CN1888026B - Gasoline catalytic converting method and reactor - Google Patents
Gasoline catalytic converting method and reactor Download PDFInfo
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- CN1888026B CN1888026B CN2005100177464A CN200510017746A CN1888026B CN 1888026 B CN1888026 B CN 1888026B CN 2005100177464 A CN2005100177464 A CN 2005100177464A CN 200510017746 A CN200510017746 A CN 200510017746A CN 1888026 B CN1888026 B CN 1888026B
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Abstract
The gasoline catalytically re-converting method and reactor belongs to the field of petroleum refining technology. Before the catalyst and reacted oil-gas flow is discharged from the reactor, partial catalyst is led out, returned through the reflux pipe to the bottom of the gasoline reactor and mixed with regenerated catalyst to lower the temperature of the regenerated catalyst, so that inferior gasoline is made to contact with low temperature and high activity catalyst in high catalyst/oil ratio and for relatively long time for catalytically converting to modify or to convert into low carbon olefin. The modifying section of the reactor may be a convenient riser, a fluidized bed or their combination. The present invention can lower the content of olefin in gasoline to below 20 % and eliminate sulfur of 70 %.
Description
Technical field
The invention belongs to the petroleum refining technology field, particularly a kind of to gasoline carry out again catalyzed conversion with improve quality method and reactor.
Background technology
About 85% from catalytic cracking unit in the Chinese commodity gasoline.The catalytically cracked gasoline quality is unsatisfactory, and general olefin(e) centent is that 45% (v)-60% (v), sulphur content is also higher.Be rich in the gasoline poor heat stability of alkene, influence combustion in IC engine, make hydrocarbon polymer, carbon monoxide emission increase contaminate environment.Environmental objective is in the requirement gasoline component, and (v), sulphur content is less than 100ppm 25% for olefin(e) centent.This has proposed stern challenge to China's oil refining apparatus.In addition, making limited petroleum resources produce Chemicals such as more low-carbon alkene as much as possible, is the new requirement that catalytic cracking unit is proposed.
In order to reduce content of olefin in gasoline in catalytic cracking unit, or produce more low-carbon alkene product, efficient ways is to build special gasoline conversion reactor on catalytic cracking unit, makes gasoline secondary response again, changes into the product of requirement.
U.S. Pat P3,784,463 have proposed to set up a riser reactor on conventional catalytic cracking unit, are specifically designed to the method for gasoline reaction.Gasoline rising pipe and the original shared revivifier of stock oil riser tube, the gasoline rising pipe form is identical with conventional stock oil riser reactor, can realize the requirement of low-carbon olefines high-output.The proposition of Chinese patent application 02139064.9,02116786.9 similar scheme, on former catalytic cracking unit, build in addition a riser reactor, make gasoline enter this riser tube and carry out catalyzed conversion.
More than in the invention,, make gasoline change into unnecessary dry gas and coke because regenerated catalyst temperature higher (about 700 ℃) during with the gasoline contact reacts, side reactions such as thermally splitting takes place.Simultaneously since the reaction heat of gasoline reaction needed seldom, and gasoline needs lower temperature of reaction, causes in the reaction process agent-oil ratio lower, has a strong impact on reaction result.
Chinese patent application 00102981.9 provides reduction regenerator method of temperature, and major measure has two: provide catalyzer from external warmer to gasoline rising pipe; Revivifier is designed to two-stage regeneration with two containers, and the catalyzer that enters gasoline rising pipe is half a lower regenerated catalyst of temperature.This method can only be implemented on the catalytic cracking unit of specific two-stage regeneration form, and its reactor still is conventional riser tube.
The settling vessel that Chinese patent application 03126213.9 has proposed to utilize former catalytic cracking unit makes the scheme of gasoline catalyzed conversion in fluidized-bed as the reactor that gasoline transforms.This scheme utilized the low temperature catalyst reaction, solved the high and cracking problem of crossing that causes of catalyst temperature, but gasoline is transformed under SA spent agent environment, and efficient is lower.
The gasoline characteristics of reaction process again is that the reaction heat process mainly is a heat of gasification, needs heat less; Conversion of olefines, desulfurization needs the long reaction times; React green coke seldom, catalyst carbon deposition is less, still has higher activity.Therefore the gasoline reaction needed was carried out under than the demulcent condition in lower temperature, high solvent-oil ratio, long residence time etc.
