CN102399579B - Catalytic cracking method - Google Patents
Catalytic cracking method Download PDFInfo
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- CN102399579B CN102399579B CN201110311147.9A CN201110311147A CN102399579B CN 102399579 B CN102399579 B CN 102399579B CN 201110311147 A CN201110311147 A CN 201110311147A CN 102399579 B CN102399579 B CN 102399579B
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Abstract
The invention discloses a catalytic cracking method, and belongs to the technical field of petrochemical engineering. A main reactor and an auxiliary reactor are adopted in the method, wherein the main reactor comprises a lower lift pipe reaction zone and an upper diameter expanded second reaction zone; in the main reactor, the reaction raw oil is in contact with a regenerated catalyst in the lift pipe reaction zone to produce cracking reaction, a part of catalyst is separated from the generated oil gas and catalyst reactant flow at the outlet of the lift pipe reaction zone, and the oil gas and the rest catalyst rise together and undergo gasoline modification reaction in the diameter expanded second reaction zone; and a part of catalyst to be generated in the auxiliary reactor is supplied to the second reaction zone to participate in the gasoline modification reaction. In the method, a part of catalyst inactivated due to coking is separated at the outlet of the lift pipe reaction zone of the main reactor, so that the catalytic activity and the reaction selectivity of the whole main reactor are reinforced; and control on the flow and the activity of the catalyst of the second reaction zone is integrally realized, and the production target of producing more gasoline with low olefins and high octane value is realized.
Description
Technical field
The present invention relates to petrochemical technology field, particularly relate to a kind of petroleum hydrocarbon raw material catalyst cracking method and device.
Background technology
Catalytic cracking unit is topmost gasoline production device, and world's overwhelming majority motor spirit is from catalytic cracking unit, and conventional catalytic cracking adopts riser reactor.
The diameter of existing riser reactor is uniform, carrying out along with catalyzed reaction, more small molecules generate, molecule expands and to make in riser tube flow velocity vertically upward sharply increase, be unfavorable for improving the carrying out of the alkene secondary reaction that quality product distributes, the Perfected process addressing this problem is to carry out hole enlargement in the middle and upper part of the riser reaction zone of homogeneous diameter, makes alkene have the longer time to participate in secondary reaction.
CN99105903.4 discloses a kind of riser reactor for fluidized catalytic conversion, vertically be followed successively by from bottom to up coaxial each other pre lift zone, the first reaction zone, enlarged-diameter second reaction zone, reduced ， outlet area, outlet area end be connected with one section of level pipe.In this technology, the first reaction zone of bottom is a pyrolysis reaction zone, temperature of reaction is higher, residence time of material is shorter, and the temperature of reaction of the second reaction zone on top reduces, residence time of material is longer, and material carries out alkylated reaction and hydrogen transfer reactions, improves the content of isoparaffin in gasoline composition; CN01102240.X discloses a kind of catalysis conversion method of producing low-alkene gasoline and high-yield diesel oil, stock oil and hot regenerated catalyst are contacted in the first reaction zone of reactor macromole cracking reaction occurs, and the oil gas of generation and band Pd/carbon catalyst go upward to second reaction zone and carry out cracking reaction, hydrogen transfer reactions and isomerization reaction; In engineering design, second reaction zone is thicker than the first reaction zone, and its effect is flow velocity and the temperature of reaction that reduces oil gas and catalyzer.
Above-mentioned technology is the MIP technique of Research Institute of Petro-Chemical Engineering exploitation, and full scale plant operation result shows, this Technology can significantly reduce the olefin(e) centent in gasoline, and product liquid is received to be increased, coke selectivity grow, and dry gas and slurry oil productive rate decline.
