CN100523141C - Heavyoil catalytic cracking and gasoline modifying mutual control method and apparatus - Google Patents
Heavyoil catalytic cracking and gasoline modifying mutual control method and apparatus Download PDFInfo
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- CN100523141C CN100523141C CN 200610144163 CN200610144163A CN100523141C CN 100523141 C CN100523141 C CN 100523141C CN 200610144163 CN200610144163 CN 200610144163 CN 200610144163 A CN200610144163 A CN 200610144163A CN 100523141 C CN100523141 C CN 100523141C
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Abstract
The invention relates to the method and the device to adjust and control in heavy oil catalytic cracking and gasoline modified process. It adds the catalyst circular mixer and the regenerative catalyst cooler into the heavy oil catalytic cracking system with the gasoline modified assistant fluidized reactor. So it can lead the future and regenerative catalyst from the gasoline modified assistant fluidized reactor to the mixer and mix uniformly in the water vapour, then the mixture go into the heavy oil reactor riser to crack with the raw oil; the regenerative catalyst used for the gasoline modified is cooled in cooler before going into the assistant fluidized reactor and reacts with the vapour gasoline material. The invention can decrease the gasoline alkene content to 18%(V) and it is proper for the country environment protecting rule but improve the yield of the light oil.
Description
Technical field
The present invention relates to the catalytic conversion process of petroleum hydrocarbon, particularly relate to the coupling technique and the device of realizing this technology that reduce the catalytic conversion process of olefin(e) centent by heavy oil fluid catalytic cracking conversion and catalytic gasoline upgrading, belong to the petrochemical technology field.
Background technology
Along with the increasingly stringent of environmental protection standard, issued new gasoline standard in succession both at home and abroad in recent years, olefin content in gasoline, sulphur content etc. has been proposed strict requirement.In China, on July 1st, 2003 began to carry out new petrol and diesel oil standard, the olefin(e) centent of gasoline ≯ 35% (v), sulphur content ≯ 800ppm; The operative norm on July 1st, 2005 requires content of sulfur in gasoline ≯ 500ppm; Required the gasoline quality standard of some areas will reach EUROIII Emission Standard in 2007, that is, and olefin(e) centent ≯ 18% (v), sulphur content ≯ 150ppm.China's catalytically cracked gasoline accounts for the amount of gasoline product up to 85%, so petroleum refining industry must take effective measures and improve present catalytic cracking process, just can make gasoline product satisfy the requirement of new gasoline standard.
In order to address the above problem, improve the quality of catalytically cracked gasoline, various improvement process quilt researchs and open.Chinese Petroleum Univ. has developed and has set up auxiliary fluidizing reactor catalytically cracked gasoline to be carried out the method (patent CN1233794C and CN1233794C) of upgrading on conventional catalytic cracking unit.These reduce the Technology of catalytic cracking gasoline olefine content owing to adopted auxiliary fluidizing reactor, from technological process is that high-temperature catalytic cracked regenerated catalyst mixes with normal temperature Liquid Phase by Catalytic gasoline and contacts, carry out hydrogen transference, aromizing, isomerization and the reaction of cracked upgrading, therefore this process has coke and reacted gas (most of be liquefied gas) and produces, thereby causes the yield of gasoline of oil refining enterprise and yield of light oil to have loss about 1.5%.
The loss that the measure of any enforcement catalytically cracked gasoline reduction olefin(e) centent all can bring yield of light oil and liquid yield, technically, this is the science certainty of falling olefin hydrocarbon.That is to say, should reduce the olefin(e) centent of catalytically cracked gasoline, not loss again, this is impossible in theory.Therefore, adopting reasonable process conditions to reduce in the modifying catalytically cracked gasoline process in the yield of light oil and liquid yield loss as far as possible, also should turn to attention on the heavy oil catalytic cracking process, take effective measures and improve the conversion of heavy oil deep catalytic cracking, improve yield of light oil and liquid yield, thereby remedy the loss that clean gasoline production brings.
For this reason, Chinese Petroleum Univ. has proposed to promote the heavy oil cracking of heavy oil deep catalytic cracking conversion and the Technology (patent CN1233799C and CN1233801C) that the gasoline upgrading coupling is regulated and control again, the reclaimable catalyst that has greater activity and lesser temps after these technology utilize the catalytic gasoline upgrading to react, be introduced into the heavy oil fluid catalytic cracking riser reactor the middle and upper part, reduced the temperature of reaction of introducing the some downstream, also increased the agent-oil ratio of introducing the some downstream, heavy oil catalytic cracking reaction has been carried out effective control.But these technology also exist following deficiency: at first be that the gasoline upgrading reclaimable catalyst has different activity and temperature with heavy oil riser tube inner catalyst, both mix in the heavy oil riser reactor needs the regular hour, and the ununiformity of local density of catalyst, activity and temperature can be aggravated oil gas part in riser reactor cracking reaction and heat cracking reaction were taken place in the heavy oil riser reactor in mixing process; The secondth, with the gasoline upgrading reclaimable catalyst be injected into the heavy oil fluid catalytic cracking riser reactor the middle and upper part, though reduced the temperature of reaction of introducing the some downstream, but the agent-oil ratio of introducing the some downstream has increased, can make the riser reactor downstream that more secondary cracking reaction takes place like this, yield of light oil is descended, and the reacted gas yield increases.
Heaviness day by day along with raw material; on present technical study basis; explore more scientific and reasonable technological operation; optimize the catalytic cracking process and the gasoline upgrading technology of heavy oil feedstock; effectively improve yield of light oil and transformation efficiency, further reduce the olefin(e) centent of catalytically cracked gasoline, for realizing higher standard of fuel; the protection environment has prior meaning.
Summary of the invention
The main technical problem to be solved in the present invention, the method that provides a kind of heavy oil fluid catalytic cracking and gasoline upgrading process to regulate and control mutually is provided, by the initial mixing state of stock oil and catalyzer in regulation and control heavy oil catalytic cracking reaction and the catalytic gasoline upgrading process, the yield of light oil of heavy oil catalytic cracking process and the olefin conversion in the catalytic gasoline all are improved.
The present invention also provides a kind of device of realizing that above-mentioned heavy oil fluid catalytic cracking and gasoline upgrading process are regulated and control mutually of being used to, and increases catalyzer circulation mixing tank and regenerated catalyst water cooler, changes for a short time on the basis of existing apparatus, is easy to realize and control stabilization is operated.
For catalytic cracking process, in the last few years, heaviness day by day along with raw material, increasing riser reactor adopts the reaction conditions of high temperature, short residence time(SRT), big agent ratio, to improve the reaction severity, colloid in the heavy oil and bituminous matter are formed thermal shocking, keep enough transformation efficiency and higher yield of light oil.The raising of reaction severity makes heavy oil and the catalytic initial mixing state of catalyzer seem particularly important.Good finish initial mixing state can prevent effectively that stock oil from contacting mixing moment with catalyzer because both temperature difference are big, the inhomogeneous local superheating phenomenon that causes of conducting heat, reduce the heat cracking reaction degree, impel charging to vaporize fast, the heavy oil feed that helps unit weight contacts more catalyst active center and carries out catalytic cracking reaction, promote deeply carrying out of heavy oil catalytic cracking reaction, improve yield of light oil.