Summary of the invention
The object of the invention is to provide a kind of and can implements on any catalytic cracking unit, and does not need the gasoline catalytically converting method and the reactor of the gasoline conversion reaction conditions that heat exchange can realize ideal.
For reaching above-mentioned purpose, the present invention adopts following technical scheme: a kind of gasoline catalytically converting method, the part catalyzer is drawn from reactor top, and the catalyzer return line between the material section of drawing by being connected in reactor top and the catalyst mix section of reactor bottom directly is back to reactor bottom and uses with the catalyst mix from revivifier.
Catalyst temperature before contacting with gasoline stocks is 450-650 ℃, and the mass flux ratio of reaction zone catalyzer and gas material is 6-15, and temperature of reaction is 380-530 ℃, the mean residence time 3-10 second of gas in reactor.
Temperature of reaction is 380-500 ℃, and the mean residence time of gas in reactor is 3-10 second.
Temperature of reaction is 450-530 ℃, and the mean residence time of gas in reactor is 3-6 second.
A kind of gasoline is catalytic conversion reactor again, form by the catalyst mix section, fuel evaporation section, upgrading conversion zone, the material section of drawing that connect from bottom to top, the catalyst mix section is provided with regenerated catalyst inlet and lift gas inlet, the fuel evaporation section is provided with the gasoline inlet, be provided with the catalyzer return line between catalyst mix section and the material section of drawing, the material section of drawing is provided with fairlead.
Upgrading conversion zone enlarged-diameter is 2-4 a times of fuel evaporation section.
The material section of drawing enlarged-diameter is 1.5-3 a times of fuel evaporation section, and catalyzer return line upper end is connected with this part.
The material section of drawing enlarged-diameter is 1.5-3 a times of fuel evaporation section diameter, and catalyzer return line upper end is connected with this part.
Catalyst mix section diameter is 1-2.5 a times of fuel evaporation section.
The present invention is divided into three parts in upper, middle and lower with reaction zone, and the bottom is the catalyst mix district, and the middle part is fuel evaporation and conversion reaction zone, and top is the reactant flow draw-out area; At first make from the high-temperature regenerated catalyst of revivifier and mix, form the catalyst temperature condition that is fit to gasoline reaction requirement, these catalyzer are contacted with gasoline react with the low temperature catalyst that refluxes through the catalyzer return line from gasoline reactor top.Reacted logistics is carried out product separation through the separation link that fairlead enters the back.So can realize backflow, the circulation of catalyzer at reactor self, do not change and original device between under the condition of catalyst recirculation amount, effectively improved the agent-oil ratio of reaction zone, and do not needed by other equipment such as settling vessel, strippers.The present invention utilizes settling vessel, catalyst stripping equipment and the revivifier of former catalytic cracking unit.
The upgrading reaction zone of reactor of the present invention can be conventional riser tube form, also can be the placed in-line form of riser tube and fluidized-bed.When the upgrading reaction zone uses riser tube and the placed in-line form of fluidized-bed, gasoline stocks is introduced into the riser tube conversion of gasifying, the oil gas and the catalyzer of reaction generation are up then, enter fluidized bed reaction zone and carry out desulfurization, hydrogen transference, olefin reaction, enter fairlead at last, enter follow-up Reaction Separation parts such as reacting-settler through outlet.When gasoline has the desulfurization requirement, preferentially select the reactor types that has fluidized-bed for use.
Gasoline reactor of the present invention can be used for various stock oil catalytic cracking unit for to increase the independently reactor of building on former catalytic cracking unit, realizes Gasoline On-line processing.
Gasoline reactor of the present invention especially is fit to and original stock oil reactor shared revivifier, settling vessel and a stripper.
Gasoline catalyzing method for transformation of the present invention also can form and stock oil reaction unit dual system device arranged side by side for the gasoline reaction designs revivifier, settling vessel, stripper in addition.
The present invention has realized that at reactor itself low temperature, high agent-oil ratio, low-speed etc. help that gasoline transforms, the reaction conditions of upgrading, can make that the olefin(e) centent of gasoline is near 20% (v), to remove in the gasoline 70% sulphur; When needed, can also propylene enhancing etc. Chemicals.