But due to the enlarged-diameter of riser tube second reaction zone, second reaction zone fluid velocity sharply reduces, need to supplement to second reaction zone partially catalyzed agent to regulate, to maintain the air speed needing.For addressing the above problem, in existing design, Research Institute of Petro-Chemical Engineering adopts and to second reaction zone, fills into reclaimable catalyst from settling vessel on the engineering construction of MIP technique, its concrete device design has detailed introduction in " industrial application of the catalytic cracking process of maximizing iso-paraffins " literary composition of < < refining of petroleum and chemical industry > > the 34th volume o. 11th 1-6 page in 2003: adopt MIP technique to transform Gaoqiao Petrochemical Company branch office refinery 1.4Mt/a catalytic cracking unit, riser tube integral replacing, riser tube bottom is as the first reaction zone, at riser tube middle part, increased an extension diameter section as second reaction zone, settling vessel integral raising 2m wherein, at settling vessel stripping stage upper cone section, overflow downcomer is set, overflow downcomer is provided with on sedimentation wall extracts mouth out, is communicated with, thereby the part reclaimable catalyst in settling vessel is introduced to second reaction zone by circulate pipeline to be generated and bottom, second reaction zone.
With regard to having solved second reaction zone, maintain like this problem of air speed, but existing MIP second reaction zone is reclaimable catalyst, supplementary catalyzer is also spent agent, and activity is very low, and katalysis is very limited; Although so Shi Ke institute requires make-up catalyst (the normal restriction air speed 15 ~ 20 that requires), design also has tonic measure, tonic not substantially in a lot of device operations; The value that air speed also requires far above exploitation side, temperature of reaction can not reduce a lot, and result can cause green coke to increase, and the thermopositive reaction that gasoline upgrading exists is also suppressed.
Summary of the invention
On the basis of above-mentioned catalyst cracking method, the object of the present invention is to provide a kind of petroleum hydrocarbon raw material catalyst cracking method and device, the needs that change flexibly to adapt to market, realize the target that Intensified catalytic cracking process is produced clean gasoline.
The technical solution used in the present invention is as follows:
A catalyst cracking method, arranges main reactor and auxiliary reactor, and main reactor comprises the riser reaction zone of bottom and the second reaction zone that upper diameter expands; In main reactor, reaction raw materials oil contacts with regenerated catalyst in riser reaction zone cracking reaction occurs, the oil gas generating and catalyst reaction logistics export and isolate a part of catalyzer in riser reaction zone, oil gas is up together with residual catalyst, gasoline upgrading reaction is carried out in second reaction zone in enlarged-diameter, it is characterized in that:
(1) the reclaimable catalyst that supplements a part of auxiliary reactor to second reaction zone participates in gasoline upgrading reaction; Supplementary reclaimable catalyst or draw from auxiliary reactor middle part, or draw after separated and stripping from auxiliary reactor outlet, supplementary catalyst temperature is below 550 ℃; Described second reaction zone is fast fluidized bed, and gas phase flow velocity is 1.2-5.0m/s;
(2) between riser reaction zone and second reaction zone, grid distributor is set, grid distributor is provided with opening or passage; In riser reaction zone, outlet is provided with catalyzer splitter, and outside, riser reaction zone coaxially arranges catalyst stripping section, and second reaction zone is arranged on stripping stage top;
(3) the catalyzer that participates in main reactor reaction divides two-way to enter main reaction part, first via catalyzer is the direct regenerated catalyst from revivifier or the regenerated catalyst after cooling, regenerated catalyst is introduced into the pre lift zone of raw material oil spray nozzle bottom, riser reaction zone, with reaction raw materials contact reacts, after having reacted, in catalyzer splitter, isolate a part of catalyzer, the catalyzer of not shunted upwards enters second reaction zone by grid distributor together with reaction oil gas; The second road catalyzer is described supplementary reclaimable catalyst, and the second tunnel catalyst make-up enters second reaction zone, after mixing, carries out upgrading reaction with above-mentioned catalyzer and reaction oil gas logistics.
Further, the reclaimable catalyst of two reaction zones of main reactor reactive moieties shares a stripping stage, and the catalyzer after stripping enters revivifier regeneration through standpipe.