The contriver studies show that, the gasoline upgrading reclaimable catalyst that will have greater activity and a lesser temps through the stripping rear section or all with hot regenerated catalyst thorough mixing, enter into heavy oil fluid catalytic cracking master riser reactor finish mixing zone then, the catalyst recirculation amount that increases the cracking reaction of participation heavy oil feedstock under the thermally equilibrated situation of original device can not influenced, minimizing stock oil contacts the temperature head when mixing with catalyzer, regulate the reactive behavior of catalyzer, heavy oil feedstock and the catalytic initial mixing state of catalyzer are effectively regulated and control.
For the upgrading process of catalytic gasoline, the initial mixing state of gasoline stocks and thermal regenerant also can assist the catalyst temperature of fluidizing reactor to regulate and control by changing reformulated gasoline material feeding state and entering in the auxiliary fluidizing reactor.At present gasoline stocks all is to enter with the normal temperature liquid phase state contact mixing with thermal regenerant in the auxiliary fluidizing reactor and react in the upgrading process of catalytic gasoline, relevant experiment shows, gasoline stocks is unfavorable for heat and mass transport between gasoline stocks and the catalyzer with the charging of normal temperature liquid phase state, coke in the reaction process, the productive rate of dry gas is higher, and gasoline stocks contacts the ununiformity that mixing can obviously reduce the temperature head between reformulated gasoline and the regenerated catalyst and conduct heat between the two with the gas phase state charging with catalyzer, optimize the mass transfer between gasoline and the catalyzer, conduct heat, reduce the coke in the gasoline upgrading reaction, dry gas yied reduces yield of light oil and liquid yield loss in the modifying catalytically cracked gasoline process.
Contriver's research also shows, in the reformulated gasoline gas-phase feed, regulate and the catalytic catalyst temperature of reformulated gasoline by heat exchange mode, then can further optimize mass transfer, heat transfer effect between gasoline and the catalyzer, optimize the modifying catalytically cracked gasoline process.
Based on the research to above-mentioned heavy oil fluid catalytic cracking and gasoline upgrading technology, the present invention reaches the technical problem that solution proposes by the enforcement of following technique means.
A main aspect of the present invention has provided a kind of heavy oil fluid catalytic cracking and gasoline upgrading cross complaint method, adopts the heavy oil riser reactor and the revivifier that have the auxiliary fluidizing reactor of gasoline upgrading, and described method comprises following process at least:
To introduce in the catalyzer circulation mixing tank by pipeline respectively from the reclaimable catalyst of the auxiliary fluidizing reactor of gasoline upgrading with from the regenerated catalyst of revivifier, the fluidisation water vapor is introduced from this catalyzer circulation mixing tank bottom;
Make described two strands of catalyzer after in catalyzer circulation mixing tank, carrying out thorough mixing under the effect of fluidisation water vapor, import the heavy oil riser reactor, contact with pending heavy oil feedstock, realize the catalytic cracking reaction of heavy oil, reaction oil gas and catalyzer are after reactor outlet separates, and catalyzer returns revivifier regeneration and becomes regenerated catalyst;
To introduce a regenerated catalyst water cooler from the regenerated catalyst of revivifier, it is cooled with the heat transferring medium heat exchange, assist fluidizing reactor through overcooled regenerated catalyst input gasoline upgrading;
Make and treat that reformulated gasoline is admitted to fluidizing reactor through the heat exchange processing with gas phase state and contacts, mixes and implement the upgrading reaction with described through overcooled regenerated catalyst, a reclaimable catalyst part is returned revivifier behind the upgrading, another part is injected in the described catalyzer circulation mixing tank, and upgrading oil gas enters fractionating system and carries out each fraction separation.
The present invention is to provide the technology of a kind of heavy oil fluid catalytic cracking and gasoline upgrading cross complaint, about heavy oil fluid catalytic cracking and the coupling technique of gasoline upgrading process and specifying of device, this case applicant once had a plurality of patent applications formerly to be disclosed, and the present invention will no longer do too much repeat specification to this.
The cross complaint method that proposes according to the present invention particularly, in the initial mixing condition of heavy oil riser reactor inner catalyst and heavy oil feedstock is:
Heavy oil feedstock preheating temperature: 160-350 ℃, be preferably 200-280 ℃;
Mixed catalyst temperature from catalyzer circulation mixing tank: 500-690 ℃, preferred 580-650 ℃;
The weight ratio of catalyzer and heavy oil feedstock: 5-20 is preferably 8-15.
Reaction conditions in the heavy oil riser reactor is:
Temperature of reaction: 450-550 ℃, be preferably 500-530 ℃;
The weight ratio of catalyzer and heavy oil feedstock: 5-20 is preferably 8-15;
Reaction times: 0.5-3.0s is preferably 1.5-3.0s;
Catalyst activity: 50-65;
Reaction pressure: 0.1-0.4MPa.
The method according to this invention, auxiliary fluidization reactor types can be that riser tube adds the turbulent bed reactor, the upgrading reaction conditions is:
Temperature of reaction: 350 ℃-550 ℃, be preferably 430 ℃-550 ℃, the gasoline stocks preheating temperature: 80 ℃-250 ℃, catalyzer and oil plant weight ratio: 2-20 are preferably 4-12, catalyst activity: 55-65, promote the reaction times of pipeline section: 1.0-10.0s, fluidized-bed weight space velocity: 1-1000h
-1, reaction pressure: 0.1-0.4MPa.
In heavy oil fluid catalytic cracking of the present invention and the gasoline upgrading cross complaint method, the 20-100% that generally can control the reclaimable catalyst total amount of the auxiliary fluidizing reactor output of gasoline upgrading introduces described catalyzer circulation mixing tank, and surplus is returned revivifier.For the temperature and the activity of mixing rear catalyst, can by regulate two strands of catalyzer introducing catalyzer mixed flow mixing tank (from gasoline upgrading assist the reclaimable catalyst of fluidizing reactor and from the regenerated catalyst of revivifier) logistics capacity control.
For making two strands of catalyzer energy thorough mixing that enter in the catalyzer circulation mixing tank, set catalyzer circulation mixing tank can be designed as a cylindrical tube, the inner core that coaxial setting is arranged in it, between inner core and outer cylinder body, form outer annular space, and be provided with a gas outer shroud distribution pipe in the bottom of this outer annular space, adjusting sprays into the flow of the fluidisation water vapor of outer annular space through this gas outer shroud distribution pipe, make the interior annular space of outer annular space and inner core inside have different gas speed, thereby make the density of catalyst of outer annular space and interior annular space different, rely on such density of catalyst difference to realize the close-phase circulation of catalyzer in gas mixture, promote the thorough mixing between the different catalysts.
As can be seen, at problems of the prior art, the present invention is provided with a catalyzer circulation mixing tank by the appropriate location at the riser reactor of heavy oil catalytically cracking equipment, the regenerated catalyst water cooler is set in system simultaneously, the catalyst condition of introducing heavy oil catalytically cracking equipment and the regenerated catalyst temperature of introducing the auxiliary fluidizing reactor of gasoline upgrading are regulated and control, can be realized cross complaint heavy oil fluid catalytic cracking and gasoline upgrading process.
