CN100519704C - Catalytic cracking method for producing more propylene - Google Patents
Catalytic cracking method for producing more propylene Download PDFInfo
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- CN100519704C CN100519704C CNB2005100180880A CN200510018088A CN100519704C CN 100519704 C CN100519704 C CN 100519704C CN B2005100180880 A CNB2005100180880 A CN B2005100180880A CN 200510018088 A CN200510018088 A CN 200510018088A CN 100519704 C CN100519704 C CN 100519704C
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Abstract
A catalytic cracking process and apparatus for preparing propene with high output features that two reactors are used to implement three-stage reaction. The raw oil is catalytically cracked in the 1st reactor. The 2nd reactor is used by the circulated oil and gasoline. The gasoline comes in the reactor from its lower part, where the gasoline is in contact with catalyst and then takes part in the reaction at 550 deg.C. Said circulated oil is cracked at upper part and lower temp. When the heat provided by gasoline resultant is higher than that needed by circulated oil reaction, the part of used catalyst is tapped back into the life segment of raw oil reactor.
Description
Technical field
The invention belongs to petroleum hydrocarbon catalytic conversion technique field, particularly a kind of catalysis conversion method that can improve the catalytic cracking yield, improve quality of gasoline.
Background technology
Catalytic cracking is the important secondary processing means of oil heavy ends.Especially in China, about 80% gasoline is from catalytic cracking unit.How to improve the product yield of catalytic cracking unit, it is very important to improve product distribution and quality.Conventional catalyst cracking method use riser reactor, and turning oil inlet stock oil (atmospheric residue, decompressed wax oil, wax tailings, decompression oil expression waits the catalysis charging, down together) the riser reactor reaction.Turning oil is easy to gasification than fresh feed oil and is adsorbed by catalyzer, makes catalyst active center's inactivation very soon, has influenced the cracking of other cuts; In addition, the quality product of stock oil catalytic cracking reaction is unsatisfactory, and especially (v) %, octane value is lower mostly 45～55 for content of olefin in gasoline.
For satisfying environmental protection, and to the demand of Chemicals rapid growth, effective means is to utilize catalytic cracking unit that gasoline is transformed once more.U.S. Pat P3784463 and Chinese patent application 02116786.9,02139064.9 and 02123817.0 have proposed except that the stock oil riser tube, and other builds riser reactor, make gasoline carry out the method for catalytic conversion reaction again in independent riser tube.Its benefit is to reduce content of olefin in gasoline significantly, boosting of octane rating, or be converted into low charcoal alkene, industrial chemicals such as propylene enhancing.
In these inventions, the stock oil riser tube is conventional catalytic cracking form, and turning oil and stock oil transform together, influence the reaction effect of stock oil.
Interfere with each other problem in order to solve the reaction of stock oil, turning oil and gasoline simultaneously, Chinese patent application 0311944109,200410007518.4 has proposed to build three reactors, respectively in order to the scheme of the oil that processes raw material, turning oil and gasoline.
These inventions are obviously quite complicated, implement difficulty on the engineering.Gasoline and turning oil reaction process cause changing into more dry gas and coke because the temperature of catalyzer is too high, the loss benefit.Because generally about 350 ℃, cause the agent-oil ratio of turning oil reaction is 4～5 only generally to the turning oil temperature, is difficult to obtain the ideal reaction effect.
Gasoline reacts green coke seldom, and the catalyzer that reacted still has higher activity, can be used for the turning oil reaction, and because the temperature of the reacted catalyzer of gasoline obviously reduces, can reduce the side reaction of turning oil.
Summary of the invention
The object of the invention is to provide a kind of and makes stock oil in two reactor, the catalysis conversion method that gasoline, turning oil separately react under each adaptive environment.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
Catalytically cracked stock (atmospheric residue, decompressed wax oil, depressed heavy oil, wax tailings etc.) carries out single-pass conversion in the stock oil reactor, other establishes the catalytic conversion reaction once more that second reactor is used for gasoline and turning oils such as recycle stock, slurry oil; Gasoline and turning oil reactor are divided into two sections of gasoline reaction and turning oil reactions, carry out earlier the gasoline reaction in hypomere, and gasoline is reflected under the high temperature more than 520 ℃ and carries out, and makes the olefin(e) centent reduction of gasoline, and makes part gasoline change into low charcoal alkene such as propylene; After finishing the gasoline reaction of requirement, turning oil is introduced reactor carry out cracking reaction; Turning oil also becomes the quenching medium of gasoline reaction simultaneously, the level of response of control gasoline.