Further, the reacted reclaimable catalyst in second reaction zone partly returns in second reaction zone, and part reclaimable catalyst is circulated in second reaction zone, increases the catalyzer agent-oil ratio of second reaction zone or reduces reaction velocity.
Further, the 0-80% of the reclaimable catalyst after the cracking reaction of described riser reaction zone enters second reaction zone and participates in upgrading reaction.
Further, riser reaction zone reaction conditions is, 500 ℃-620 ℃ of temperature of reaction, and reaction times 0.2-1.6s, oil gas mean flow rate is 5.0 ~ 26m/s; Second reaction zone reaction conditions is, 450 ℃-510 ℃ of temperature of reaction, and reaction times 2.0-5.0s, oil gas mean flow rate is 1.2-4.0m/s, preferably 3.0-3.5m/s.
Further, auxiliary reactor is riser reactor, and reaction raw materials is C
4one or more of the lighter hydrocarbons that component, catalytic gasoline, coker gasoline, petroleum naphtha are such; Auxiliary reactor and main reactor share a settling vessel.
Further, described second reaction zone diameter is 1.5-4.9 times of riser reaction zone diameter, and preferably 2.0-3.5 doubly.
In the inventive method, the reclaimable catalyst of employing auxiliary reactor carries out the displacement of second reaction zone catalyzer, supplements, and auxiliary reactor is realized C simultaneously
4dual-use function Deng hydrocarbon raw material cracking and catalyst transport; The reaction raw materials of auxiliary reactor can, for the light constituent in main reactor cracked product of the present invention, also can install from other.
The present invention provides a kind of catalytic cracking unit simultaneously, comprises main reactor, auxiliary reactor, settling vessel, stripping stage, revivifier and catalyst make-up pipeline, it is characterized in that:
(1) main reactor is provided with the second reaction zone of riser reaction zone, enlarged-diameter from bottom to top, and riser reaction zone outlet arranges catalyzer splitter; Stripping stage is coaxially arranged at outside, riser reaction zone, and second reaction zone is arranged on stripping stage top;
(2) main reactor, auxiliary reactor share settling vessel and stripping stage, and catalyzer return line is set between settling vessel, stripping stage, and guiding valve is set on return line;
(3) between riser reaction zone and second reaction zone, grid distributor is set, grid distributor is provided with a plurality of openings or passage;
(4) auxiliary reactor is riser reactor, its middle part is provided with reclaimable catalyst outlet, described catalyst make-up pipeline upper end is communicated with catalyzer outlet, and lower end is communicated with second reaction zone, for supplement the reclaimable catalyst of auxiliary reactor to second reaction zone.
Further, described second reaction zone diameter is 1.5-4.9 times of riser reaction zone diameter, and preferably 2.0-3.5 doubly.
Further, auxiliary reactor and main reactor share oil gas vent or auxiliary reactor oil gas vent are set separately.
In the present invention, by control enters the amount of the riser reaction zone reclaimable catalyst of second reaction zone, to second reaction zone, the amount of the reclaimable catalyst of supplementary auxiliary reactor is controlled second reaction zone air speed and catalyst activity.
In the solution of the present invention, auxiliary reactor raw material is light, catalyst deactivation is slow, catalyzer at main reactor riser reaction zone outlet cutting out partial because of coking inactivation, in second reaction zone, supplement the reclaimable catalyst of the greater activity of auxiliary reactor, can be according to the active appropriate change reaction conditions of catalyzer in engineering construction, as: suitably improve air speed, reduce temperature of reaction (at least reducing by 10 ℃), reduce the oil gas reaction times; Or suitably improve the structure of main reactor, as: adopt grid distributor to reduce catalyzer back-mixing.