Flow process of the present invention can specifically describe and be, the reclaimable catalyst of the auxiliary fluidizing reactor of gasoline upgrading is partly or entirely introduced the catalyzer circulation mixing tank of newly establishing, simultaneously the high temperature regeneration agent is introduced from revivifier, two bursts of catalyst stream are that fluidizing medium carries out uniform mixing with the water vapor in the circulation mixing tank, enter then in the heavy oil riser reactor pre lift zone and after promoting, contact mixing, cracking reaction takes place with heavy raw oil.Heavy oil feedstock oil mixes the back along the up reaction of heavy oil riser reactor fully with catalyzer, arrive and to enter settling vessel after the riser reactor outlet and carry out separating of catalyzer and oil gas, the oil gas that comes out enters fractionating system and carries out fractionation, carry out the water vapor stripping and the reclaimable catalyst of separating enters stripping stage, enter revivifier behind the stripping and regenerate.
Simultaneously, catalysis (upgrading) gasoline stocks enters before the auxiliary fluidizing reactor, can use conventional heat exchange mode that gasoline stocks is vaporized, and makes it enter auxiliary fluidizing reactor and regenerated catalyst contact reacts with gas phase state.Temperature head when initially contacting mixing with catalyzer and the ununiformity of conducting heat between the two in order further to reduce gasoline, before regenerated catalyst enters the auxiliary fluidizing reactor of reformulated gasoline, handle through the heat exchange of supercooler earlier, but the heat transferring medium water in the water cooler, water vapor and other oil product etc. enter auxiliary fluidizing reactor again and treat reformulated gasoline raw material contact reacts from the regenerated catalyst of revivifier is first after supercooler heat exchange cooling.The catalytic catalyst temperature of charging of gasoline stocks gas phase state and adjusting and gasoline stocks can help the conversion of gasoline olefin more, reduces the reaction of disadvantageous heat cracking reaction of gasoline upgrading process and green coke.
In the design of specific embodiments of the present invention, catalyzer circulation mixing tank can be arranged on riser reactor bottom, bottom or the next door of heavy oil catalytically cracking equipment; The regenerated catalyst water cooler also can be arranged on the revivifier next door or the auxiliary fluidization reactor bottom of heavy oil catalytically cracking equipment.Concrete scheme can comprise:
Described catalyzer circulation mixing tank is arranged at heavy oil riser reactor bottom, the top of this catalyzer circulation mixing tank and bottom all are connected with the heavy oil riser reactor, make regenerated catalyst from revivifier enter heavy oil riser reactor bottom and under the pre-lifting that promotes steam, enter catalyzer circulation mixing tank, with the thorough mixing under the fluidisation water vapor acting that is introduced into after promote steam in advance and upwards promoting of fluidisation water vapor enters the heavy oil riser reactor; Perhaps,
Described catalyzer circulation mixing tank is arranged at heavy oil riser reactor bottom, the top of this catalyzer circulation mixing tank is connected with the heavy oil riser reactor, to introduce simultaneously in this catalyzer circulation mixing tank from the regenerated catalyst of revivifier with from the reclaimable catalyst of the auxiliary fluidizing reactor of gasoline upgrading, two strands of catalyzer are under the effect of fluidisation water vapor of introducing from catalyzer circulation mixing tank bottom and pre-lifting steam, carry out thorough mixing, be raised then and enter the heavy oil riser reactor; Perhaps,
Described catalyzer circulation mixing tank is arranged at heavy oil riser reactor next door, the top of this catalyzer circulation mixing tank has catalyst transport to link to each other with heavy oil riser reactor bottom with revivifier respectively with the bottom, to assist the reclaimable catalyst of fluidizing reactor to be incorporated into simultaneously in the catalyzer circulation mixing tank from the regenerated catalyst of revivifier with from gasoline upgrading, make two strands of catalyzer under the effect of the fluidisation water vapor of introducing from catalyzer circulation mixing tank bottom, carry out thorough mixing, send into the heavy oil riser reactor through the catalyst transport of mixing tank bottom then.
Setting and use at the regenerated catalyst water cooler, above-mentioned concrete scheme can also comprise: described regenerated catalyst water cooler is located at the revivifier next door, to be incorporated into from the regenerated catalyst of revivifier and carry out heat exchange with heat transferring medium in this water cooler and be cooled, this process cooled regenerated catalyst part turns back in the revivifier by regenerated catalyst, and another part is transported to the auxiliary fluidizing reactor of reformulated gasoline; Perhaps,
Described regenerated catalyst water cooler is located at the bottom of the auxiliary fluidizing reactor of gasoline upgrading, to be incorporated into from the regenerated catalyst of revivifier and carry out heat exchange with heat transferring medium in this water cooler and be cooled, be admitted to auxiliary fluidizing reactor through cooled regenerated catalyst.
Another aspect of the present invention has provided the device of the cross complaint method that is used to realize above-mentioned heavy oil fluid catalytic cracking and gasoline upgrading, only need to transform in the suitable link of existing apparatus, set up catalyzer circulation mixing tank and regenerated catalyst water cooler, can realize method of the present invention.
The invention provides a kind of device of realizing above-mentioned heavy oil fluid catalytic cracking and gasoline upgrading cross complaint, comprise the heavy oil riser reactor and the revivifier that have the auxiliary fluidizing reactor of gasoline upgrading, wherein,
Be provided with a catalyzer circulation mixing tank in described heavy oil riser reactor bottom, the top of this mixing tank all is connected with the heavy oil riser tube with the bottom, the auxiliary fluidizing reactor of gasoline upgrading is respectively arranged with the reclaimable catalyst transfer lime that is connected and is connected with revivifier with this catalyzer circulation mixing tank, and revivifier is connected by the riser reactor of first regenerated catalyst with described catalyzer circulation mixing tank bottom;
Described device also comprises a regenerated catalyst water cooler, and revivifier is communicated with this water cooler catalyst inlet by second regenerated catalyst, and the catalyst outlet of water cooler is communicated with auxiliary fluidizing reactor by the 3rd regenerated catalyst.
The present invention also provides a kind of device of realizing above-mentioned heavy oil fluid catalytic cracking and gasoline upgrading cross complaint, comprises the heavy oil riser reactor and the revivifier that have the auxiliary fluidizing reactor of gasoline upgrading, wherein,
Described heavy oil riser reactor bottom is provided with a catalyzer circulation mixing tank, this catalyzer circulation mixing tank top is connected with the heavy oil riser reactor, the bottom is an end socket, the auxiliary fluidizing reactor of gasoline upgrading is respectively arranged with the reclaimable catalyst transfer lime that is connected and is connected with revivifier with this catalyzer circulation mixing tank, and revivifier is connected with described catalyzer circulation mixing tank bottom by first regenerated catalyst;
Described device also comprises a regenerated catalyst water cooler, and revivifier is communicated with this water cooler catalyst inlet by second regenerated catalyst, and the catalyst outlet of water cooler is communicated with auxiliary fluidizing reactor.
As specific embodiment, the present invention provides a kind of device of realizing above-mentioned heavy oil fluid catalytic cracking and gasoline upgrading cross complaint again, comprises the heavy oil riser reactor and the revivifier that have the auxiliary fluidizing reactor of gasoline upgrading, wherein,
Described heavy oil riser reactor next door is provided with a catalyzer circulation mixing tank, this mixing tank top communicates with revivifier by the 4th regenerated catalyst, the bottom communicates with the heavy oil riser reactor by the mixed catalyst transfer lime, the auxiliary fluidizing reactor of gasoline upgrading is respectively arranged with the reclaimable catalyst transfer lime that is connected and is connected with revivifier with this catalyzer circulation mixing tank, and revivifier is connected with described catalyzer circulation mixing tank bottom by first regenerated catalyst;
Described device also comprises a regenerated catalyst water cooler, and revivifier is communicated with this water cooler catalyst inlet by second regenerated catalyst, and the catalyst outlet of water cooler is communicated with auxiliary fluidizing reactor.
