CN1212371C - Method of catalytic gasoline upgrading and lowering olefin hydrocarbon with high light oilyield and its device - Google Patents
Method of catalytic gasoline upgrading and lowering olefin hydrocarbon with high light oilyield and its device Download PDFInfo
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- CN1212371C CN1212371C CN 02146136 CN02146136A CN1212371C CN 1212371 C CN1212371 C CN 1212371C CN 02146136 CN02146136 CN 02146136 CN 02146136 A CN02146136 A CN 02146136A CN 1212371 C CN1212371 C CN 1212371C
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Abstract
The present invention discloses a method and device for modifying catalytic gasoline with high yield of light oil and reducing the content of olefin. On the basis of an original industrial catalytic cracker and a conventional catalytic cracking process, a sloped tube for leading out high-temperature regenerating catalyst material flow and a single novel fluidization catalysis modifying reactor are additionally arranged on a regenerator to catalyze and modify the fraction of the catalytic cracking gasoline to obtain the purposes of greatly reducing the content of the olefin and increasing octane number, and meanwhile, the high yield of the light oil is ensured. The added novel fluidization reactor is in a turbulent flow bed type or a quick bed type, and is provided with a gas lifting system and a settling system. The technical skill has the advantages of small change to an original catalytic cracker, simple process, easy realization, easy control and stable operation. The content of the olefin of the catalytic cracking gasoline can be reduced to 25 (v) %, the requirements of environment protecting regulations are achieved, and the yield of the light oil in the modifying process can be kept above 93%.
Description
Technical field
The present invention relates to the catalytic conversion process of petroleum hydrocarbon, be meant that especially the high modifying catalytically cracked gasoline of light oil yield reduces the catalytic conversion process technology of olefin(e) centent, belongs to the petrochemical technology field.
Background technology
The octane value of alkene is higher, is to keep the high-octane main ingredient of catalytically cracked gasoline, and still, the alkene chemical property is active, NO in volatilization back and the atmosphere
XMix,, atmosphere is caused severe contamination through the poisonous photo-chemical smog of solar ultraviolet irradiation formation based on ozone; In addition, when olefin(e) centent is high in the gasoline, can cause that electronic fuel injection engine nozzle, feed valve carbon deposit are serious, cause controlled deviation, cause fuel oil consumption to increase.Therefore, along with the increasingly stringent of environmental requirement, the U.S., Japan and European various countries have issued new gasoline standard in succession in recent years.China has also formulated " motor spirit objectionable impurities standard " in December, 1999, require olefin content in gasoline ≯ 35 (v) %, simultaneously, require octane value (organon) ≮ 90, aromaticity content ≯ 40 (v) %, sulphur content ≯ 800ppm, and stipulate to rise on January 1st, 2003 in China and implement.
At present, motor spirit has data to show that catalytically cracked gasoline accounts for the amount of gasoline product up to 85% still based on catalytically cracked gasoline.The volume fraction of alkene is 45%-55% in the catalytically cracked gasoline, far above the gasoline standard of new prescription.Therefore, the olefin(e) centent in the reduction catalytically cracked gasoline becomes the urgent task in the current petroleum refining industry.Because refinery's processing is paraffinic crude, its gasoline octane rating (organon) reaches standard reluctantly generally at 89-90, if olefin(e) centent is descended significantly, certainly will can't meet the demands by octane value.How satisfying in the gasoline olefin(e) centent simultaneously is no more than 35 (the v) requirement of % guarantees that also octane value reaches standard, just becomes a very urgent and difficult problem.
In order to reduce the olefin(e) centent of catalytically cracked gasoline, the general measure of adopting of petroleum refining industry has: the pre-hydrotreatment of fcc raw material, adopt olefine lowering catalyst.But these method effects are limited, and content of olefin in gasoline maximum 10-12 the volume percentage point that only descend, octane value also reduce sometimes to some extent, can not reach the requirement of new gasoline standard.Catalytically cracked gasoline is carried out independent upgrading comprise petroleum naphtha etherificate, catalytically cracked gasoline desulfurating and reducing olefinic hydrocarbon, catalytic gasoline hydrogenation isomery aromizing, catalytic gasoline hydrogenation desulfurization-reformation etc. with some research reports that reduce olefin(e) centent, but, these methods and technology or complex process, investment are greatly, many refinerys adopt still very big difficulty, perhaps that is that all right is ripe for Technology, does not realize industrial applications.