Adopt technical scheme of the present invention, at least there is following beneficial effect:
(1) due to what supplement to second reaction zone, be highly active reclaimable catalyst, catalytic activity and reaction preference in whole main reactor have been strengthened generally, effectively suppressed thermal response, can make slurry oil in reactor product reduce 1.0-2.0%, react the increase of total liquid receipts more than 1.0%;
(2) the reclaimable catalyst of riser reaction zone first carried out catalyzer shunting before entering second reaction zone, thereby control the reclaimable catalyst and the supplementary reclaimable catalyst ratio that enters second reaction zone that enter second reaction zone, realize on the whole the control to second reaction zone catalyst flow and catalyst activity, realize the productive target of voluminous low alkene stop bracket gasoline;
(3) adopt and by the suitable hole enlargement in second reaction zone, to second reaction zone, supplement high activated catalyst, before catalyzer enters second reaction zone, first shunt, the measure such as mixing, strengthened the isomerization reaction of second reaction zone, realize the target of voluminous low alkene stop bracket gasoline, reduced the sulphur content in gasoline simultaneously.
Accompanying drawing explanation
Fig. 1 is catalyst cracking method apparatus structure schematic diagram of the present invention.
Number description: 11 riser reaction zone; 12 second reaction zone; 13,51 feed nozzles; 14 grid distributors; 15 catalyst make-up pipelines; 16 pre lift zones; 18 catalyzer splitters; 20 settling vessels; 21 catalyzer return lines; 22 stripping stages; 23,25 oil gas vents; 24 regeneration standpipes; 30 revivifiers; 31 exhanst gas outlets; 32,33 standpipes; 34 heat collectors; 50 auxiliary riser line reactors; 52 catalyzer outlets.
Embodiment
Below in conjunction with accompanying drawing, describe technical scheme of the present invention in detail, but protection scope of the present invention includes, but are not limited to this:
Fig. 1 is catalyst cracking method apparatus structure schematic diagram of the present invention, and catalytic cracking unit comprises main reactor, auxiliary riser line reactor 50, settling vessel 20, stripping stage 22, revivifier 30 and catalyst make-up pipeline 15; Main reactor, auxiliary riser line reactor 50 share settling vessel 20, and oil gas vent 23 and 25 are set separately respectively; Main reactor comprises pre lift zone 16, riser reaction zone 11, catalyzer splitter 18, grid distributor 14 and the second reaction zone 12 arranging from bottom to top, second reaction zone 12 diameters are 1.5-4.9 times of riser reaction zone 11 diameters, and grid distributor 14 is provided with a plurality of openings; Stripping stage 22 is coaxially arranged at 11 outsides, riser reaction zone, and second reaction zone 12 is arranged on stripping stage 22 tops, shares stripping stage 22 with riser reaction zone 11; Between settling vessel 20 and stripping stage 22, by catalyzer return line 21, be communicated with, on return line 21, be provided with guiding valve; Auxiliary riser line reactor 50 middle parts are provided with reclaimable catalyst outlet 52, and catalyst make-up pipeline 15 upper ends are communicated with catalyzer outlet 50, and lower end is communicated with second reaction zone 12; Main reactor, auxiliary riser line reactor 50 are respectively arranged with feed nozzle 13 and 51; Between stripping stage 22 and revivifier 30, be provided with regeneration standpipe 24, main reactor, auxiliary riser line reactor 50 and 30 of revivifiers are respectively equipped with standpipe 32 and 33; Revivifier 30 is provided with exhanst gas outlet 31 and heat collector 34; Stripping stage 22, grid distributor 14 is interior all according to requirement of engineering, corresponding gas distributor is set.