Description of drawings
Fig. 1 for utilize of the present invention anti--refill the interposed structure synoptic diagram;
Fig. 2 is a structure of reactor synoptic diagram among the embodiment 2;
Fig. 3 is a structure of reactor synoptic diagram among the embodiment 3;
Fig. 4 is a structure of reactor synoptic diagram among the embodiment 4.
Embodiment
Embodiment 1, gasoline is catalytic conversion reactor again, form by the catalyst mix section 12, fuel evaporation section 13, upgrading conversion zone 14, the material section of drawing 15 that connect from bottom to top, catalyst mix section 12 is provided with regenerated catalyst inlet pipe 11 and promotes medium inlet 17-1, fuel evaporation section 13 is provided with gasoline inlet 18-1, be provided with catalyzer return line 16 between catalyst mix section 12 and the material section of drawing 15, the material section of drawing 15 is provided with fairlead 15-1.
Instead-again install by stock oil riser reactor 2, gasoline reactor 1, settling vessel 3, stripper 4, revivifier 5 and form.Hydrocarbon raw material carries out catalytic cracking reaction in stock oil riser reactor 2; Gasoline is at gasoline reactor 1 internal reaction.
In gasoline reactor 1, regenerated catalyst 52 from regeneration standpipe 53 and guiding valve 54, enter in the catalyst mix section 12 through entering pipe 11, mix with low temperature catalyst 19 from return line 16, when meeting the requirements of temperature, on under the effect that promotes medium 17, be advanced into gasoline rising pipe gasification zone 13, contact with the gasoline 18 that enters through atomizing at this, make fuel evaporation, and carry out initial reaction, reactant flow continues upwards to enter fluidized-bed zone of transformation 14, finish conversion of olefines at this, desulphurization reaction after fairlead 15-1 leaves reactor, enters settling vessel 3 and revivifier 5; The catalyzer that partial reaction is crossed from the section of drawing 15 in return line 16 is back to the mixing section 12 of reactor bottom.The mixing section inner catalyst temperature change as requested of the quantity of reflux of catalyzer is by guiding valve 20 controls.
Reaction oil gas reaches with after entering the cyclonic separator 31 of catalyzer in fairlead enters settling vessel 3 of pipe 11 equivalent, isolating catalyzer, and oil gas is sent instead-again device, the product separation part that enters the back through pipeline 32.Cyclonic separator 31 isolated catalyzer then flow into stripper 4 downwards, contact with stripped vapor, displace entrained oil gas after, flow into revivifier 5, oxygen 51 reactions with from the regenerator bottoms import recover to enter reactor 1,2 again after the activity, finish reaction cycle.57 is external warmer.2-1 is the stock oil nozzle, and 2-2 is the recycle stock nozzle.
At a cover crude runs 100 * 10
4On the catalytic cracking unit of t/a, processing 40 * 10
4T/a gasoline; Content of sulfur in gasoline 1000ppm, olefin(e) centent 50% is (v); To have adopted above-mentioned reaction method in the catalytic cracking unit of producing high-grade gasoline.Instead-refill and put 50 meters of height overalls, the gasoline reactor catalyst enters pipe diameter 350mm, catalyst mix section diameter 1000mm, high 6000mm, gasification section riser diameter 600mm, high 3000mm, fluidized-bed conversion zone diameter 2000mm, high 5000mm, fairlead diameter 700mm, the section of drawing is 1500mm in the hole enlargement of the catalyzer place of drawing, return line diameter 400mm.
40 ℃ of gasoline feedings, 410 ℃ of gasoline temperature of reaction, 550 ℃ of mixing section catalyst temperatures are from the catalyst recirculation amount 200t/h of regeneration standpipe, atomizing steam amount 600kg/h, settling vessel 3 working pressure 0.25Mpa (a), revivifier 5 working pressure 0.34MPa (a).
Gasoline reaction result: yield of gasoline 93%, diesel oil 2%, liquefied petroleum gas (LPG) 3.5%, dry gas and coke 1.5%; Product gasoline olefin(e) centent 18% (v), sulphur content 300ppm.