In order to reduce the olefin(e) centent of catalytically cracked gasoline effectively, reach the requirement of environmental regulation and new gasoline standard, proposed on conventional catalytic cracking unit, to set up the scheme of service hoisting pipe reactor, catalytically cracked gasoline is carried out further upgrading, and applied for relevant patent, comprise: the method and the device of easy catalytic cracking sasoline modifincation and olefine reducing, application number: 02116786.9; Reduce the method and system of catalytic cracking gasoline olefine content, application number: 02123817.0, the method for modifying of heavily reducing olefinic hydrocarbon and increasing octane rating for catalytically cracked gasoline and device, application number: 02123655.0, reduce catalytic cracking gasoline olefine content and keep the method and system of octane value, application number: 02123494.9, the method for modifying of gasoline catalyzing and olefine reducing boosting of octane rating and device, application number: 02123658.9, reduce the method and the device of catalytic cracking gasoline olefine content, application number: 02116787.7.These reduce the method and apparatus of catalytic cracking gasoline olefine content owing to adopted the service hoisting pipe reactor, from technological process is that the high temperature regeneration agent mixes with normal temperature Liquid Phase by Catalytic gasoline and contacts, carry out hydrogen transference, aromizing, isomerization and the reaction of cracked upgrading, therefore the reacted gas productive rate of this process is higher, mainly be liquefied gas wherein, thereby cause yield of gasoline and yield of light oil to reduce.For the bad oil refining enterprise in liquefied gas market, this result is unfavorable.Analyzing reason mainly is higher the causing of initial contact mixing temperature of finish.
Summary of the invention
Main purpose of the present invention is to provide the high catalytic gasoline upgrading of a kind of light oil yield to fall the method and apparatus of alkene, can improve yield of light oil, reduces the content of alkene in the catalytically cracked gasoline and keeps the constant or slightly raising of octane value.
The objective of the invention is to be achieved through the following technical solutions:
The method of alkene falls in the catalytic gasoline upgrading that a kind of light oil yield is high, and the technical process of this method comprises at least:
Step 1: the catalytically cracked gasoline cut enters the fluidized catalytic reforming reactor from the bottom, contacts, gasifies, mixes and react with catalyzer in the bed;
Step 2: reacted reclaimable catalyst is got back to former catalytic cracking unit revivifier behind stripping, after upgrading oil gas is drawn from sedimenting system top, be introduced into the main oil gas piping of former catalytic cracking unit, mix with the reaction oil gas of main riser reactor then, enter the main fractionating tower bottom again and carry out separating of rich gas, raw gasline lighting end, raw gasline last running, diesel oil, recycle stock and slurry oil; Perhaps entering independent fractionating system separates.
The condition of described upgrading reaction is:
Temperature of reaction: 350-500 ℃;
Gasoline stocks preheating temperature: 40-300 ℃;
Catalyst activity: 50-65;
Reaction pressure: 0.1-0.4MPa.
The catalytically cracked gasoline cut is the full cut of raw gasline or raw gasline lighting end (＜80-110 ℃) or raw gasline last running (＞60-80 ℃).
Described catalyzer is the catalyzer of former heavy oil catalytic cracking unit, comprises amorphous silicon aluminium catalyzer or molecular sieve catalyst at least.
When upgrading is carried out in last running to the catalytic cracking raw gasline, corresponding raw gasline lighting end directly and the gasoline fraction behind the upgrading mix, perhaps carry out behind the upgrading again mixing with gasoline fraction behind the upgrading.
The device of alkene falls in the catalytic gasoline upgrading that a kind of light oil yield is high, the structure of this device is: inclined tube and a catalyzer inclined tube to be generated of being provided with and drawing a high-temperature regenerated catalyst logistics on the revivifier of original heavy oil catalytically cracking equipment, it links to each other with a fluidized catalytic reforming reactor, the bottom of this fluidized catalytic reforming reactor connects the regeneration system rapidly of former catalytic cracking unit, this fluidized catalytic reforming reactor top connects main fractionating tower by the main oil gas piping of former catalytic cracking unit, perhaps connects fractionating system separately.
