CN102311767B - Gasoline olefin reducing catalytic cracking method and device - Google Patents
Gasoline olefin reducing catalytic cracking method and device Download PDFInfo
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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 in the situation that not there is not 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 catalytic cracking unit:
First, regenerator temperature cannot realize flexible control, the regeneration temperature of catalyzer is generally all higher than 650 DEG C, make in riser reactor finish moment Contact Temperature higher, too high finish Contact Temperature can aggravate heat cracking reaction, reduce the degree of catalytic cracking reaction, result is that product distribution worsens, dry gas and coke yield rise, total liquid yield declines, and (total liquid yield refers to liquefied gas yield, gasoline yield and diesel yield sum), due to higher regenerated catalyst temperature, limited by device thermal equilibrium, make the agent-oil ratio of heavy oil riser reactor relatively little, be generally 5～8.
The second, owing to promoting the length of tubular reactor and determined the reaction times (generally in 4s left and right) of raw material.The long reaction times has also been aggravated the secondary reaction of raw material cracking resultant in improving raw material per pass conversion, make reacted gas gain in yield, thereby has reduced the yield of vapour, diesel oil distillate.
The 3rd, because the oil gas linear speed promoting in tubular reactor causes the landing of coked catalyst to form back-mixing higher than catalyzer linear speed, thus, promoting tubular type reactor feedstocks nozzle top, the catalyzer of coking landing contacts with initial stage cracking resultant again with atomized feed, thereby worsen product distribution, reduced the product selectivity of catalyzer to raw material cracking.
The 4th, catalytic cracking occupies extremely important status as the Main Means of oil secondary processing in China.Due to technique 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 catalytic cracking unit 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 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 for reducing content of olefin in gasoline, Research Institute of Petro-Chemical Engineering of China Petrochemical Industry has developed the GOR catalyst series (" refining of petroleum and chemical industry " 2002 7 phases 5th～8 pages) that reduces catalytic gasoline olefin(e) centent, this catalyzer is by introducing y-type zeolite and the modification ZRP zeolite of oxide surface modification, there is very high hydrogen transfer activity and higher isomerization activity, can make FCC gasoline olefin reduce by 10 percentage points of left and right.Refining institute of Luoyang Petrochemical engineering corporation of China Petrochemical Industry has developed the LAP series auxiliary agent (23rd～27 pages of " oil refining design " 9 phases of calendar year 2001) that reduces catalytic gasoline olefin(e) centent, this auxiliary agent is selected shape zeolite as main active component taking poly-metal deoxide modification, there is very high gasoline olefin aromatization activity and higher cracking of olefins activity, while adding 5% LAP auxiliary agent in catalyzer, can make FCC gasoline olefin reduce by 10 percentage points of left and right.In processing method, Research Institute of Petro-Chemical Engineering of China Petrochemical Industry has developed has the MGD technique (" refining of petroleum and chemical industry " 2002 2 phase 19th～22 pages) that reduces content of olefin in gasoline function, MGD technique is divided into two sections main conventional FCC riser reactor, hypomere is as gasoline upgrading reaction zone, epimere is as the main riser reaction zone of FCC, utilize high agent-oil ratio and high activated catalyst reformulated gasoline, this technique will be taken into account the reaction conditions of main riser tube heavy oil fluid catalytic cracking, the amount of gasoline upgrading is limited, it is also not ideal that alkene amplitude is fallen, can make FCC gasoline olefin reduce by 10～12 percentage points.
The 5th, due to revivifier carbon-burning capacity and to burn efficiency relatively low, make that the size of revivifier is large 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 (be equivalent to regenerator activity 90%), low temperature (500 DEG C of left and right) after lighter hydrocarbons riser tube reaction is partly or entirely returned to the mixing tank that heavy oil riser tube bottom arranges, after mixing with from the regenerated catalyst of revivifier, enter heavy oil riser tube and heavy oil contact reacts in mixing tank.Because making the temperature of mixed catalyst, the heat exchange action of two strands of catalyzer in mixing tank effectively drops to 630 DEG C of left and right, enter 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, liquid yield improves, and product distributes and improves.Catalytic gasoline is through lighter hydrocarbons riser tube upgrading, and after upgrading, content of olefin in gasoline is down to 10～25v%, 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 there is following some deficiency in this technology: 1. regenerator temperature cannot realize flexible control, and this technical superiority is only embodied in the catalytic cracking unit of more than two riser tube.2. because this technology is traditional lifting tubular type catalytic cracking, still shown that long reaction time, dry gas and coke yield are relatively high, product distribution relative mistake, revivifier carbon-burning capacity is low and plant energy consumption is high deficiency.When catalytic gasoline upgrading and regenerated catalyst Contact Temperature high, and long reaction time causes the dry gas of device and coke yield further to increase, reformulated gasoline yield reduces.