Embodiment 2, gasoline is catalytic conversion reactor again, form by the catalyst mix section 12, fuel evaporation section 13, upgrading conversion zone 14, the material section of drawing 15 that connect from bottom to top, catalyst mix section 12 is provided with regenerated catalyst inlet pipe 11 and promotes medium inlet 17-1, fuel evaporation section 13 is provided with gasoline inlet 18-1, be provided with catalyzer return line 16 between catalyst mix section 12 and the material section of drawing 15, the material section of drawing 15 is provided with fairlead 15-1.19 are the backflow catalyzer, and 20 is guiding valve.52 is regenerated catalyst, and 54 is guiding valve, and 11 enter pipe for regenerated catalyst.
Instead-again install by stock oil riser reactor, gasoline reactor, settling vessel, stripper, revivifier and form.Hydrocarbon raw material carries out catalytic cracking reaction in the stock oil riser reactor, gasoline 18 is at gasoline reactor internal reaction.
At a cover crude runs 100 * 10
4On the catalytic cracking unit of t/a, make 20 * 10
4The t/a inferior gasoline upgrading, and take into account the production liquid hydrocarbon.Content of olefin in gasoline 50% (v), sulphur content 800ppm before the upgrading.
Catalyzer enters pipe 11 diameter 300mm, catalyst mix section 12 diameter 800mm, high 5000mm, fuel evaporation section 13 and upgrading conversion zone 14 diameter 400mm, reactor diameter is expanded as 1.0 meters at backflow catalyzer outlet place, catalyzer return line 16 diameter 300mm.
40 ℃ of inferior patrol feeding temperatures, 480 ℃ of temperature of reaction, the mixed catalyst temperature is 550 ℃ before the reaction, catalyst recirculation amount 125t/h from the regeneration standpipe, atomizing steam amount 300kg/h, oil gas is at the mean residence time of reaction zone 3 seconds, settling vessel 3 working pressure 0.25Mpa (a), revivifier 5 working pressure 0.34MPa (a).
The gasoline reaction result: yield of gasoline 85%, diesel oil 3.5%, liquefied petroleum gas (LPG) 9.7%, dry gas adds coke 1.8%.Product gasoline olefin(e) centent 15% (v), sulphur content 500ppm.
Embodiment 3, gasoline is catalytic conversion reactor again, form by the catalyst mix section 12, fuel evaporation section 13, upgrading conversion zone 14, the material section of drawing 15 that connect from bottom to top, catalyst mix section 12 is provided with regenerated catalyst inlet pipe 11 and lift gas inlet 17-1, upgrading conversion zone 14 is provided with gasoline inlet 18-1, be provided with catalyzer return line 16 between catalyst mix section 12 and the material section of drawing 15, the material section of drawing 15 is provided with fairlead 15-1.Catalyst mix section 12 diameters are fuel evaporation section 13, upgrading conversion zone 14, the material section of drawing 15 diameters 2 times.17 is lift gas, and 18 is gasoline, and 19 are the backflow catalyzer, and 20 is guiding valve.52 is regenerated catalyst, and 54 is guiding valve, and 11 enter pipe for regenerated catalyst.
Embodiment 4, gasoline is catalytic conversion reactor again, form by the catalyst mix section 12, fuel evaporation section 13, upgrading conversion zone 14, the material section of drawing 15 that connect from bottom to top, catalyst mix section 12 is provided with regenerated catalyst inlet pipe 11 and lift gas inlet 17-1, upgrading conversion zone 14 is provided with gasoline inlet 18-1, be provided with catalyzer return line 16 between catalyst mix section 12 and the material section of drawing 15, the material section of drawing 15 is provided with fairlead 15-1.Catalyst mix section 12, upgrading conversion zone 14 diameters are 2 times of fuel evaporation section 13 diameters, and the backflow catalyzer outlet section of the drawing 15A of place diameter is 1.5 times of fuel evaporation section 13 diameters.17 is lift gas, and 18 is gasoline, and 19 are the backflow catalyzer, and 20 is guiding valve.52 is regenerated catalyst, and 54 is guiding valve, and 11 enter pipe for regenerated catalyst.