According to said apparatus provided by the invention, described catalyzer circulation mixing apparatus has a cylindrical outer cylinder body, is provided with a co-axial cylindrical inner core in it, forms annular space between the inside and outside cylindrical shell; Outer cylinder body top and bottom are communicated with heavy oil riser reactor and/or revivifier respectively, are communicated with the outer cylinder body side from the reclaimable catalyst transfer lime of the stripping stage of auxiliary fluidizing reactor; The ratio of described inner diameter of steel flue and urceolus diameter is 1:5-3:5, and the ratio of inner core height and urceolus height is 1:4-3:4; Described annular space bottom is provided with the water vapor distribution pipe.
Being provided with the regenerated catalyst water cooler is one of key of the present invention, according to the specific design scheme, described regenerated catalyst water cooler is arranged at the revivifier next door, the catalyst outlet of water cooler is communicated with auxiliary fluidizing reactor by the 3rd regenerated catalyst, also is provided with the regenerated catalyst loop between water cooler and the revivifier; Perhaps,
Described regenerated catalyst water cooler is arranged at the bottom of the auxiliary fluidizing reactor of gasoline upgrading, the top of regenerated catalyst water cooler is a catalyst outlet, be connected with auxiliary fluidizing reactor, the bottom is an end socket, is located between the lateral catalyst inlet of its cylindrical shell and the revivifier this moment to be communicated with by second regenerated catalyst.
Auxiliary fluidizing reactor of the present invention can be that riser tube adds the turbulent bed reactor.In addition, auxiliary fluidizing reactor of the present invention has independent stripping system and sedimenting system.
The cross complaint method of heavy oil fluid catalytic cracking of the present invention and gasoline upgrading, used catalyzer 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 contain 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.
The advantage of Technology provided by the invention is for utilizing catalyzer circulation mixing tank, with the high reactivity behind the process stripping in the auxiliary fluidizing reactor of gasoline upgrading, the reclaimable catalyst of low temperature and the high-temperature regenerated catalyst that attracts from revivifier mix the back and introduce in the heavy oil riser reactor contact with stock oil (heavy oil) and mix the generation catalytic cracking reaction, by regulating the introducing amount of two bursts of catalyst stream, the temperature and the active regulation and control that can realize counterweight oil riser catalyst in reactor and stock oil contact reacts initial mixing state of mixing rear catalyst, obviously improve the ununiformity that stock oil and catalyzer initially contact the temperature head when mixing and conduct heat between the two, reduce coke and dry gas yied; Simultaneously, make the catalytic gasoline raw material enter auxiliary fluidizing reactor by conventional heat exchange with gas phase state, utilize the regenerated catalyst water cooler that the catalyst temperature that enters auxiliary fluidizing reactor is regulated, further optimize mass transfer, heat transfer effect between gasoline and the catalyzer, thereby realize heavy oil catalytic cracking reaction and the effective cross complaint of gasoline upgrading process.The present invention is by the flexible mutual regulation and control of adjusting catalyst temperature, activity and the realization of reformulated gasoline feed state of participation heavy oil catalytic cracking reaction to heavy oil fluid catalytic cracking and gasoline upgrading process, improving the heavy oil fluid catalytic cracking product distributes, can strengthen simultaneously the effect that auxiliary fluidizing reactor reduces olefin(e) centent and sulphur content again, device is changed little, flow process is simple, be easy to realize, and be easy to control, stable operation.Test shows that enforcement of the present invention can be reduced to catalytic cracking gasoline olefine content 18 and (v) below the %, when satisfying the national environmental protection laws and regulations requirement, improve the yield of lightweight oil.
Description of drawings
Fig. 1 is that the embodiment of the invention 1 adopts heavy oil riser reactor and the revivifier that has the auxiliary fluidization reactor assembly of gasoline upgrading, realizes the schematic flow sheet of heavy oil fluid catalytic cracking and gasoline upgrading cross complaint.
Fig. 2 is the process flow diagram of the embodiment of the invention 2, and catalyzer circulation mixing tank wherein is provided with different with embodiment 1.
Fig. 3 is the process flow diagram of the embodiment of the invention 3, and catalyzer circulation mixing tank setting wherein is also different with embodiment 1.
Fig. 4-Fig. 6 is respectively to device and process flow diagram after the setting of regenerated catalyst water cooler changes among Fig. 1-Fig. 3.
Embodiment
Further specify implementation process of the present invention and characteristics below in conjunction with the drawings and specific embodiments, be intended to help the reader to understand design philosophy of the present invention and implementation result better, can not be interpreted as any qualification embodiment of the present invention.
The visible Fig. 1 of technical process: set up a catalyzer circulation mixing tank 12 in industrial catalyticing cracking device heavy oil riser reactor 4 bottoms that have the auxiliary fluidizing reactor of catalytic gasoline upgrading, the top of catalyzer circulation mixing tank 12, bottom all are connected with heavy oil riser reactor 4.Catalyzer circulation mixing tank 12 is cylindrical tubes, the inside is coaxial to be provided with an inner core 14, in, form outer ring space between the outer cylinder body, a gas outer shroud distribution pipe 13 is set in the bottom of this annular space, water vapor 32 enters annular space in the catalyzer circulation mixing tank 12 as fluidizing medium by gas outer shroud distribution pipe 13, by regulating the flow that water vapor 32 enters catalyzer circulation mixing tank 12, make the gas speed of catalyzer circulation mixing tank 12 outer annular space be lower than the gas speed of the interior annular space that inner core 14 surrounds, so just make the density of catalyst of outer annular space be higher than the density of catalyst of interior annular space, rely on the density of catalyst difference between the inner and outer ring can realize the close phase annularly flow of catalyzer in mixing tank, promote the thorough mixing between the different catalysts.
Regenerated catalyst from revivifier 1 enters into heavy oil riser reactor 4 bottoms through first regenerated catalyst 11 and catalyst stream control valve 17, under the pre-lifting that promotes steam 28, enter catalyzer circulation mixing tank 12 from the bottom, (this part is the 20-100% of this reclaimable catalyst total amount to a part by the next reclaimable catalyst of the auxiliary fluidization reactive system of catalytic gasoline upgrading simultaneously, another part turns back to revivifier 1 through reclaimable catalyst transfer lime 23 and reclaimable catalyst flowrate control valve 24) through reclaimable catalyst transfer lime 25 and reclaimable catalyst flowrate control valve 26 also introduce 12, two bursts of catalyst stream of catalyzer circulation mixing tank at fluidisation water vapor 32 that catalyzer circulation mixing tank 12 bottom gas outer shroud distribution pipes 13 are introduced and under through the acting in conjunction of the pre-lifting steam 28 of heavy oil riser reactor 4 inflow catalyst circulation mixing tanks 12 by close-phase circulation and thorough mixing.For temperature of mixing rear catalyst and active can control by regulating two bursts of catalyst stream amount ratios introducing catalyzer circulation mixing tank 12, the temperature of catalyzer after heat exchange from catalyzer circulation mixing tank generally can be 500 ℃-690 ℃, is preferably 580 ℃-650 ℃.