The related high efficiency regenerating technology for molecular sieve catalyst technology of Chinese patent ZL97106088.6 mainly comprises: 1. reclaimable catalyst enters external cyclone water-separator group after the first root regeneration pipe regeneration, enters the second root regeneration pipe through dipleg.2. the second root regeneration pipe external cyclone water-separator group dipleg directly enters external warmer, and through bottom, inclined tube enters riser reactor.Technology was burnt the time in 10 seconds, and the coke burning degree burning carbon amount of catalyzer per ton (per hour) is 10 times of left and right of prior art.But also there are following 2 deficiencies in this technology: 1. employing promotes tubular reactor and cannot realize the raw material short reaction time.2. technological process and complicated operation, be difficult to carry out in engineering.3. this technology does not relate to catalytic gasoline upgrading.
The related a kind of catalyst cracking lift tube burning regenerator technical characterstic of Chinese patent ZL93242428.7 is: riser regenerator is provided with multistage air inlet and carries out reclaimable catalyst regeneration, strengthen the coke burning regeneration process of reclaimable catalyst, it is simple in structure, easy to operate.But there is lifting tubular reactor and cannot realize raw material short reaction time operation in this technology.This technology does not relate to catalytic gasoline upgrading yet.
The related technology features of US Patent No. P:5462652 is: 1. reacting-settler top arranges catalyst mix tank, and mixing tank adopts water vapor to carry out the even mixing of catalyzer; Reacting-settler top arranges mixed catalyst chamber, and catalyzer enters reacting-settler by mixed catalyst chamber central opening.Catalyzer and raw material react and the stripping of reclaimable catalyst all carries out in reacting-settler, the catalyzer direction that flows is downward, the raw material injection direction of nozzle and the catalyzer direction angle in 90 ° that flows, the plug-in cyclonic separator of reacting-settler.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 catalyst mix tank by second air-lift tube, and the catalyzer after regeneration is promoted to catalyst mix tank by the 3rd air-lift tube and mixes to reduce the mixed catalyst temperature that enters reacting-settler with reclaimable catalyst.Due to above feature, US Patent No. P:5462652 technology realizes the raw material short reaction time in reacting-settler, low finish Contact Temperature, and high agent-oil ratio operation, declines the dry gas of device, coke yield, and liquid yield improves, and product distributes and improves.But still there is following some deficiency in this technology: 1. adopt conventional catalytic cracking regenerator, its carbon-burning capacity is low.2. the catalyzer that participates in reaction is catalyzer after regeneration and the mixture of reclaimable catalyst, and this mixed catalyst must be affected to the cracking activity of raw material, also certainly will distribute and bring disadvantageous effect product.3. technological process and complicated operation.4. this technique does not relate to 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 and improve regeneration carbon-burning capacity and burn efficiency, reduce total dry gas (even comprising liquefied gas) and coke yield and improve reformulated gasoline yield the product that improves catalytic cracking reaction is distributed and product property, reduce plant energy consumption, reduce the catalyst inventory of revivifier, dwindle revivifier size, reduce facility investment and there is important effect.
Summary of the invention
Technical problem to be solved by this invention is that the Contact Temperature of the control flexibly of the catalyst temperature of existing catalytic cracking process in revivifier, regenerated catalyst and raw material is high, long reaction time, agent-oil ratio are low and device carbon-burning capacity is low etc.
The object of this invention is to provide a kind of catalyst cracking method and device that reduces gasoline olefin, in catalytic cracking unit, implement reclaimable catalyst tubular type coke burning regeneration and control the regenerated catalyst temperature (between 580～650 DEG C) of revivifier, heavy oil fluid catalytic cracking and catalytic gasoline upgrading are separate and all adopt low finish Contact Temperature, the short reaction time between 0.1～1.0s, under high agent-oil ratio condition, operate, reach and reduce reacted gas and coke yield, improve gasoline and diesel oil distillate yield, reduce the olefin(e) centent of catalytic gasoline, improve the object 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 revivifier 2 enters respectively regenerated catalyst 4 and regenerated catalyst 21, 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 enters in settling vessel 13, heavy oil reaction generates oil gas 7 and enters separation column, and isolated reclaimable catalyst enters 3 regeneration; The catalyzer contact reacts of inferior patrol charging 26 and regenerated catalyst 21 bottoms, reclaimable catalyst after upgrading separates with cyclonic separator 29 with the cyclonic separator 30 that generation oil gas enters in settling vessel 13, isolated oil gas 24 enters gasoline fractionating system through oil gas collection chamber 25 and carries out fractionation, and isolated reclaimable catalyst enters step 2);
2) from step 1) reclaimable catalyst after stripped vapor 31 strippings, enter tubular type at the stripping stage 15 of settling vessel 13 and burn device 20 and carry out coke burning regeneration, the catalyzer of half regeneration enters cyclonic separator 19 in revivifier 2 to carry out catalyzer with cyclonic separator 1 and separates with flue gas, flue gas 17 after separation is discharged, half regenerated catalyst after separation enters regenerated catalyst dense bed 3 and regenerates with cooling, and the cooled regenerated catalyst of regenerating 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 enters regenerated catalyst 4 and regenerated catalyst 21 is 580～650 DEG C, the reaction times that heavy raw oil 10 contacts with regenerated catalyst is 0.1～1.0s; Temperature of reaction is 480～580 DEG C, and agent-oil ratio is 5～30, and 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 DEG C, and agent-oil ratio is 5～30, and 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 device is 600～720 DEG C, and air linear speed is 1.0～5m/s, and coke burning degree 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 DEG C.
