287522B1 (en) * | 1998-10-05 | 2001-09-11 | Uop Llc | FCC apparatus with dual riser |
| CN1710029A (en) * | 2005-07-01 | 2005-12-21 | 中国石油化工集团公司 | Catalytic cracking method and apparatus |
| CN102268291A (en) * | 2010-06-02 | 2011-12-07 | 中国石油化工集团公司 | Catalytic cracking technology and device for reducing olefins in gasoline |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585882A (en) * | 2012-03-06 | 2012-07-18 | 东北石油大学 | Novel fluid catalytic cracking (FCC) device and stripping coupling technology |
| CN104099129A (en) * | 2013-04-08 | 2014-10-15 | 中石化洛阳工程有限公司 | Short-reaction-time catalytic cracking method |
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