After fully mixed mixed catalyst promotes upwards promoting of steam 28 and fluidisation water vapor 32 and enters heavy oil riser reactor 4 through pre-in catalyzer circulation mixing tank 12, contact with the heavy oil feedstock 30 that contains atomizing steam, gasification, mix and catalytic cracking reaction, temperature during initial mixing in heavy oil riser reactor 4 of control catalyst and stock oil (heavy oil feedstock) is 500 ℃-690 ℃, be preferably 580 ℃-650 ℃, the weight ratio of catalyzer and oil plant is 5-20 during mixing, be preferably 8-15, the heavy oil feedstock preheating temperature is 160 ℃-350 ℃, is preferably 200 ℃-280 ℃.Mixing back oil gas and catalyzer upwards flows along heavy oil riser reactor 4, control that temperature of reaction is 450 ℃-550 ℃ in this heavy oil riser reactor 4, be preferably 500-530 ℃, reaction times is 0.5-3.5s, 1.5-3.0s preferably, catalyst activity is 50-65, and reaction pressure is 0.1-0.4MPa.Reaction oil gas arrives the outlet of heavy oil riser reactor, revolves 6 with reaction oil gas 8 and reclaimable catalyst separately by fast gas-solid separator 5 and settling vessel top, and reclaimable catalyst enters stripping stage 10 through settling vessel 9, enters revivifier 1 through behind the stripping.Reaction oil gas 8 enters the separation that fractionation plant carries out rich gas, raw gasline lighting end, raw gasline last running, diesel oil, recycle stock, slurry oil through collection chamber 7.
Set up a regenerated catalyst water cooler 37 on revivifier 1 next door, regenerated catalyst enters regenerated catalyst water cooler 37 through second regenerated catalyst 2 from catalyst inlet and cools off with heat transferring medium 39 (comprising water, water vapor and other oil product etc.) heat-shift, the cooled regenerated catalyst temperature is 500 ℃-690 ℃, and optimum value is 580 ℃-650 ℃.A cooled regenerated catalyst part is returned revivifier 1 through catalyst recirculation pipe 38 under the effect that promotes wind 40 (comprising air and water vapor), a part enters auxiliary fluidizing reactor 18 (riser tube adds the turbulent bed reactor) from catalyst outlet through the 3rd regenerated catalyst and flowrate control valve 3.Simultaneously, catalytic gasoline raw material 29 is entering auxiliary fluidizing reactor 18 through conventional heat exchange vaporization back with atomizing steam, with be 350-550 ℃ from regenerated catalyst water cooler 37 and the regenerated catalyst that promotes by water vapor 27 in temperature of reaction, the gasoline stocks preheating temperature is 80-250 ℃, catalyzer and oil plant (gasoline stocks) weight ratio is 2-20, preferred 4-12, catalyst activity is 55-65, reaction times is 1.0-10.0s, reaction pressure is to contact under the condition of 0.1-0.4MPa, mix and the upgrading reaction, oil gas, water vapor passes through auxiliary fluidizing reactor 18 with catalyzer, upgrading oil gas 21 passes through elementary cyclonic separator with catalyzer and enter fractionation plant 19 back separating in settling vessel 20, reclaimable catalyst enters stripping stage 22, through the reclaimable catalyst transfer lime 25 of a part of reclaimable catalyst through being connected behind water vapor 31 strippings with settling vessel 20, reclaimable catalyst flowrate control valve 26 enters (this part is the 20-100% of total amount) in the catalyzer circulation mixing tank 12, and a part of reclaimable catalyst carries out coke burning regeneration through reclaimable catalyst transfer lime 23 and reclaimable catalyst flowrate control valve 24 introducing revivifiers 1.
Referring to flow process shown in Figure 2, be summarized as follows: set up a catalyzer circulation mixing tank 12 in industrial catalyticing cracking device heavy oil riser reactor 4 bottoms that have the auxiliary fluidizing reactor of catalytic gasoline upgrading, the top of catalyzer circulation mixing tank 12 is connected with heavy oil riser reactor 4, and the bottom of catalyzer circulation mixing tank 12 is an end socket.Catalyzer circulation mixing tank 12 is cylindrical tubes, the inside is provided with an inner core 14, form outer annular space between the outer wall of inner core 14 and catalyzer circulation mixing tank 12, a gas outer shroud distribution pipe 13 is set in the bottom of this annular space, water vapor 32 enters outer annular space in the catalyzer circulation mixing tank 12 by gas outer shroud distribution pipe 13, the pre-lifting steam 28 of original weight oil riser reactor 4 bottoms enters the interior annular space of catalyzer circulation mixing tank 12, by regulating as the water vapor 32 of fluidizing medium and promoting the flow that steam 28 enters catalyzer circulation mixing tank 12 in advance, make the gas speed of the high cycle speed of the interior annular space that inner core 14 surrounds in the catalyzer circulation mixing tank 12 in outer annular space, be lower than the density of catalyst of outer annular space like this with regard to the density of catalyst of annular space in making, rely on the density difference between the inner and outer ring can realize the close phase annularly flow of catalyzer in mixing tank, promote the thorough mixing between the different catalysts.
Enter into the bottom of catalyzer circulation mixing tank 12 through first regenerated catalyst 11 and catalyst stream control valve 17 from the regenerated catalyst of revivifier 1, (this part is the 20-100% of total amount to the reclaimable catalyst that a part is come by the auxiliary fluidization reactive system of catalytic gasoline upgrading, another part turns back in the revivifier 1 through reclaimable catalyst transfer lime 23 and reclaimable catalyst flowrate control valve 24) also introduce 12, two bursts of catalyst stream of catalyzer circulation mixing tank through reclaimable catalyst transfer lime 25 and reclaimable catalyst flowrate control valve 26 and under fluidisation water vapor 32 that catalyzer circulation mixing tank 12 bottom gas outer shroud distribution pipes 13 are introduced and the pre-acting in conjunction that promotes steam 28, produce close-phase circulation and thorough mixing.For temperature of mixing rear catalyst and active can control by regulating two bursts of catalyst stream amounts introducing catalyzer circulation mixing tank 12, the temperature of catalyzer after heat exchange from catalyzer circulation mixing tank generally can be 500 ℃-690 ℃, is preferably 580 ℃-650 ℃.
After fully mixed catalyzer upwards promotes and enters heavy oil riser reactor 4 through pre-steam 28 and the fluidisation water vapor 32 of promoting in catalyzer circulation mixing tank 12, contact with the heavy oil feedstock 30 that contains atomizing steam, gasify, mixing and catalytic cracking reaction, temperature during initial mixing in heavy oil riser reactor 4 of control catalyst and stock oil is 500-690 ℃, be preferably 580-650 ℃, catalyzer oil plant weight ratio is 5-20 during mixing, be preferably 8-15, the heavy oil feedstock preheating temperature is 160-350 ℃, is preferably 200-280 ℃.Mixing back oil gas and catalyzer upwards flows along heavy oil riser reactor 4, controlling these heavy oil riser reactor 4 temperature of reaction is 450-550 ℃, be preferably 500-530 ℃, reaction times is 0.5-3.5s, 1.5-3.0s preferably, catalyst activity is 50-65, and reaction pressure is 0.1-0.4MPa.Reaction oil gas arrives the outlet of heavy oil riser reactor, revolves 6 with reaction oil gas 8 and catalyzer separately by fast gas-solid separator 5 and settling vessel top, and reclaimable catalyst enters stripping stage 10 through settling vessel 9, enters revivifier 1 through behind the stripping.Reaction oil gas 8 enters the separation that fractionation plant carries out rich gas, raw gasline lighting end, raw gasline last running, diesel oil, recycle stock, slurry oil through collection chamber 7.