The present invention also provides a kind of catalytic cracking unit that reduces gasoline olefin, be characterised in that: comprise revivifier 2, the regenerated catalyst 4 of heavy oil cracking, the regenerated catalyst 21 of catalytic gasoline upgrading, settling vessel 13 and tubular type are burnt device 20, revivifier 2 is communicated with settling vessel 13 by 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, tubular type is burnt device 20 outlets and is communicated with the cyclonic separator 19 of revivifier 2.
Described a kind of catalytic cracking unit that reduces gasoline olefin, is characterised in that: interior cyclonic separator 19, cyclonic separator 1 and the distributor pipe of cardinal wind 5 of arranging of revivifier 2.
Described a kind of catalytic cracking unit that reduces gasoline olefin, is characterised in that: settling vessel 13 arranges 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.
Described a kind of catalytic cracking unit that reduces gasoline olefin, is characterised in that: tubular type is burnt device 20 and comprised and burn wind distribution pipe 34.
Described a kind of catalytic cracking unit that reduces gasoline olefin, is characterised in that: in the regenerated catalyst 4 of heavy oil cracking and the regenerated catalyst 21 of catalytic gasoline upgrading, control valve 6 and control valve 23 are set respectively.
Described a kind of catalytic cracking unit that reduces gasoline olefin, is characterised in that: revivifier is positioned at reacting-settler top.
Described a kind of catalytic cracking unit that reduces gasoline olefin, is characterised in that: regenerated catalyst 21 cross sections of the regenerated catalyst 4 of heavy oil cracking and catalytic gasoline upgrading are for circular.
Described a kind of catalytic cracking unit that reduces gasoline olefin, is characterised in that: heavy feedstocks nozzle 11 is identical or different from 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 of inferior gasoline upgrading 21 liner insulated linings, Φ 200～3000mm.
The catalyst cracking method that the present invention is a kind of reduces gasoline olefin compared with prior art, has following beneficial effect:
1. burn in device in tubular type, Air for burning coke flow can be adjusted flexibly, and the reclaimable catalyst amount of unit time enters tubular type and burns device bottom and contact and strengthened the carbon-burning capacity that tubular type is burnt device with enough, the rich oxygen containing fresh air that burns all the time, make tubular type burn device coke burning degree and increase, improved the efficiency of burning that tubular type is burnt device.Tubular type burn device can burning-off reclaimable catalyst on 70～80% coke.Tubular type is burnt device, and to burn temperature be that 600～720 DEG C, air linear speed are 1.0～5m/s, burn time 8～40s; It is 300～1000kg/ (t.h) that tubular type is burnt the device coke burning degree burning carbon amount of catalyzer per ton (per hour), and tubular type is burnt device and have stronger carbon-burning capacity and turndown ratio more flexibly compared with conventional catalytic cracking unit regeneration.
2. the finish Contact Temperature of heavy oil fluid catalytic cracking and catalytic gasoline upgrading is high can aggravate the heat cracking reaction of raw material, the degree of reduction catalytic cracking reaction, result is that product distribution worsens, and dry gas and coke yield rise, total liquid yield declines (total liquid yield refers to liquefied gas yield, gasoline yield and diesel yield sum).Adopt the cooling regenerated catalyst technology of revivifier main air, can effectively control regenerated catalyst temperature between 580～650 DEG C, thereby reduce the Contact Temperature of regenerated catalyst and raw material, reach the dry gas, the coke yield that reduce device, improve liquid yield, improve product and distribute, improve the object of the economic benefit of refinery.
3. in heavy feed stock catalytic cracking process, the longer reaction times has also been aggravated the secondary reaction of raw material cracking resultant in improving raw material per pass conversion, makes reacted gas gain in yield, thereby has reduced the yield of vapour, diesel oil distillate; High agent-oil ratio operation can make up the raw material per pass conversion dampening factor bringing due 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, the yield of vapour, diesel oil distillate is increased, improved the utilization ratio of petroleum resources.