Second reactor and the shared settling vessel of stock oil reactor, reaction oil gas enters separation column after merging, and finishes post catalyst reaction and enters common regenerator regeneration from common stripping stage and regeneration standpipe, recovers active.
Second reactor outlet can be established second settling vessel and stripper, makes gasoline and turning oil reaction oil gas enter the after-fractionating tower and isolates product; Enter revivifier regeneration behind the independent stripping of reacted catalyzer.
In second reactor, the position before back, turning oil inlet are finished in gasoline reaction is drawn catalyzer and is returned gasoline admission port upstream (below), reduces the temperature of regenerator, improves the reagent oil ratio of gasoline reactive moieties, and minimizing gasoline loses.
When amount of gasoline excessive, when the heat that the reactant flow that the gasoline reaction forms provides exceeds needing of turning oil reaction, finish position before back, turning oil enter the mouth in gasoline reaction, from second reactor, draw the incoming stock oil reactor pre lift zone of catalyzer, reduce the regenerator temperature, improve the agent-oil ratio of stock oil reaction, improve the yield of stock oil reaction.
The heat that provides when the gasoline reactant flow is during less than the needing of turning oil reaction, can draw catalyzer from settling vessel or stripper and return gasoline admission port upstream (below), reduce the temperature of regenerator, improve the flow of regenerator, increase heat supplied to the turning oil conversion zone.
The gasoline conversion zone of gasoline reactor can be the riser tube pattern, also can be composited by riser tube evaporation, reaction zone and fast fluidized bed reaction zone.
In second reactor, the high temperature scheme is adopted in the gasoline reaction, produces low charcoal alkene such as propylene, and the temperature out of gasoline conversion zone is 520～600 ℃; Turning oil is reflected at 490～520 ℃ of temperature, reacts under 15～40 the high agent-oil ratio condition.
In the method for the invention, the stock oil reaction process is: in method shown in Figure 1, regenerated catalyst is through the pre lift zone part incoming stock oil reactor of regeneration standpipe below the stock oil admission port; Stock oil is incoming stock oil reactor above pre lift zone, contacts with catalyzer and up along reactor, carries out catalytic cracking reaction simultaneously; Reaction oil gas enters reacting-settler with reclaimable catalyst subsequently; After settling vessel was isolated catalyzer, oil gas entered separation column through pipeline; Isolated catalyzer in stripper by steam displace carry oil gas secretly after, return revivifier from regeneration standpipe.
In method shown in Figure 2, from second reactor, draw the incoming stock oil reactor pre lift zone of catalyzer that part gasoline reacted, reduce the temperature of regenerator, make the total catalyst levels increment that participates in reaction add 19A for 52B, increased actual agent-oil ratio.
Gasoline reaction process of the present invention is: regenerated catalyst enters the pre lift zone of second reactor through the pre lift zone of standpipe below the gasoline admission port, simultaneously before the turning oil inlet, the catalyzer that gasoline conversion zone exit was reacted part gasoline is back to this reactor pre lift zone, mix with regenerator, form about 580～640 ℃ catalyzer; Gasoline contacts with catalyzer after entering reactor, and up, carries out catalytic conversion reaction.
In method shown in Figure 3, be that second reactor is provided with the second independent settling vessel.Below the turning oil admission port, make the reacted catalyzer of part gasoline return the second reactor pre lift zone, reduce the regenerator temperature, the agent-oil ratio of gasoline reaction is provided.
When second settling vessel is set, draws the part catalyzer in second settling vessel or the stripper and be back to pre lift zone, reduce the regenerator temperature, improve the agent-oil ratio of gasoline reaction.
The present invention makes the total catalyst levels increment that participates in the gasoline reaction add 19C for 52A under the constant situation of the regeneration dosage 52A that enters the gasoline reactor and temperature of reaction, has increased actual agent-oil ratio.
Turning oil reaction process of the present invention is: the second reactor upper area as the turning oil reaction zone; The position of turning oil after the gasoline reaction is finished enters second reactor, carries out cracking reaction, and product is with the gasoline outflow reactor.It is 520～600 ℃ that the rear catalyst temperature is finished in the gasoline reaction, and the catalyst recirculation amount is bigger, can satisfy the requirement of turning oil gasification and cracking reaction, and the side reaction (thermally splitting) of turning oil cracking process obviously is suppressed.The heat of the logistics that generates when gasoline reaction makes the reacted catalyzer of part gasoline draw from the gasoline reactor before the turning oil inlet during greater than the needing of turning oil reaction, and through transfer lime charging feed oil reactor pre lift zone, continues to participate in the heavy oil reaction.When the heat of gasoline reactant flow during less than the needing of turning oil reaction, draw the pre lift zone that the part catalyzer returns second reactor from settling vessel or stripping stage, increase the regenerator flow.