The condition of described upgrading reaction is:
Temperature of reaction: 350-500 ℃;
Gasoline stocks preheating temperature: 40-300 ℃;
Catalyst activity: 50-65;
Reaction pressure: 0.1-0.4MPa.
Described fluidized catalytic reforming reactor comprises turbulent bed type reforming reactor or fast bed type reforming reactor at least.
When adopting turbulent bed type reforming reactor, the turbulent bed weight space velocity is 1-1000hr
-1When adopting fast bed type reforming reactor, the bed linear speed is 0.6-2.5m/s, and the reaction times is 0.1～10.0 minute.
On the original conventional condensation cooling system of heavy oil catalytically cracking equipment fractionator overhead, set up the B-grade condensation system, in order to obtain the full cut of raw gasline or to obtain the raw gasline lighting end or obtain raw gasline last running.By above technical scheme, the present invention has following effect:
The advantage of Technology of the present invention is the change minimum to former catalytic cracking unit, and flow process is simple, is easy to realize, and is easy to control, stable operation.Catalytic cracking gasoline olefine content can be reduced to 25 and (v) below the %, can satisfy the requirement of environmental regulation, and the light oil yield of maintenance upgrading process be more than 93%.
Description of drawings
Fig. 1 is original heavy oil catalytic cracking process schema;
Fig. 2 is the process flow sheet of turbulent bed type reactor upgrading catalytic gasoline;
Fig. 3 is the process flow sheet of fast bed type reactor upgrading catalytic gasoline;
Fig. 4 is the process flow sheet of the another embodiment of turbulent bed type reactor upgrading catalytic gasoline;
Fig. 5 is the fast bed type reactor upgrading catalytic gasoline process flow sheet of an embodiment again.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments:
Fractionator overhead B-grade condensation system sets up through changing design on the conventional condensation cooling system of original fractionation cat head.When upgrading is carried out in raw gasline lighting end or raw gasline last running, can operate by B-grade condensation, when the full cut of raw gasline is carried out upgrading, condensation cooling operation routinely.If upgrading is carried out in last running to the catalytic cracking raw gasline, so corresponding raw gasline lighting end can directly mix with gasoline fraction, also can carry out upgrading after (as etherificate, isomery aromizing etc.) mix with gasoline fraction again.The visible Fig. 1 of this part flow process, also can be referring to patent of invention " reducing the method and system of catalytic cracking gasoline olefine content ", application number: 02123817.0, be summarized as follows: by the top of separation column 1 oil gas 2 (comprising raw gasline and rich gas) that comes out, 3 condensations of process condenser are cooled to suitable temp, and (if upgrading is carried out in last running to the catalytic cracking raw gasline, this temperature is 50-60 ℃; If upgrading is carried out in lighting end to the catalytic cracking raw gasline, this temperature is 62-80 ℃) after enter separating tank 4 and carry out the separation of profit gas, condensed water 5 detaches separating tank 4 by condensate pump 6.The product liquid that condensation is got off is raw gasline last running 7, extracts out from separating tank 4 through last running petrol-feed pump 8, and a part refluxes 9 as the top of separation column 1, and another part 10 further is cooled to 40 ℃ through supercooler 11.
If to the full fraction upgrading of raw gasline, at this moment valve 23,30 and 31 is opened, valve 24 is closed, raw gasline last running 10 and raw gasline lighting end 21 are mixed into gets certain appropriate amount 25 behind the full cut 22 of raw gasline and enters the novel fluidized catalytic reforming reactor of newly establishing and carry out upgrading, and rest part 26 enters absorbing-stabilizing system; If to raw gasline last running upgrading, at this moment valve 23,24 and 30 all open, valve 31 is closed, the raw gasline last running 27 of getting certain appropriate amount by flow control directly enters the novel fluidized catalytic reforming reactor of newly establishing and carries out upgrading, rest part 28 enters absorbing-stabilizing system after being mixed into the full cut 22 of raw gasline with raw gasline lighting end 21, at this moment petroleum naphtha 21 can directly with after raw gasline last running 28 mixes enter absorbing-stabilizing system, also can carry out earlier as the petroleum naphtha etherificate, behind the upgrading of aspects such as isomery aromizing, enter absorbing-stabilizing system again with after raw gasline last running 28 mixes.If upgrading is carried out in the raw gasline lighting end, at this moment valve 23,29 and 30 is all opened, valve 24 and 31 is closed, the raw gasline lighting end 32 of getting certain appropriate amount by flow control directly enters the novel fluidized catalytic reforming reactor of newly establishing and carries out upgrading, and rest part and raw gasline last running 28 enter absorbing-stabilizing system after being mixed into the full cut 22 of raw gasline.