The technical process of this catalyst cracking method is as follows:
In main reactor, regenerated catalyst from revivifier 30 enters in the pre lift zone 16 of main reactor along standpipe 32, under the lifting of pre-lift steam, enter riser reaction zone 11, the stock oil contact reacts spraying into from feed nozzle 13 with preheating, reaction mixture upwards flows in splitter 18 along main reactor, isolated catalyzer directly enters in stripping stage 22 downwards, all the other catalyzer and reaction oil gas evenly upwards enter in second reaction zone 12 through grid distributor 14, contact mixing with the reclaimable catalyst of the auxiliary riser line reactor 50 of introducing through catalyst make-up pipeline 15, carry out gasoline upgrading reaction, reaction finishes, and oil gas and catalyzer enter settling vessel 20 and carry out separatedly, and oil gas enters fractionating system through oil gas vent 23, and catalyzer enters stripping stage 22 along catalyzer return line 21 to carry out stripping and return to revivifier 30 regeneration by regeneration standpipe 24,
In auxiliary riser line reactor, regenerated catalyst from revivifier 30 enters auxiliary riser line reactor 50 bottoms along standpipe 33, the light hydrocarbon feedstocks spraying into from feed nozzle 51 oil contact reacts with preheating, at auxiliary riser line reactor 50 middle parts, part reclaimable catalyst is drawn through catalyst make-up pipeline 15 and is supplemented and in the second reaction zone 12 that enters main reactor, participate in upgrading reaction through catalyzer outlet 52, all the other catalyzer and reaction oil gas continue along the up reaction of reactor 50, reaction finishes, oil gas enters settling vessel 20 with catalyzer and carries out separated, oil gas enters fractionating system through oil gas vent 25, catalyzer enters stripping stage 22 along catalyzer return line 21 to carry out stripping and returns to revivifier 30 regeneration by regeneration standpipe 24.
Embodiment:
1,000,000 tons/year of gasoline upgrading catalytic cracking unit of certain refinery, comprise main reactor and subsidiary riser, two reactors share settling vessel, main reactor pre lift zone diameter 1.1m, height 5m, riser reaction zone diameter 1.4m, high 20.4m, second reaction zone diameter 4.0m, high 19.5m, stripping stage and riser reaction zone coaxially arrange, and diameter 4.2m is highly 8.9m; Subsidiary riser diameter 0.8m, subsidiary riser arranges separately oil gas vent, and oil gas separates and carries out subsequent disposal with main reactor oil gas; The reclaimable catalyst of riser reaction zone has 22% to enter second reaction zone, and the reclaimable catalyst carbon content of second reaction zone is controlled at 0.5%; 520 ℃ of riser reaction zone temperature of reaction, reaction times 0.6s; 490 ℃ of second reaction zone temperature of reaction, reaction times 3.2s; The reclaimable catalyst that adds to second reaction zone accounts for 65% of second reaction zone total catalyst internal circulating load; In bottom, second reaction zone, spray into part quenched water.
In the present embodiment, main reactor adopts distillate to mix refining 12% vacuum residuum; Subsidiary riser adopts C
4lighter hydrocarbons charging, 63% is main reactor product component, rest part installs from other.
Result shows, adopts identical reaction raw materials and reaction conditions, compares with existing heavy oil list riser reactor, and in main reactor product gasoline, olefin(e) centent is down to below 26%, and MON increases by 1.2, and sulphur content reduces.
It should be noted last that: above explanation is only unrestricted in order to the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiments, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement the present invention, and not departing from the spirit and scope of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (7)
1. a catalyst cracking method, arranges main reactor and auxiliary reactor, and main reactor comprises the riser reaction zone of bottom and the second reaction zone that upper diameter expands; In main reactor, reaction raw materials oil contacts with regenerated catalyst in riser reaction zone cracking reaction occurs, the oil gas generating and catalyst reaction logistics export and isolate a part of catalyzer in riser reaction zone, oil gas is up together with residual catalyst, gasoline upgrading reaction is carried out in second reaction zone in enlarged-diameter, it is characterized in that:
(1) the reclaimable catalyst that supplements a part of auxiliary reactor to second reaction zone participates in gasoline upgrading reaction; Supplementary reclaimable catalyst or draw from auxiliary reactor middle part, or draw after separated and stripping from auxiliary reactor outlet, supplementary catalyst temperature is below 550 ℃; Described second reaction zone is fast fluidized bed, and gas phase flow velocity is 1.2-5.0m/s;
(2) between riser reaction zone and second reaction zone, grid distributor is set, grid distributor is provided with opening or passage; In riser reaction zone, outlet is provided with catalyzer splitter, and outside, riser reaction zone coaxially arranges catalyst stripping section, and second reaction zone is arranged on stripping stage top;
(3) the catalyzer that participates in main reactor reaction divides two-way to enter main reaction part, first via catalyzer is the direct regenerated catalyst from revivifier or the regenerated catalyst after cooling, regenerated catalyst is introduced into the pre lift zone of raw material oil spray nozzle bottom, riser reaction zone, with reaction raw materials contact reacts, after having reacted, in catalyzer splitter, isolate a part of catalyzer, the catalyzer of not shunted upwards enters second reaction zone by grid distributor together with reaction oil gas; The second road catalyzer is described supplementary reclaimable catalyst, and the second tunnel catalyst make-up enters second reaction zone, after mixing, carries out upgrading reaction with above-mentioned catalyzer and reaction oil gas logistics.