4. when catalytic gasoline carries 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 are low, and reformulated gasoline yield is high.The present invention due to heavy oil fluid catalytic cracking and catalytic gasoline upgrading and fractionation separate, through the catalytic gasoline of upgrading, content of olefin in gasoline can be down to 10～25v%, can dispatch from the factory as gasoline products separately, the blend component that also can be used as gasoline products meets state's III oil quality that China carries out now and requires the olefin(e) centent of gasoline to be not more than the gasoline products of 35v% for being in harmonious proportion.Gasoline octane rating (RON) after upgrading improves 0.1～1.5 unit; Content of sulfur in gasoline reduces by 15～35%.
5. device dry gas, coke yield decline, and can make the Energy Intensity Reduction of device.Tubular type is burnt the device coke burning degree burning carbon amount of catalyzer per ton (per hour) and can reduce greatly the catalyst inventory of revivifier, and the size of revivifier is dwindled, and plant investment declines.
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.
Inferior gasoline upgrading reactive system is mainly applicable to the catalytic gasoline of self or other devices, also can upgrading coker gasoline, the inferior patrol such as straight-run spirit.
Below in conjunction with accompanying drawing, embodiment and embodiment, the present invention is further detailed explanation.But do not limit the scope of protection of present invention.
Brief description of the drawings
Accompanying drawing 1 is a kind of catalytic cracking unit schematic diagram that reduces gasoline olefin of the present invention.
1. cyclonic separator, 2. revivifier, 3. regenerated catalyst dense bed, 4. the regenerated catalyst of heavy oil cracking, 5. distributor pipe of cardinal wind, 6. the regenerated catalyst flowrate control valve of heavy oil cracking, 7. heavy oil cracking reaction generates oil gas, 8. heavy oil cracking reaction generates oil gas collection chamber, 9. cyclonic separator, 10. heavy raw oil, 11. heavy feed stock oil burner nozzles, 13. settling vessels, 14. reclaimable catalyst dense beds, 15. settling vessel stripping stages, 16. inclined tubes to be generated, 17. flue gases, 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 airs, 23. catalytic gasoline upgradings regenerated catalyst flowrate control valve, the reaction of 24. catalytic gasoline upgradings generates oil gas, 25. catalytic gasoline upgrading reactions generate oil gas collection chamber, 26. catalytic gasoline chargings, 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, 34. burn wind distribution pipe.
Embodiment
A kind of catalytic cracking unit of producing low-alkene gasoline of the present invention as shown in drawings, this device comprises that revivifier 2, settling vessel 13, tubular type burn device 20 three parts compositions.Press the flow process of device inner catalyst, be provided with successively the regenerated catalyst 4 of revivifier 2, heavy oil cracking, the regenerated catalyst 21 of catalytic gasoline upgrading, 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 by the regenerated catalyst 4 of heavy oil cracking and the regenerated catalyst 21 of catalytic gasoline upgrading, in the regenerated catalyst 4 of the heavy oil cracking between revivifier 2 and settling vessel 13, the regenerated catalyst 21 of catalytic gasoline upgrading, regenerated catalyst flowrate control valve 6 and 23 is set respectively, the bottom of settling vessel 13 is 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 arrange 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 the cyclonic separator 19 in revivifier 2.The dipleg of cyclonic separator 19 enters in regenerated catalyst dense bed 3.
Described revivifier 2 comprises cyclonic separator 1, cyclonic separator 19, and its size and structure are determined the general feature that meets conventional lifting tubular type For Fcc Regenerator.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 cross section, liner insulating and wearing-resistant lining, internal diameter is Φ 200～2000mm, and its diameter is determined according to the stream pipe method of calculation of flooding in routine list or double lifting leg formula For Fcc Regenerator.
Described regenerated catalyst flowrate control valve 6 and 23 is located at respectively in the regenerated catalyst 21 of regenerated catalyst 4, catalytic gasoline upgrading of the heavy oil cracking being connected between revivifier 2 and settling vessel 13, can adopt various conventional flowrate control valves (as adopted guiding valve), to regulate regenerated catalyst flow, realize temperature of reaction control.
The entrance 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, regenerated catalyst dense bed 3 belows, interface, its set-up mode can be determined with reference to the stream pipe that floods in conventional For Fcc Regenerator.The outlet of the regenerated catalyst 4 of heavy oil cracking, the regenerated catalyst 21 of catalytic gasoline upgrading is entered with settling vessel 13 and is connected by the side wall 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 are determined the general calculated characteristics that meets conventional lifting tubular type catalytic cracking unit 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 on settling vessel 13 diameters by metal partion (metp) 28.
Heavy feedstocks nozzle 11 in described settling vessel 13 and catalytic gasoline feed nozzle 27 Way outs point to and enter the regenerated catalyst Way out of settling vessel and arrange 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 catalytic cracking unit feed nozzle.