The operation of former catalytic-cracking reaction system is constant, the raw material 33 that promptly contains atomizing steam enters main riser tube 34 and is 460-530 ℃ by the high temperature regeneration agent 37 that water vapour 36 promotes in temperature of reaction from revivifier 35 from the bottom, the heavy oil feedstock preheating temperature is 160-250 ℃, catalyzer oil plant weight ratio is 5-8, catalyst activity is 50-65, reaction times is 2.5-3.0s, reaction pressure is to contact under the 0.1-0.4MPa, gasification, mix and reaction, oil gas, water vapour passes through main riser reactor 34 with catalyzer, revolve 39 separately to the outlet of main riser reactor by efficient fast gas-solid separator 38 and settling vessel top with main reaction oil gas 42 and catalyzer, catalyzer enters stripping stage 41 through settling vessel 40, enters revivifier 35 through behind the stripping.In the independent separation scheme of catalytic gasoline upgrading oil gas, main reaction oil gas 42 (promptly 44) leaves settling vessel 40 and enters the separation that rich gas, raw gasline lighting end, raw gasline last running, diesel oil, recycle stock, slurry oil are carried out in main fractionating tower 1 bottom.In the not independent isolating scheme of catalytic gasoline upgrading oil gas, main reaction oil gas 42 and novel fluidized catalytic reforming reactor outlet oil gas are mixed into oil gas 44 and leave settling vessel 40 and enter main fractionating tower 1 bottom and carry out separating of rich gas, raw gasline lighting end, raw gasline last running, diesel oil, recycle stock, slurry oil.
Embodiment 1:
Reforming reactor for the turbulent bed type, the visible Fig. 2 of flow process of the present invention, be summarized as follows: regenerated catalyst is guided to catalyzer riser tube 47 by an inclined tube 45 of drawing the high-temperature regenerated catalyst logistics of setting up on the revivifier 35, rise to the fluidized catalytic reforming reactor 48 interior reaction beds of setting up 49 that form by catalyzer riser tube 47 by promoting steam 46 again, the last spout of catalyzer riser tube 47 is at the top of reaction bed 49, the catalytically cracked gasoline cut 50 (being the full cut 25 of catalytic cracking raw gasline or raw gasline last running (＞60-80 ℃) 27 or the raw gasline lighting end cut (＜80-110 ℃) 32 among Fig. 1) that contains atomizing steam enters the bottom of fluidized catalytic reforming reactor bed 49 by shower nozzle, contacts with catalyzer in the bed 49, gasification, mix and reaction.In the reaction bed 49 of the fluidized catalytic reforming reactor of setting up 48, keeping temperature of reaction is 350-500 ℃, and the gasoline stocks preheating temperature is 40-300 ℃, and catalyst activity is 50-65, and the turbulent bed weight space velocity is 1-1000hr
-1, reaction pressure is 0.1-0.4Mpa.The reacted catalyzer of upgrading enters the stripping stage 54 of fluidized catalytic reforming reactor, carries out counter current contact with the stripped vapor of introducing from stripping stage 54 bottoms 55, goes out the oil gas of catalyst entrainment with stripping.Catalyzer behind the stripping enters former revivifier 35 by the inclined tube of newly establishing to be generated 56.Reacted upgrading oil gas enters the settling section 51 of fluidized catalytic reforming reactor 48, entering top cyclonic separator 52 again separates with the catalyzer that carries, after upgrading oil gas 53 complete and catalyst separating leaves the fluidized catalytic reforming reactor, the main oil gas piping of incorporating former catalytic cracking unit into mixes laggardly to go into the main fractionating tower bottom and carry out separating of rich gas, raw gasline lighting end, raw gasline last running, diesel oil, recycle stock and slurry oil with the reaction oil gas of main riser reactor.