Stock oil reaction conditions of the present invention is: 480～550 ℃ of temperature of reaction (reactor outlet), the mean residence time of oil gas in reactor 1.0～5 seconds is (when mainly considering liquid yield, reaction times is 1～2 second, when requiring heavy oil reaction direct production low-alkene gasoline, the reaction times is 3～5 seconds).The gasoline reaction conditions is: 520～600 ℃ of temperature of reaction, 580～640 ℃ of reaction procatalyst mixing temperatures, the mean residence time of oil gas in reactor 2～5 seconds.The reaction conditions of turning oil is: 500～520 ℃ of temperature of reaction, agent-oil ratio 15～40,520～600 ℃ of reaction procatalyst temperature, 1～3 second reaction times.
The temperature of reaction of stock oil and gasoline realizes by regeneration guiding valve control regenerator flow; The temperature of gasoline reaction procatalyst is regulated by the quantity of reflux of catalyzer; The temperature of reaction of recycle stock is by regulating from the catalytic amount of the second reactor charging feed oil reactor or from the catalytic amount that settling vessel, stripping stage reflux.
The inventive method has solved the problem that influences each other of turning oil and stock oil with two reactors, has realized that simultaneously gasoline reacts again, makes stock oil, gasoline and turning oil respectively in reactor separately, carries out catalyzed conversion by the reaction conditions of requirement separately; The reacted catalyzer of gasoline no longer directly enters revivifier, but is directly used in the turning oil reaction; Gasoline contacts temperature with turning oil low, reacts under the high agent-oil ratio condition, and side reaction is inhibited, and yield improves; The present invention can make stock oil reagent oil ratio improve 30～50%, and transformation efficiency improves 3～5 percentage points; Make gasoline reagent oil ratio improve 50～150%, content of olefin in gasoline is reduced to below 20%, and octane value increases a unit, and productivity of propylene can reach 9～10%, and the gasoline loss reduces 30%～50%; Turning oil reagent oil ratio improves 3～5 times.
Description of drawings
Fig. 1 is the double-reactor device synoptic diagram of the inventive method.
Fig. 2 is the double-reactor coupling device synoptic diagram of the inventive method.
Fig. 3 is the device synoptic diagram that the present invention establishes two settling vessels.
Fig. 4 is that gasoline conversion zone of the present invention is the second reactor synoptic diagram of fast bed.
Fig. 5 is a coupling reactor synoptic diagram of the present invention.
The numbering tag content is as follows among the figure: 1 second reactor; 11 gasoline reacting section catalysts inlet, 12 catalyst mix pre lift zones, the gasification of 13 gasoline rising pipes, reaction zone; 14 commutating zones, 14A gasoline fast bed reaction zone; 16, the reacted catalyst transport of 16-1 gasoline, 16-1A turning oil reaction back spent agent catalyst transport; 16A, the 16B guiding valve; 17 catalyzer promote medium in advance; 17-1 promotes the medium inlet in advance; 18 gasoline, 18-1 gasoline inlet; 19,19A, 19B, 19C, 52A, 52B catalyst stream; 2 heavy oil reactors; 28 heavy oil, 28-1 heavy oil inlet; 21 heavy oil reactor catalysts inlet; 22 pre lift zones; 27 catalyzer promote medium in advance, and 27-1 promotes the medium inlet in advance; 25-1 heavy oil reactor outlet pipe; 3 reacting-settlers; 31 heavy oil reactant flow gas-solid separators, 35 second reactor reaction logistics gas-solid separators, 35A separator outlet pipe, 35B dipleg; 32 oil gas pipes; 15 turning oil conversion zones, 15-1 second reactor outlet, 38 turning oils, 38-1 turning oil inlet; 4 second settling vessels, 41 cyclonic separators, 42 gas pipelines, 43 strippers; 5 catalyst stripping equipments, 51 regeneration standpipes; 7 revivifiers; 71A, the 71B standpipe of regenerating; 54A, the 54B guiding valve of regenerating; 75 air.