Described inclined tube to be generated 16, it is circular metal tube that pipeline adopts cross section, liner insulating and wearing-resistant lining, internal diameter is Φ 300～2000mm, its diameter promotes tubular type catalytic cracking unit inclined tube method of calculation to be generated according to routine and determines.Reclaimable catalyst flowrate control valve 32 is located on inclined tube 16 to be generated, can adopt various conventional flowrate control valves (as adopted guiding valve), to regulate reclaimable catalyst flow.
Described tubular type is burnt device 20, and to adopt cross section be circular metal tube, liner insulating and wearing-resistant lining, and length is 20～40M, Φ 400～2500mm; Tubular type is burnt device 20 bottoms settings and is burnt wind distribution pipe 34, and the distribution pipe method of calculation that its size promotes tubular type catalytic cracking unit according to routine are determined.The concrete diameter that tubular type is burnt device 20 determines 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 determined 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 as follows as shown in drawings: the regenerated catalyst in revivifier 2 divides two-way to enter regenerated catalyst 4 and 21 downwards, in regenerated catalyst 4 and 21 bottoms and the heavy oil feed 10 and catalytic gasoline charging 26 contact reactss that enter through heavy oil feed nozzle 11 and catalytic gasoline feed nozzle 27.The reacted reclaimable catalyst of heavy oil feed 10 separates with 9 with the cyclonic separator 12 that generation oil gas enters in settling vessel; Reclaimable catalyst after catalytic gasoline charging 26 upgradings separates with 29 with the cyclonic separator 30 that generation oil gas enters in settling vessel.Heavy oil reaction generation oil gas 7 after separation stripping and stripped vapor enter independently fractionating system through oil gas collection chamber 8 and carry out fractionation.The fractionating system that catalytic gasoline upgrading generation oil gas 24 enters self through oil gas collection chamber 25 is carried out fractionation.Isolated reclaimable catalyst enters tubular type by 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 up reclaimable catalyst coke burning regeneration that carries out of device 20 along tubular type after water vapor 31 strippings.Burning half regenerated catalyst after device 20 regeneration by tubular type enters cyclonic separator 19 and 1 in revivifier 2 and carries out catalyzer and separate with flue gas.Half regenerated catalyst after separation enters in the catalyzer dense bed 3 of revivifier 2 through the dipleg of cyclonic separator 19 and 1, main air 22 enters revivifier 2 bottom by distribution pipe 5 contacts residual coke the cooling regenerated catalyst on burning-off half regenerated catalyst with half regenerated catalyst, regeneration rear catalyst enters two root regeneration catalyst transports and recycles.The flue gas 17 generating is discharged revivifier 2 through cyclonic separator 1 by regenerated flue gas collection chamber 18.Above-mentioned operating process continuous circulation carries out.
The present invention adopt tubular type burn and revivifier main air cooling, can effectively control regenerated catalyst temperature, thereby reduce the Contact Temperature 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, improve liquid yield, improve product and distribute and quality product, improve the economic benefit of refinery; Adopt the short reaction time, high agent-oil ratio operation has reduced the secondary reaction in raw material cracking and catalytic gasoline upgrading process, and reacted gas (comprising dry gas and liquefied gas) productive rate is declined, and the yield of vapour, diesel oil distillate is increased; Adopt tubular type to burn device and improved the carbon-burning capacity of device and burnt efficiency, reduced the catalyst inventory of revivifier, dwindled the size of revivifier, appliance arrangement investment is declined.Device dry gas, coke yield decline, and make the Energy Intensity Reduction of device.
The interior regenerated catalyst temperature of described revivifier 2 is 580～650 DEG C, and definitely regeneration pressure is 0.15～0.40MPa, the catalyzer residence time 3～6min.Other operating parameterss meet the general feature of conventional For Fcc Regenerator.
The main air 22 of described revivifier 2 is pressurized air, the Main Function of this main air 22 is temperature of the catalyzer dense bed 3 of residual coke on burning-off half regenerated catalyst cooling revivifier 2, reaches catalyzer dense bed 3 temperature of controlling revivifier 2 the object of 580～650 DEG C.The air quantity of main air 22 is determined by heat calculation according to the catalyst inventory of revivifier 2 and control target temperature.
Described heavy raw oil 10 cracking operational conditions are: temperature of reaction is 480～580 DEG C, preferably 500～560 DEG C, is preferably 530～550 DEG C; Heavy raw oil 10 is 0.1～1.0s by feed nozzle 11 with the reaction times contacting of regenerated catalyst, and preferably 0.05～0.5s, is preferably 0.1～0.3s; Agent-oil ratio is 5～30, and the heat calculation of agent-oil ratio when reacting determined; Reaction absolute pressure is 0.15～0.40MPa;
Described catalytic gasoline 26 upgrading operational conditions are: temperature of reaction is 400～550 DEG C, preferably 420～530 DEG C, are preferably 450～500 DEG C; Catalytic gasoline raw material 26 is 0.01～1.0s by catalytic gasoline feed nozzle 27 with the reaction times contacting of regenerated catalyst, and preferably 0.05～0.5s, is preferably 0.1～0.3s; Agent-oil ratio is 5～30, and the heat calculation of agent-oil ratio when reacting determined; Reaction absolute pressure is 0.15～0.40MPa;
The stripping condition of the stripping stage 15 of described settling vessel 13 is also conventional, and stripping medium is water vapor, and stripping temperature is 480～520 DEG C.