Embodiment 2:
Reforming reactor for the fast bed type, the visible Fig. 3 of flow process of the present invention, be summarized as follows: the middle part of regenerated catalyst being introduced fast bed 57 by an inclined tube 45 of drawing the high-temperature regenerated catalyst logistics of setting up on the revivifier 35, in fast bed 57, form closeer mobile bed, the catalytically cracked gasoline cut 50 (being the full cut 25 of catalytic cracking raw gasline or raw gasline last running (＞60-80 ℃) 27 or the raw gasline lighting end cut (＜80-110 ℃) 32 among Fig. 1) that contains atomizing steam enters the bottom of fluidized catalytic reforming reactor fast bed 57 by shower nozzle, contacts with catalyzer in the fast bed 57, gasification, mix and reaction.In setting up fluidized catalytic reforming reactor 57, keeping temperature of reaction is 350-500 ℃, and the gasoline stocks preheating temperature is 40-300 ℃, catalyst activity is 50-65, the bed linear speed is 0.6-2.5m/s, and the reaction times is 0.1-10.0min, and reaction pressure is 0.1-0.4MPa.Then, reaction oil gas and catalyzer enter the dilute phase riser 58 of fluidized catalytic reforming reactor, put 59 separately by being located at the outspoken packing of going out of dilute phase riser top again with catalyzer and reaction oil gas, catalyzer enters stripping stage 54, carry out counter current contact with the stripped vapor of introducing from stripping stage 54 bottoms 55, go out the oil gas of catalyst entrainment with stripping.Catalyzer behind the stripping enters former revivifier 35 by the inclined tube of newly establishing to be generated 56.Reacted upgrading oil gas enters the settling section 51 of fluidized catalytic reforming reactor, entering top cyclonic separator 52 again separates with the catalyzer that carries, after upgrading oil gas 53 complete and catalyst separating leaves the fluidized catalytic reforming reactor, the main oil gas piping of incorporating former catalytic cracking unit into mixes laggardly to go into the main fractionating tower bottom and carry out separating of rich gas, raw gasline lighting end, raw gasline last running, diesel oil, recycle stock and slurry oil with the reaction oil gas of main riser reactor.
The present invention also comprises for the separate mode of upgrading oil gas:
Embodiment 3:
Referring to Fig. 2, Fig. 4, wherein the flow process of upgrading is consistent with embodiment 1, different is: the oil gas 53 behind the upgrading enters independent separation system, rather than is mixed into the main oil gas piping that oil gas 44 together enters former catalytic cracking unit with novel fluidized catalytic reforming reactor outlet oil gas.
Embodiment 4:
Referring to Fig. 3, Fig. 5, wherein the flow process of upgrading is consistent with embodiment 2, different is: the oil gas 53 behind the upgrading enters independent separation system, rather than is mixed into the main oil gas piping that oil gas 44 together enters former catalytic cracking unit with novel fluidized catalytic reforming reactor outlet oil gas.
The used catalyzer of the present invention can be any catalyzer that is applicable to catalytic cracking process, i.e. modifying catalytically cracked gasoline reaction is realized by former heavy oil catalytic cracking unit catalyzer.For example, amorphous silicon aluminium catalyzer or molecular sieve catalyst, wherein, the active ingredient of molecular sieve catalyst is selected from one or more in Y type or HY type zeolite, the ultrastable Y that contains or do not conform to rare earth and/or phosphorus, the ZSM-5 series zeolite that contains or do not contain rare earth and/or phosphorus or the supersiliceous zeolite with five-membered ring structure, β zeolite, the ferrierite.