Set up a regenerated catalyst water cooler 37 on revivifier 1 next door, regenerated catalyst enters regenerated catalyst water cooler 37 through second regenerated catalyst 2 from catalyst inlet and cools off with heat transferring medium 39 (comprising water, water vapor and other oil product etc.) heat-shift, the cooled regenerated catalyst temperature is 500-690 ℃, and optimum value is 580-650 ℃.A cooled regenerated catalyst part is returned revivifier 1 through catalyst recirculation pipe 38 under the effect that promotes wind 40 (comprising air and water vapor), a part enters auxiliary fluidizing reactor 18 (riser tube adds the turbulent bed reactor) from catalyst outlet through the 3rd regenerated catalyst and flowrate control valve 3.Simultaneously, catalytic gasoline raw material 29 is entering auxiliary fluidizing reactor 18 through conventional heat exchange vaporization back with atomizing steam, with be 350-550 ℃ from regenerated catalyst water cooler 37 and the regenerated catalyst that promotes by water vapor 27 in temperature of reaction, the gasoline stocks preheating temperature is 80-250 ℃, catalyzer and oil plant weight ratio are 2-20, preferred value is 4-12, catalyst activity is 55-65, reaction times is 1.0-10.0s, reaction pressure is to contact under the condition of 0.1-0.4MPa, mix and the upgrading reaction, oil gas, water vapor passes through auxiliary fluidizing reactor 18 with catalyzer, upgrading oil gas 21 passes through elementary cyclonic separator with catalyzer and enter fractionation plant 19 back separating in settling vessel 20, reclaimable catalyst enters stripping stage 22, through the reclaimable catalyst transfer lime 25 of a part of reclaimable catalyst through being connected behind water vapor 31 strippings with settling vessel 20, reclaimable catalyst flowrate control valve 26 enters (this part is the 20-100% of total amount) in the catalyzer circulation mixing tank 12, and a part of reclaimable catalyst carries out coke burning regeneration through reclaimable catalyst transfer lime 23 and reclaimable catalyst flowrate control valve 24 introducing revivifiers 1.
Referring to flow process shown in Figure 3, be summarized as follows: set up a catalyzer circulation mixing tank 12 on industrial catalyticing cracking device heavy oil riser reactor 4 next doors that have the auxiliary fluidizing reactor of catalytic gasoline upgrading, the top of catalyzer circulation mixing tank 12 is connected with the 4th regenerated catalyst 15, and the bottom of catalyzer circulation mixing tank 12 is connected with mixed catalyst transfer lime 16.Catalyzer circulation mixing tank 12 is cylindrical tubes, the inside is provided with an inner core 14, form outer annular space between the outer wall of inner core 14 and catalyzer circulation mixing tank 12, a gas outer shroud distribution pipe 13 is set in the bottom of this annular space, water vapor 32 enters outer annular space in the catalyzer circulation mixing tank 12 by gas outer shroud distribution pipe 13, the gas speed of the interior annular space that the high cycle speed that makes the outer annular space in the catalyzer circulation mixing tank 12 surrounds in inner core 14, so just make the density of catalyst of outer annular space be lower than the density of catalyst of interior annular space, rely on the density difference between the inner and outer ring can realize the close phase annularly flow of catalyzer in mixing tank, promote the thorough mixing between the different catalysts.
Enter into the bottom of catalyzer circulation mixing tank 12 through first regenerated catalyst 11 from the regenerated catalyst of revivifier 1, (this part is the 20-100% of total amount to the reclaimable catalyst that a part is come by the auxiliary fluidization reactive system of catalytic gasoline upgrading, another part turns back in the former revivifier 1 through reclaimable catalyst transfer lime 23 and reclaimable catalyst flowrate control valve 24) also introduce in this catalyzer circulation mixing tank 12 through reclaimable catalyst transfer lime 25 and reclaimable catalyst flowrate control valve 26, close-phase circulation takes place and thorough mixing in two bursts of catalyst stream under the effect of the fluidisation water vapor 32 that catalyzer circulation mixing tank 12 bottom gas outer shroud distribution pipes 13 are introduced, the fluidizing medium of carrying little amount of catalyst secretly returns in the revivifier 1 through the 4th catalyst transport 15.For temperature of mixing rear catalyst and active can control by regulating two bursts of catalyst stream amounts introducing catalyzer circulation mixing tank 12, the temperature of catalyzer after heat exchange from catalyzer circulation mixing tank generally can be 500-690 ℃, is preferably 580-650 ℃.
After fully mixed catalyzer enters the bottom of heavy oil riser reactor 4 through mixed catalyst transfer lime 16 and catalyst stream control valve 17 in catalyzer circulation mixing tank 12, upwards promote by pre-lifting steam 28, contact with the heavy oil feedstock 30 that contains atomizing steam, gasification, mix and catalytic cracking reaction, temperature during initial mixing in heavy oil riser reactor 4 of control catalyst and stock oil is 500-690 ℃, be preferably 580-650 ℃, catalyzer oil plant weight ratio is 5-20 during mixing, be preferably 8-15, the heavy oil feedstock preheating temperature is 160-350 ℃, is preferably 200-280 ℃.Mixing back oil gas and catalyzer upwards flows along heavy oil riser reactor 4, controlling these heavy oil riser reactor 4 temperature of reaction is 450-550 ℃, be preferably 500-530 ℃, reaction times is 0.5-3.5s, 1.5-3.0s preferably, catalyst activity is 50-65, and reaction pressure is 0.1-0.4MPa.Reaction oil gas arrives the outlet of heavy oil riser reactor, revolves 6 with reaction oil gas 8 and catalyzer separately by fast gas-solid separator 5 and settling vessel top, and reclaimable catalyst enters stripping stage 10 through settling vessel 9, enters revivifier 1 through behind the stripping.Reaction oil gas 8 enters the separation that fractionation plant carries out rich gas, raw gasline lighting end, raw gasline last running, diesel oil, recycle stock, slurry oil through collection chamber 7.
Set up a regenerated catalyst water cooler 37 on revivifier 1 next door, regenerated catalyst enters regenerated catalyst water cooler 37 through second regenerated catalyst 2 from the regenerated catalyst inlet and cools off with heat transferring medium 39 (comprising water, water vapor and other oil product etc.) heat-shift, the cooled regenerated catalyst temperature is 500-690 ℃, and optimum value is 580-650 ℃.A cooled regenerated catalyst part is returned revivifier 1 through catalyst recirculation pipe 38 under the effect that promotes wind 40 (comprising air and water vapor), a part enters auxiliary fluidizing reactor 18 (riser tube adds the turbulent bed reactor) from the regenerated catalyst outlet through the 3rd regenerated catalyst and flowrate control valve 3.Simultaneously, catalytic gasoline raw material 29 is entering auxiliary fluidizing reactor 18 through conventional heat exchange vaporization back with atomizing steam, with be 350-550 ℃ from regenerated catalyst water cooler 37 and the regenerated catalyst that promotes by water vapor 27 in temperature of reaction, the gasoline stocks preheating temperature is 80-250 ℃, catalyzer and oil plant weight ratio are 2-20, preferred 4-12, catalyst activity is 55-65, reaction times is 1.0-10.0s, reaction pressure is to contact under the condition of 0.1-0.4MPa, mix and the upgrading reaction, oil gas, water vapor passes through auxiliary fluidizing reactor 18 with catalyzer, upgrading oil gas 21 passes through elementary cyclonic separator with catalyzer and enter fractionation plant 19 back separating in settling vessel 20, reclaimable catalyst enters stripping stage 22, through the reclaimable catalyst transfer lime 25 of a part of reclaimable catalyst through being connected behind water vapor 31 strippings with settling vessel 20, reclaimable catalyst flowrate control valve 26 enters (this part is the 20-100% of total amount) in the catalyzer circulation mixing tank 12, and a part of reclaimable catalyst carries out coke burning regeneration through reclaimable catalyst transfer lime 23 and reclaimable catalyst flowrate control valve 24 introducing revivifiers 1.