Embodiment
180～250 ℃ stock oil 28 is by after the nozzle atomization, through the incoming stock oil riser reactor 2 of inlet 28-1, after mixing, the catalyzer 52B that comes with carrying through regeneration standpipe 71B gasified, and it is upwards mobile along riser reactor with the flow velocity about 10m/s, under 480～550 ℃ of temperature environments, through 1.0～5s (second, down with) after the time finishes reaction, enter settling vessel 3, isolated catalyzer by gas-solid separator 31, oil gas flows out reaction unit through gas pipeline 32, enters follow-up separation column and isolates product.40～70 ℃ gasoline 18 enters the gasoline conversion zone 13 of second reactor 1 through inlet 18-1, contact with the catalyzer 19 about 580 ℃～640 ℃, limit upwards mobile limit reaction, 520～600 ℃ of temperature, after 2～5s time is finished reaction, enter turning oil conversion zone 15, be recycled the oil cooling inhibited reaction; Turning oil 38 about 350 ℃ enters reactor through inlet 38-1, and with the catalyzer 19B contact reacts from the gasoline conversion zone, reactant flow enters settling vessel 3 through outlet pipe 15-1, and separated device 35 is sent reaction unit from pipeline 32 after isolating catalyzer; Isolated catalyzer is through stripper 5, and regeneration standpipe 51 is sent into revivifier; Revivifier 7 interior contacts under 660～720 ℃ of temperature with air are regenerated; Catalyzer after the regeneration is respectively through standpipe 71A, and 71B enters two reactor bottoms, finishes circulation.
In second reactor 1, after gasoline reaction was finished, the pre lift zone 12 that catalyzer 19C that part gasoline reacted returns second reactor was drawn in the position before the turning oil inlet, and 52A mixes with regenerator, the catalyst stream 19 that formation temperature is suitable is carried out the gasoline reaction.
In second reactor 1, the heat that the reactant flow that generates when the gasoline conversion zone provides is during greater than the needing of turning oil reaction, after the gasoline reaction is finished, the catalyzer 19A charging feed oil reactor pre lift zone 22 that part gasoline reacted is drawn in position before the turning oil inlet, improves the agent-oil ratio of stock oil reaction.
When second reactor is provided with second settling vessel 4 and stripper 43, the heat that the reactant flow that generates when the gasoline conversion zone provides is during less than the needing of turning oil reaction, draw the part spent agent from this settling vessel or stripper and return the second reactor pre lift zone 12, by increasing the method for catalyst recirculation amount, increase heat capacity to the turning oil conversion zone.
Draw catalyzer from second settling vessel or stripping stage and return second reactor gasoline inlet upstream, mixes, reduce the regenerator temperature, minimizing heat cracking reaction, dose oil ratio, fortifying catalytic cracking reaction with regenerator.
The concrete application example of the present invention is as follows:
Embodiment.Reaction raw materials oil is: the defeated atmospheric residue of pipe, and 100t/h heavy oil, gasoline feeding are that heavy oil reacts self-produced gasoline, 40t/h makes the gasoline propylene enhancing; Turning oil is recycle stock 15t/h, 350 ℃ of temperature; 220 ℃ of heavy oil preheatings, 40 ℃ in gasoline; The gasoline conversion zone of second reactor is the fast fluidized bed form, oil gas flow velocity 4m/s; Second reactor is provided with second settling vessel and stripper; The turning oil conversion zone is the riser tube pattern; The stock oil reactor is the riser tube form; Reaction product in the stock oil and second reactor separately, the separation column that enters separately through separately gas pipeline carries out product separation.505 ℃ of stock oil temperature of reaction, reaction times 1.5s, 545 ℃ of gasoline temperature of reaction, reaction times 2.8s; 610 ℃ of the mixing temperatures of the second reactor pre lift zone inner catalyst; 505 ℃ of turning oil temperature of reaction, reaction times 1.6s; 700 ℃ of regeneration temperatures.Use conventional catalytic cracking catalyst.
Reaction-the regenerating unit that uses in the present embodiment is seen Fig. 3.
Comparative Examples: adopt existing independently double lifting leg, two settling vessels, two separation column technology.Stock oil reactive moieties and present embodiment do not exist together, the incoming stock oil riser reaction of recycle stock.What the gasoline reactive moieties was different with present embodiment is, from the high temperature catalyst of revivifier directly and the gasoline contact reacts, the reacted catalyzer of gasoline enters revivifier separately.
Product contrast reaction result provides in table 1.As can be seen, under identical reaction conditions, liquid product yield of the present invention has increased by 1.8 percentage points, generates gasoline olefin and reduces by 3 percentage points, and productivity of propylene is identical, and coke and dry gas yied descend 1 percentage point.