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (8)
- The method of alkene falls in the catalytic gasoline upgrading that 1, a kind of light oil yield is high, it is characterized in that: the technical process of this method comprises at least:Step 1: the catalytically cracked gasoline cut enters the fluidized catalytic reforming reactor from the bottom, contacts, gasifies, mixes and react with catalyzer in the bed, and the condition of upgrading reaction is:Temperature of reaction: 350-500 ℃;Gasoline stocks preheating temperature: 40-300 ℃;Catalyst activity: 50-65;Reaction pressure: 0.1-0.4MPa;Step 2: reacted reclaimable catalyst is got back to former catalytic cracking unit revivifier behind stripping, after upgrading oil gas is drawn from sedimenting system top, be introduced into the main oil gas piping of former catalytic cracking unit, mix with the reaction oil gas of main riser reactor then, enter the main fractionating tower bottom again and carry out separating of rich gas, raw gasline lighting end, raw gasline last running, diesel oil, recycle stock and slurry oil; Perhaps entering independent fractionating system separates.
- The method of alkene falls in the catalytic gasoline upgrading that 2, light oil yield according to claim 1 is high, it is characterized in that: the catalytically cracked gasoline cut is the full cut of raw gasline or boiling range less than the raw gasline last running greater than 60 ℃ of 110 ℃ raw gasline lighting end or boiling range.
- The method of alkene falls in the catalytic gasoline upgrading that 3, light oil yield according to claim 1 is high, it is characterized in that: described catalyzer is the catalyzer of former heavy oil catalytic cracking unit, comprises amorphous silicon aluminium catalyzer or molecular sieve catalyst at least.
- The method of alkene falls in the catalytic gasoline upgrading that 4, light oil yield according to claim 1 is high, it is characterized in that: when upgrading is carried out in last running to the catalytic cracking raw gasline, corresponding raw gasline lighting end directly and the gasoline fraction behind the upgrading mix, perhaps carry out behind the upgrading again mixing with gasoline fraction behind the upgrading.
- 5, the device of alkene falls in the catalytic gasoline upgrading that a kind of light oil yield is high, it is characterized in that: the structure of this device is: inclined tube and a catalyzer inclined tube to be generated of being provided with and drawing a high-temperature regenerated catalyst logistics on the revivifier of original heavy oil catalytically cracking equipment, it links to each other with a fluidized catalytic reforming reactor, the bottom of this fluidized catalytic reforming reactor connects the regeneration system rapidly of former catalytic cracking unit by described catalyzer inclined tube to be generated, this fluidized catalytic reforming reactor top connects main fractionating tower by the main oil gas piping of former catalytic cracking unit, perhaps connects fractionating system separately.
- 6, the device of alkene falls in the catalytic gasoline upgrading that light oil yield is high according to claim 1 or 5, it is characterized in that: described fluidized catalytic reforming reactor comprises turbulent bed type reforming reactor or fast bed type reforming reactor at least.
- The device of alkene falls in the catalytic gasoline upgrading that 7, light oil yield according to claim 5 is high, it is characterized in that: when adopting turbulent bed type reforming reactor, the turbulent bed weight space velocity is 1-1000hr -1When adopting fast bed type reforming reactor, the bed linear speed is 0.6-2.5m/s, and the reaction times is 0.1～10.0 minute.
- The device of alkene falls in the catalytic gasoline upgrading that 8, light oil yield according to claim 5 is high, it is characterized in that: on the original conventional condensation cooling system of heavy oil catalytically cracking equipment fractionator overhead, set up the B-grade condensation system, in order to obtain the full cut of raw gasline or to obtain the raw gasline lighting end or obtain raw gasline last running.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02146136 CN1212371C (en) | 2002-11-01 | 2002-11-01 | Method of catalytic gasoline upgrading and lowering olefin hydrocarbon with high light oilyield and its device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02146136 CN1212371C (en) | 2002-11-01 | 2002-11-01 | Method of catalytic gasoline upgrading and lowering olefin hydrocarbon with high light oilyield and its device |
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| CN1493658A CN1493658A (en) | 2004-05-05 |
| CN1212371C true CN1212371C (en) | 2005-07-27 |
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| CN101921611B (en) * | 2009-06-12 | 2013-07-31 | 中国石油天然气股份有限公司 | Catalytic cracking method and system for reducing sulphur content of petrol |
| CN102950031B (en) * | 2011-08-31 | 2014-07-02 | 中国石油化工股份有限公司 | Method and equipment for quickly stabilizing activity of catalytic cracking catalyst |
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