Described reclaimable catalyst burns device 20 bottoms and burns that wind 33 contacts and burn on the up burning-off reclaimable catalyst of device 20 70～80% coke along tubular type in tubular type.Tubular type is burnt device 20, and to burn temperature be 600～720 DEG C, the air linear speed that tubular type is burnt device 20 is 1.0～5m/s, it is 300～1000kg/ (t.h) that tubular type is burnt the device coke burning degree burning carbon amount of catalyzer per ton (per hour), burns time 8～40s.Burn wind 33 for pressurized air, this pressurized air meets the compressed-air actuated general feature of conventional catalytic cracking unit, and its flow can be multiplied by the required air quantity calculating in the time burning of unit weight coke according to total green coke amount of raw material unit time to be determined.
Described heavy raw oil 10 and catalytic gasoline raw material 26 meet the conventional ingredient requirement that promotes tubular type catalytic cracking unit.
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 according to concrete operations situation.
Comparative example and embodiment
Comparative example 1
Test raw material adopts Daqing atmospheric residue, and catalyzer adopts commercially available CC-20 catalytic cracking industry equilibrium catalyst, and micro-activity is 65.Catalytic cracking heavy oil is tested on catalytic cracking riser pilot plant.Pilot plant riser reactor is simulated full freshening operation, and the regeneration temperature of revivifier inner catalyst is 700 DEG C, and the carbon content of regenerated catalyst is 0.03w%, and micro-activity is 65.The stripping medium of reacting-settler stripping stage is water vapor, and stripping temperature is 500 DEG C.
Catalytic cracking heavy feedstocks character is in table 1, and the operational condition of catalytic cracking reaction, product distribute in table 3.Comparative example 2
Test raw material adopts the generation gasoline of Daqing atmospheric residue catalytic cracking.Catalyzer adopts commercially available CC-20 catalytic cracking industry equilibrium catalyst, and micro-activity is 65.Catalytic gasoline upgrading is tested on catalytic cracking riser pilot plant, and the regeneration temperature of revivifier inner catalyst is 700 DEG C, and the carbon content of regenerated catalyst is 0.03w%, and micro-activity is 65.The stripping medium of reacting-settler stripping stage is water vapor, and stripping temperature is 500 DEG C.Catalytic gasoline upgrading feedstock property is in table 2, and catalytic gasoline upgraded condition, product distribution and some properties are in table 4.
Embodiment 1
Test raw material adopts Daqing atmospheric residue, and catalyzer adopts commercially available CC-20 catalytic cracking industry equilibrium catalyst, and micro-activity is 65.
Catalytic cracking scheme is carried out on laboratory room small-sized fluidizer, and reclaimable catalyst enters in revivifier after adopting tubular type to burn, and micro-activity is 65.The stripping medium of settling vessel stripping stage is water vapor, and stripping temperature is 500 DEG C.The present embodiment catalytic cracking unit adopts full freshening operating operation condition, product distribution and portioned product character in table 5.
Embodiment 2
Press embodiment 1, difference is from the temperature of reaction of the temperature of the regenerated catalyst of revivifier, raw material, agent-oil ratio and reaction times.Operational condition, product distribution and the portioned product character of the present embodiment catalytic cracking unit are in table 6.
Embodiment 3
Press embodiment 1, difference is from the temperature of the regenerated catalyst of revivifier, agent-oil ratio and the reaction times of raw material in the time reacting.Operational condition, product distribution and the portioned product character of the present embodiment catalytic cracking unit are in table 7.
Embodiment 4
Press embodiment 1, difference is from the temperature of the regenerated catalyst of revivifier, agent-oil ratio and the reaction times of raw material in the time reacting.Operational condition, product distribution and the portioned product character of the present embodiment catalytic cracking unit are in table 8.
Embodiment 5
Press embodiment 1, difference is from the temperature of the regenerated catalyst of revivifier, temperature of reaction, agent-oil ratio and the reaction times of raw material in the time reacting.Operational condition, product distribution and the portioned product character of the present embodiment catalytic cracking unit are in table 9.
Embodiment 6
Press embodiment 1, difference is from the temperature of the regenerated catalyst of revivifier, temperature of reaction, agent-oil ratio and the reaction times of raw material in the time reacting.Operational condition, product distribution and the portioned product character of the present embodiment catalytic cracking unit are in table 10.