Embodiment 4
The present invention also realizes by the different set-up modes to regenerated catalyst water cooler 37 for the regulative mode that enters the regenerated catalyst temperature that auxiliary fluidizing reactor comes in contact, mixes and react with catalytic gasoline.
Referring to Fig. 4,, the regenerated catalyst water cooler assists the fluidization reactor bottom for being arranged at the difference of embodiment 1.Idiographic flow is described as: the bottom of the auxiliary fluidizing reactor that the catalytic gasoline upgrading is used is provided with a regenerated catalyst water cooler 37, the top of regenerated catalyst water cooler 37 is connected with auxiliary fluidizing reactor 18, the bottom of regenerated catalyst water cooler 37 is an end socket, and catalyst inlet is located at the water cooler side.Heat transferring medium 39 (comprising water, water vapor and other oil product etc.) enters regenerated catalyst water cooler 37 and carries out thermal exchange from revivifier 1 through the regenerated catalyst of second catalyst transport 2 and regenerated catalyst flowrate control valve 3, the cooled regenerated catalyst temperature is 500-690 ℃, and optimum value is 580-650 ℃.
In catalyst cooler 37, upwards promote and enter auxiliary fluidization riser reactor 18 through the pre-steam 27 that promotes through the regenerated catalyst after the abundant heat exchange, contact, gasify, mix and react with the catalytic gasoline raw material 29 after the conventional heat exchange vaporization of the process that contains atomizing steam, temperature of reaction in the auxiliary fluidizing reactor 18 of control is 350-550 ℃, the gasoline stocks preheating temperature is 80-250 ℃, catalyzer oil plant weight ratio is 2-20, catalyst activity is 55-65, reaction times is 1.0-10.0s, and reaction pressure is 0.1-0.4MPa.Upgrading oil gas 21 passes through elementary cyclonic separator with catalyzer and enter fractionation plant 19 back separating in settling vessel 20, reclaimable catalyst enters stripping stage 22, enter (this part is the 20-100% of total amount) in the catalyzer circulation mixing tank 12 through a part of reclaimable catalyst behind water vapor 31 strippings through reclaimable catalyst transfer lime 25, the reclaimable catalyst flowrate control valve 26 that settling vessel 20 is connected, another part reclaimable catalyst enters revivifier 1 through reclaimable catalyst transfer lime 23 and reclaimable catalyst flowrate control valve 24 and carries out coke burning regeneration.
The flow process of other parts is all identical with embodiment 1 with processing condition among this embodiment.
Similarly, on the basis of embodiment 2 and 3, change the set-up mode of regenerated catalyst water cooler, obtain the flow process of Fig. 5 and Fig. 6 respectively, no longer be repeated in this description.
The test example
For verifying implementation result of the present invention, adopt the flow process (flow process shown in Figure 1) of embodiment 1 and the heavy oil fluid catalytic cracking of routine and the comparison that the catalytic gasoline modifying process carries out heavy oil fluid catalytic cracking and gasoline upgrading operation at present, table 1 and table 2 are raw material condition, table 3 is the main technique condition, the CC-20D catalyzer that all tests all use the Chang Ling catalyst plant to produce, test-results is listed in table 4.
Table 1 heavy oil feedstock character
| Project | Data | Project | Data |
| Density (20 ℃) kg/m 3 | 960 | Nitrogen content, ppm | 2000 |
| Carbon residue, wt% | 5.6 | Hydrocarbon group composition analysis | |
| Ultimate analysis | Stable hydrocarbon, wt% | 57.61 | |
| Hydrogen richness, wt% | 11.71 | Aromatic hydrocarbons, wt% | 24.96 |
| Carbon content, wt% | 86.62 | Colloid, wt% | 13.34 |
| Sulphur content, wt% | 0.6 | Bituminous matter, wt% | 0.44 |
Table 2 is wanted the gasoline stocks character of upgrading
| Project | Data | Project | Data |
| Density (20 ℃) kg/m 3 | 731.0 | Mercaptan sulfur, ppm | 68 |
| Octane value | Total sulfur, wt% | 0.04 | |
| RON | 78.7 | Hydrocarbon group composition analysis | |
| MON | 89.5 | Stable hydrocarbon, v% | 35.6 |
| Initial boiling point, ℃ | 39.0 | Alkene, v% | 51.2 |
| Final boiling point, ℃ | 193.0 | Aromatic hydrocarbons, v% | 13.2 |
Table 3 main technique condition
In table 3, the prior art option A adopts conventional heavy oil fluid catalytic cracking and catalytic gasoline modifying process technology: 700 ℃ of the temperature of revivifier inner catalyst, enter heavy oil riser reactor, the auxiliary fluidizing reactor of gasoline upgrading and the catalytic catalyst temperature of stock oil up to 680 ℃, the preheating temperature of heavy oil feedstock oil, catalytic gasoline raw material is respectively 180 ℃ and 40 ℃, and the temperature difference of raw material and catalyzer is very big.Can cause the inhomogeneous of raw material and catalyzer mass transfer and heat transfer like this, heat cracking reaction aggravation, the result can make the gain in yield of dry gas and coke in the product.
Unlike the prior art, among the solution of the present invention B, guaranteeing under 700 ℃ of constant conditions of revivifier inner catalyst temperature, utilize the regenerated catalyst water cooler to make to enter the catalyst temperature of the auxiliary fluidizing reactor of gasoline upgrading to be reduced to 600 ℃, use conventional heat exchange to make under the condition of upgrading catalytic gasoline raw material with 200 ℃ of gas phase states and enter auxiliary fluidizing reactor, the temperature difference of raw material and catalyzer is dwindled greatly, can further optimize the gasoline upgrading reaction like this under the condition of rising agent oil ratio.
Simultaneously the reclaimable catalyst that still has greater activity behind the catalytic gasoline upgrading being introduced the circulation mixing tank mixes with high-temperature regenerated catalyst, realization is participated in catalysts temperature and active regulation and control to entering the heavy oil riser reactor, temperature is 630 ℃ after two kinds of catalyst mix, the catalyst temperature that enters the heavy oil riser reactor than scheme A has reduced by 50 ℃, can improve raw material preheating temperature to 260 ℃ like this, agent-oil ratio 10 situation under realize regulation and control to heavy oil catalytic cracking reaction.