Claims (9)
1. gasoline catalytically converting method, it is characterized in that, the part catalyzer is drawn from reactor top, and the catalyzer return line between the material section of drawing by being connected in reactor top and the catalyst mix section of reactor bottom directly is back to reactor bottom and uses with the catalyst mix from revivifier.
2. the method for claim 1, it is characterized in that the catalyst temperature before contacting with gasoline stocks is 450-650 ℃, the mass flux ratio of reaction zone catalyzer and gas material is 6-15, temperature of reaction is 380-530 ℃, the mean residence time 3-10 second of gas in reactor.
3. method as claimed in claim 2 is characterized in that, temperature of reaction is 380-500 ℃, and the mean residence time of gas in reactor is 3-10 second.
4. method as claimed in claim 2 is characterized in that, temperature of reaction is 450-530 ℃, and the mean residence time of gas in reactor is 3-6 second.
5. the gasoline of realizing the described method of claim 1 is catalytic conversion reactor again, it is characterized in that, form by the catalyst mix section, fuel evaporation section, upgrading conversion zone, the material section of drawing that connect from bottom to top, the catalyst mix section is provided with regenerated catalyst inlet and lift gas inlet, the fuel evaporation section is provided with the gasoline inlet, be provided with the catalyzer return line between catalyst mix section and the material section of drawing, the material section of drawing is provided with fairlead.
6. reactor as claimed in claim 5 is characterized in that, upgrading conversion zone enlarged-diameter is 2-4 a times of fuel evaporation section.
7. reactor as claimed in claim 5 is characterized in that, the material section of drawing enlarged-diameter is 1.5-3 a times of fuel evaporation section, and catalyzer return line upper end is connected with this part.
8. reactor as claimed in claim 6 is characterized in that, the material section of drawing enlarged-diameter is 1.5-3 a times of fuel evaporation section diameter, and catalyzer return line upper end is connected with this part.
9. as claim 5,6,7 or 8 described reactors, it is characterized in that catalyst mix section diameter is 1-2.5 a times of fuel evaporation section.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2005100177464A CN1888026B (en) | 2005-06-30 | 2005-06-30 | Gasoline catalytic converting method and reactor |
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| CN2005100177464A CN1888026B (en) | 2005-06-30 | 2005-06-30 | Gasoline catalytic converting method and reactor |
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| Publication Number | Publication Date |
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| CN1888026A CN1888026A (en) | 2007-01-03 |
| CN1888026B true CN1888026B (en) | 2010-04-28 |
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| CN2005100177464A Expired - Fee Related CN1888026B (en) | 2005-06-30 | 2005-06-30 | Gasoline catalytic converting method and reactor |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3888762A (en) * | 1972-10-12 | 1975-06-10 | Universal Oil Prod Co | Fluid catalytic cracking process |
| CN1345362A (en) * | 2000-02-16 | 2002-04-17 | 印度石油股份有限公司 | Multi-stage selective catalytic cracking process and system for producing high yield of middle distillate products from heavy hydrocarbon feedstocks |
| CN1498946A (en) * | 2002-11-07 | 2004-05-26 | 石油大学(北京) | Method and device of catalysis for transnaturing gasoline and lowering olefin |
-
2005
- 2005-06-30 CN CN2005100177464A patent/CN1888026B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3888762A (en) * | 1972-10-12 | 1975-06-10 | Universal Oil Prod Co | Fluid catalytic cracking process |
| CN1345362A (en) * | 2000-02-16 | 2002-04-17 | 印度石油股份有限公司 | Multi-stage selective catalytic cracking process and system for producing high yield of middle distillate products from heavy hydrocarbon feedstocks |
| CN1498946A (en) * | 2002-11-07 | 2004-05-26 | 石油大学(北京) | Method and device of catalysis for transnaturing gasoline and lowering olefin |
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| CN1888026A (en) | 2007-01-03 |
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Address after: 471000 Tsinghua Science Park, three mountain road, hi tech Zone, Henan, Luoyang 609 Patentee after: Luoyang Petro-Chemical Equipment Inst. Address before: 471003 Zhongzhou West Road, Henan, China, No. 27, No. Patentee before: Luoyang Petro-Chemical Equipment Inst. |
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Granted publication date: 20100428 Termination date: 20130630 |