Embodiment 7
Test raw material adopts the generation gasoline of Daqing atmospheric residue 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 laboratory room small-sized fluidizer, and reclaimable catalyst enters in revivifier after adopting tubular type to burn, and micro-activity is 65.The stripping medium of settling vessel stripping stage is water vapor, and stripping temperature is 500 DEG C.Operational condition, product distribution and the portioned product character of the present embodiment catalytic cracking unit upgrading catalytic gasoline are in table 11.
Embodiment 8
Press embodiment 7, difference is temperature of reaction, agent-oil ratio and the reaction times of raw material at reacting-settler.Operational condition, product distribution and the portioned product character of the present embodiment catalytic cracking unit upgrading catalytic gasoline are in table 12.
Table 1 catalytic cracking heavy feedstocks character (comparative example)
| Catalytic cracking charging | Daqing atmospheric residue |
| Density (20 DEG C), kgm -3 | 908.2 |
| Carbon residue, % by weight | 4.2 |
| Group composition, % by 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 |
| Raw material | Daqing atmospheric residue |
| Temperature of reaction, DEG C | 530 |
| Reaction times, s | 0.2 |
| Catalyzer | Catalyzer (CC-20) |
| Raw material preheating temperature, DEG C | 220 |
| Agent-oil ratio | 19.0 |
| Reaction absolute pressure, MPa | 0.25 |
| Regenerator temperature, DEG C | 600 |
| Tubular type is burnt device coke burning degree, 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, % by weight | |
| Dry gas | 2.10 |
| Liquefied gas | 8.38 |
| Gasoline (180 DEG C of <) | 49.60 |
| Diesel oil (360 DEG C of <) | 33.35 |
| Coke | 6.18 |
| Loss | 0.39 |
| Add up to | 100 |
| Total liquid yield, % by weight | 91.33 |
| Gasoline+diesel yield, % by weight | 82.95 |
| Gasoline RON | 89.8 |
| Gasoline endpoint, DEG C | 198 |
| Diesel cetane-number | 32.5 |
Table 9 operational condition, product distribute and portioned product character
| Project | Reactor |
| Raw material | Daqing atmospheric residue |
| Temperature of reaction, DEG C | 565 |
| Reaction times, s | 0.1 |
| Catalyzer | Catalyzer (CC-20) |
| Raw material preheating temperature, DEG C | 220 |
| Agent-oil ratio | 23.0 |
| Reaction absolute pressure, MPa | 0.25 |
| Regenerator temperature, DEG C | 630 |
| Tubular type is burnt device coke burning degree, 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, % by weight | |
| Dry gas | 3.35 |
| Liquefied gas | 14.81 |
| Gasoline (180 DEG C of <) | 48.26 |
| Diesel oil (360 DEG C of <) | 24.95 |
| Coke | 8.23 |
| Loss | 0.40 |
| Add up to | 100 |
| Total liquid yield, % by weight | 88.02 |
| Gasoline+diesel yield, % by weight | 73.21 |
| Gasoline RON | 90.5 |
| Gasoline endpoint, DEG C | 200 |
| Diesel cetane-number | 26.4 |
Table 10 operational condition, product distribute and portioned product character
| Project | Reactor |
| Raw material | Daqing atmospheric residue |
| Temperature of reaction, DEG C | 520 |
| Reaction times, s | 0.50 |
| Catalyzer | Catalyzer (CC-20) |
| Raw material preheating temperature, DEG C | 220 |
| Agent-oil ratio | 18 |
| Reaction absolute pressure, MPa | 0.25 |
| Regenerator temperature, DEG C | 590 |
| Tubular type is burnt device coke burning degree, 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, % by weight | |
| Dry gas | 1.95 |
| Liquefied gas | 8.06 |
| Gasoline (180 DEG C of <) | 49.98 |
| Diesel oil (360 DEG C of <) | 32.02 |
| Coke | 7.61 |
| Loss | 0.38 |
| Add up to | 100 |
| Total liquid yield, % by weight | 90.06 |
| Gasoline+diesel yield, % by weight | 82.00 |
| Gasoline RON | 90.2 |
| Gasoline endpoint, DEG C | 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 (12)
1. a catalyst cracking method that reduces gasoline olefin, is characterised in that, step is:
1) regenerated catalyst in revivifier (2) enters respectively the regenerated catalyst (4) of heavy oil cracking and the regenerated catalyst (21) of catalytic gasoline upgrading, the catalyzer contact reacts of regenerated catalyst (4) bottom of heavy oil feed (10) and heavy oil cracking, reacted reclaimable catalyst separates with the 4th sedimentation cyclonic separator (12) that generation oil gas enters in settling vessel (13), heavy oil reaction generates oil gas (7) and enters separation column through heavy oil cracking reaction generation oil gas collection chamber (8), isolated reclaimable catalyst enters the regenerated catalyst dense bed (3) of revivifier (2) and regenerates, the catalyzer contact reacts of regenerated catalyst (21) bottom of the catalytic gasoline upgrading of inferior patrol charging (26) and catalytic gasoline upgrading, reclaimable catalyst after upgrading separates with the second sedimentation cyclonic separator (29) with the first sedimentation cyclonic separator (30) that generation oil gas enters in settling vessel (13), isolated oil gas (24) enters gasoline fractionating system through catalytic gasoline upgrading reaction generation oil gas collection chamber (25) and carries out fractionation, and isolated reclaimable catalyst enters step 2),