2. catalyst cracking method according to claim 1, is characterized in that: the reclaimable catalyst of two reaction zones of main reactor reactive moieties shares a stripping stage, and the catalyzer after stripping enters revivifier regeneration through standpipe.
3. catalyst cracking method according to claim 1, it is characterized in that: the reacted reclaimable catalyst in second reaction zone partly returns in second reaction zone, part reclaimable catalyst is circulated in second reaction zone, increase the catalyzer agent-oil ratio of second reaction zone or reduce reaction velocity.
4. catalyst cracking method according to claim 1, is characterized in that: the 0-80% of the reclaimable catalyst after the cracking reaction of described riser reaction zone enters second reaction zone and participates in upgrading reaction.
5. catalyst cracking method according to claim 1, is characterized in that: riser reaction zone reaction conditions is, 500 ℃-620 ℃ of temperature of reaction, and reaction times 0.2-1.6s, oil gas mean flow rate is 5.0 ~ 26m/s; Second reaction zone reaction conditions is, 450 ℃-510 ℃ of temperature of reaction, and reaction times 2.0-5.0s, oil gas mean flow rate is 1.2-4.0m/s.
6. catalyst cracking method according to claim 1, is characterized in that: auxiliary reactor is riser reactor, and reaction raw materials is C
4one or more of the lighter hydrocarbons that component, catalytic gasoline, coker gasoline, petroleum naphtha are such; Auxiliary reactor and main reactor share a settling vessel.
7. realize catalyst cracking method claimed in claim 1, it is characterized in that: described second reaction zone diameter is 1.5-4.9 times of riser reaction zone diameter.
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| CN110240932B (en) * | 2018-05-29 | 2020-07-21 | 石宝珍 | Petroleum hydrocarbon multistage fluidized catalytic reaction method and reactor |
| CN113926396B (en) * | 2020-07-13 | 2022-12-13 | 中国石油化工股份有限公司 | Heavy oil catalytic conversion reactor and method for preparing propylene by heavy oil catalytic cracking |
| CN113926390B (en) * | 2020-07-13 | 2022-12-13 | 中国石油化工股份有限公司 | Catalytic conversion reactor, catalytic conversion device and method for preparing propylene by catalytic cracking of heavy oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1046696A2 (en) * | 1999-04-23 | 2000-10-25 | China Petrochemical Corporation | A catalytic conversion process for producing isobutane and isoparaffin-enriched gasoline |
| CN201901660U (en) * | 2010-12-02 | 2011-07-20 | 石宝珍 | Catalytic cracking unit |
| CN201962247U (en) * | 2011-01-27 | 2011-09-07 | 青岛京润石化设计研究院有限公司 | Catalytic cracking device |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1046696A2 (en) * | 1999-04-23 | 2000-10-25 | China Petrochemical Corporation | A catalytic conversion process for producing isobutane and isoparaffin-enriched gasoline |
| CN201901660U (en) * | 2010-12-02 | 2011-07-20 | 石宝珍 | Catalytic cracking unit |
| CN201962247U (en) * | 2011-01-27 | 2011-09-07 | 青岛京润石化设计研究院有限公司 | Catalytic cracking device |
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