Table 1, embodiment scheme and prior art contrast
Claims (9)
1, a kind of catalytic cracking of petroleum hydrocarbon reaction method, it is characterized in that, catalytic cracking fresh feed oil carries out single-pass conversion in the stock oil reactor, other establishes the catalytic conversion reaction once more that second reactor is used for gasoline and turning oil, second reactor is divided into the gasoline reaction and turning oil reacts two sections, in hypomere, carry out earlier the gasoline reaction, the olefin(e) centent of gasoline is reduced, and make part gasoline change into low charcoal alkene, after finishing the gasoline reaction of requirement, turning oil is introduced reactor carry out cracking reaction, turning oil also becomes the quenching medium of gasoline reaction, the level of response of control gasoline; Turning oil is recycle stock or slurry oil.
2, the method for claim 1 is characterized in that, the temperature out of gasoline conversion zone is 520～600 ℃; Turning oil reacts under 15～40 the agent-oil ratio condition 490～520 ℃ of temperature.
3, the method for claim 1, it is characterized in that, second reactor and the shared settling vessel of stock oil reactor, reaction oil gas enters same separation column after merging, finish reacted catalyzer and enter common regenerator regeneration, recover active from common stripping stage, regeneration standpipe.
4, method as claimed in claim 3 is characterized in that, the reactant flow of two reactors merges in settling vessel, or directly merges at reactor outlet.
5, the method for claim 1 is characterized in that, second reactor outlet is established second settling vessel and stripper, and the reaction oil gas of formation enters the after-fractionating tower from pipeline independently and carries out product separation; Enter common regenerator regeneration behind the independent stripping of reacted catalyzer.
6, the method for claim 1 is characterized in that, in second reactor, the position before back, turning oil inlet are finished in gasoline reaction is drawn catalyzer and returned gasoline admission port upstream, the temperature of reduction regenerator, the reagent oil ratio of raising gasoline reactive moieties.
7, the method for claim 1, it is characterized in that, in second reactor, when the heat that provides when the gasoline reactant flow exceeds needing of turning oil reaction, draw the incoming stock oil reactor pre lift zone of catalyzer in the position that gasoline reaction is finished before back, turning oil enter the mouth, reduce the regenerator temperature, improve the agent-oil ratio of fresh feed oil reaction.
8, method as claimed in claim 5 is characterized in that, draws catalyzer from second settling vessel or stripper and returns gasoline admission port upstream, reduces the temperature of regenerator, improves the reagent oil ratio of second reactor internal reaction part.
9, the method for claim 1 is characterized in that, the gasoline conversion zone of second reactor is composited by riser tube evaporation, reaction zone and fast fluidized bed reaction zone.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100180880A CN100519704C (en) | 2005-10-12 | 2005-10-12 | Catalytic cracking method for producing more propylene |
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| CNB2005100180880A CN100519704C (en) | 2005-10-12 | 2005-10-12 | Catalytic cracking method for producing more propylene |
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| CN100519704C true CN100519704C (en) | 2009-07-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286972A (en) * | 2017-07-21 | 2017-10-24 | 石宝珍 | A kind of catalysis conversion method of producing more propylene |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101104815B (en) * | 2007-07-13 | 2010-12-15 | 中国石油化工集团公司 | Upgrading method and device for gasoline |
| CN110240932B (en) * | 2018-05-29 | 2020-07-21 | 石宝珍 | Petroleum hydrocarbon multistage fluidized catalytic reaction method and reactor |
| CN110724562B (en) * | 2018-07-16 | 2021-05-14 | 中国石油化工股份有限公司 | Catalytic cracking method and system for producing propylene and high-octane gasoline |
| CN110724552B (en) * | 2018-07-16 | 2021-05-14 | 中国石油化工股份有限公司 | Method and system for catalytic cracking by adopting fast fluidized bed and turbulent fluidized bed |
| CN110724554B (en) * | 2018-07-16 | 2021-03-16 | 中国石油化工股份有限公司 | Method and system for catalytic cracking by adopting fast fluidized bed and dilute phase transport bed |
| CN110724559B (en) * | 2018-07-16 | 2021-05-18 | 中国石油化工股份有限公司 | Catalytic cracking method and system for producing propylene and high-octane gasoline |
| CN110724553B (en) * | 2018-07-16 | 2021-04-06 | 中国石油化工股份有限公司 | Method and system for catalytic cracking by adopting dilute phase conveying bed and rapid fluidized bed |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107286972A (en) * | 2017-07-21 | 2017-10-24 | 石宝珍 | A kind of catalysis conversion method of producing more propylene |
| CN107286972B (en) * | 2017-07-21 | 2019-11-22 | 石宝珍 | A kind of catalysis conversion method of producing more propylene |
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