2) from step 1) reclaimable catalyst after stripped vapor (31) stripping, enter tubular type at the stripping stage (15) of settling vessel (13) and burn device (20) and carry out coke burning regeneration, the catalyzer of half regeneration enters the first regenerator cyclones (19) in revivifier (2) to carry out catalyzer with the second regenerator cyclones (1) and separates with flue gas, flue gas (17) after separation is discharged, half regenerated catalyst after separation enters regenerated catalyst dense bed (3) temperature and is 580～650 DEG C and regenerates and cooling, the cooled regenerated catalyst of regenerating 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 enters the regenerated catalyst (4) of heavy oil cracking and the regenerated catalyst (21) of catalytic gasoline upgrading is 580～650 DEG C, and the reaction times that heavy oil feed (10) contacts with regenerated catalyst is 0.1～1.0s; Temperature of reaction is 480～580 DEG C, and agent-oil ratio is 5～30, and 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 DEG C, and agent-oil ratio is 5～30, and reaction absolute pressure is 0.15～0.40MPa.
3. the catalyst cracking method that reduces gasoline olefin according to claim 1, is characterised in that: the temperature of burning that tubular type is burnt in device is 600～720 DEG C, and air linear speed is 1.0～5m/s, and coke burning degree is 300～1000kg/t.h, burns time 8～40s.
4. one kind is reduced the catalytic cracking unit of gasoline olefin, be characterised in that: comprise revivifier (2), the regenerated catalyst (4) of heavy oil cracking, the regenerated catalyst (21) of catalytic gasoline upgrading, settling vessel (13) and tubular type are burnt device (20), revivifier (2) is communicated with settling vessel (13) by the regenerated catalyst (4) of heavy oil cracking and the regenerated catalyst (21) of gasoline upgrading, heavy oil cracking reaction is generated to oil gas collection chamber (8) with metal partion (metp) (28) and the reaction of catalytic gasoline upgrading generates oil gas collection chamber (25) isolation, settling vessel stripping stage (15) burns device (20) with tubular type and is communicated with, tubular type is burnt device (20) outlet and is communicated with the cyclonic separator (19) of revivifier (2).
5. according to a kind of catalytic cracking unit that reduces gasoline olefin described in claim 4, be characterised in that: the first regenerator cyclones (19), the second regenerator cyclones (1) and distributor pipe of cardinal wind (5) are set in revivifier (2).
6. according to a kind of catalytic cracking unit that reduces gasoline olefin described in claim 4, be characterised in that: settling vessel (13) arranges metal partion (metp) (28), heavy oil cracking reaction generates oil gas collection chamber (8), catalytic gasoline upgrading reaction spanning set air chamber (25), the 3rd sedimentation cyclonic separator (9), the 4th sedimentation cyclonic separator (12), the second sedimentation cyclonic separator (29), the first sedimentation cyclonic separator (30) and settling vessel stripping stage (15).
7. according to a kind of catalytic cracking unit that reduces gasoline olefin described in claim 4, be characterised in that: tubular type is burnt device (20) and comprised and burn wind distribution pipe (34).
8. according to a kind of catalytic cracking unit that reduces gasoline olefin described in claim 4, be characterised in that: the regenerated catalyst (4) of heavy oil cracking arranges control valve (6), the regenerated catalyst (21) of gasoline upgrading arranges control valve (23).
9. according to a kind of catalytic cracking unit that reduces gasoline olefin described in claim 4, be characterised in that: revivifier is positioned at reacting-settler top.
10. according to a kind of catalytic cracking unit that reduces gasoline olefin described in claim 4, be characterised in that: regenerated catalyst (21) cross section of the regenerated catalyst (4) of heavy oil cracking and gasoline upgrading is for circular.
11. according to a kind of catalytic cracking unit that reduces gasoline olefin described in claim 4, be characterised in that: heavy feedstocks nozzle (11) is identical with the distance of settling vessel (13) wall with inferior patrol feed nozzle (27), is 2～5 meters.
12. according to a kind of catalytic cracking unit that reduces gasoline olefin described in claim 4, be characterised in that: heavy feedstocks nozzle (11) and inferior patrol feed nozzle (27) are not identical with the distance of settling vessel (13) wall, are 2～5 meters.
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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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| 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 |
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