Table 4 product distributes and character
| Product distributes and character | The prior art option A | The present invention program B |
| H 2S | 0.5 | 0.7 |
| Fuel gas | 6.2 | 5.7 |
| Liquefied gas | 15.5 | 16.2 |
| Gasoline | 41.1 | 43.3 |
| Diesel oil | 20.3 | 19.4 |
| Clarified oil | 6.8 | 5.7 |
| Coke | 9.6 | 9.0 |
| Add up to | 100.0 | 100.0 |
| Stable gasoline character | The prior art option A | The present invention program B |
| Olefin(e) centent | 33.8 | 18.5 |
| Saturated hydrocarbon content | 50.8 | 58.2 |
| Aromaticity content | 15.4 | 23.3 |
| Sulphur content | 281 | 112 |
| Octane value RON | 89.3 | 90.8 |
Claims (19)
1, a kind of heavy oil fluid catalytic cracking and gasoline upgrading cross complaint method, employing has the heavy oil riser reactor and the revivifier of the auxiliary fluidizing reactor of gasoline upgrading, and the auxiliary fluidization reactor types of gasoline upgrading is that riser tube adds the turbulent bed reactor, and described method comprises following process at least:
To introduce in the catalyzer circulation mixing tank by pipeline respectively from the reclaimable catalyst of the auxiliary fluidizing reactor of gasoline upgrading with from the regenerated catalyst of revivifier, the fluidisation water vapor is introduced from this catalyzer circulation mixing tank bottom;
Make described two strands of catalyzer after in catalyzer circulation mixing tank, carrying out thorough mixing under the effect of fluidisation water vapor, import the heavy oil riser reactor, contact with pending heavy oil feedstock, realize the catalytic cracking reaction of heavy oil, reaction oil gas and catalyzer are after reactor outlet separates, and catalyzer returns revivifier regeneration and becomes regenerated catalyst;
To introduce a regenerated catalyst water cooler from the regenerated catalyst of revivifier, and make it be cooled to 500-690 ℃, should import gasoline upgrading through overcooled regenerated catalyst and assist fluidizing reactor with the heat transferring medium heat exchange;
Make and treat that reformulated gasoline is admitted to fluidizing reactor through the heat exchange processing with gas phase state and contacts, mixes and implement the upgrading reaction with described through overcooled regenerated catalyst, a reclaimable catalyst part is returned revivifier behind the upgrading, another part is injected in the described catalyzer circulation mixing tank, and upgrading oil gas enters fractionating system and carries out each fraction separation.
2, heavy oil fluid catalytic cracking according to claim 1 and gasoline upgrading cross complaint method, wherein, described catalyzer circulation mixing tank is two cylindrical shells of coaxial setting, form outer annular space between inside and outside cylindrical shell, introduce the fluidisation water vapor by the gas outer shroud distribution pipe that is arranged at this outer annular space bottom, and the flow of adjusting fluidisation water vapor, the interior annular space that outer annular space and inner barrel are surrounded has different gas speed, utilizes catalyzer to form circulation and realize thorough mixing to two strands of catalyzer at inner and outer rings spatial density difference.
3, heavy oil fluid catalytic cracking according to claim 1 and gasoline upgrading cross complaint method, wherein,
Initial mixing condition at heavy oil riser reactor inner catalyst and heavy oil feedstock is:
Heavy oil feedstock preheating temperature: 160-350 ℃;
Mixed catalyst temperature from catalyzer circulation mixing tank: 500-690 ℃;
The weight ratio of catalyzer and heavy oil feedstock: 5-20.
4, heavy oil fluid catalytic cracking according to claim 1 and gasoline upgrading cross complaint method, wherein, the reaction conditions in the heavy oil riser reactor is:
Temperature of reaction: 450-550 ℃;
The weight ratio of catalyzer and heavy oil feedstock: 5-20;
Reaction times: 0.5-3.0s;
Catalyst activity: 50-65;
Reaction pressure: 0.1-0.4MPa.
5, heavy oil fluid catalytic cracking according to claim 1 and gasoline upgrading cross complaint method, wherein, the auxiliary fluidization reactor types of described gasoline upgrading is that riser tube adds the turbulent bed reactor, the upgrading reaction conditions is:
Temperature of reaction: 350-550 ℃, gasoline stocks preheating temperature: 80-250 ℃, catalyzer oil plant weight ratio: 2-20, catalyst activity: 55-65, the reaction times of lifting pipeline section: 1.0-10.0s, fluidized-bed weight space velocity: 1-1000h
-1, reaction pressure: 0.1-0.4MPa.
6, according to each described heavy oil fluid catalytic cracking of claim 2-5 and gasoline upgrading cross complaint method, wherein, the 20-100% of the reclaimable catalyst total amount of the auxiliary fluidizing reactor output of gasoline upgrading introduces described catalyzer circulation mixing tank, and surplus is returned revivifier.
7, heavy oil fluid catalytic cracking according to claim 1 and gasoline upgrading cross complaint method, wherein, described catalyzer circulation mixing tank is arranged at heavy oil riser reactor bottom, the top of this catalyzer circulation mixing tank and bottom all are connected with the heavy oil riser reactor, make regenerated catalyst from revivifier enter heavy oil riser reactor bottom and under the pre-lifting that promotes steam, enter catalyzer circulation mixing tank, with the thorough mixing under the fluidisation water vapor acting that is introduced into after promote steam in advance and upwards promoting of fluidisation water vapor enters the heavy oil riser reactor.
8, heavy oil fluid catalytic cracking according to claim 1 and gasoline upgrading cross complaint method, wherein, described catalyzer circulation mixing tank is arranged at heavy oil riser reactor bottom, the top of this catalyzer circulation mixing tank is connected with the heavy oil riser reactor, to introduce simultaneously in this catalyzer circulation mixing tank from the regenerated catalyst of revivifier with from the reclaimable catalyst of the auxiliary fluidizing reactor of gasoline upgrading, two strands of catalyzer are under the effect of fluidisation water vapor of introducing from catalyzer circulation mixing tank bottom and pre-lifting steam, carry out thorough mixing, be raised then and enter the heavy oil riser reactor.
9, heavy oil fluid catalytic cracking according to claim 1 and gasoline upgrading cross complaint method, wherein, described catalyzer circulation mixing tank is arranged at heavy oil riser reactor next door, the top of this catalyzer circulation mixing tank has catalyst transport to link to each other with heavy oil riser reactor bottom with revivifier respectively with the bottom, to assist the reclaimable catalyst of fluidizing reactor to be incorporated into simultaneously in the catalyzer circulation mixing tank from the regenerated catalyst of revivifier with from gasoline upgrading, make two strands of catalyzer under the effect of the fluidisation water vapor of introducing from catalyzer circulation mixing tank bottom, carry out thorough mixing, send into the heavy oil riser reactor through the catalyst transport of mixing tank bottom then.
10, according to claim 1,7,8 or 9 described heavy oil fluid catalytic cracking and gasoline upgrading cross complaint method, wherein, described regenerated catalyst water cooler is located at the revivifier next door, to be incorporated into from the regenerated catalyst of revivifier and carry out heat exchange with heat transferring medium in this water cooler and be cooled, this process cooled regenerated catalyst part turns back in the revivifier by regenerated catalyst, and another part is transported to auxiliary fluidizing reactor.
11, according to claim 1,7,8 or 9 described heavy oil fluid catalytic cracking and gasoline upgrading cross complaint method, wherein, described regenerated catalyst water cooler is located at the bottom of the auxiliary fluidizing reactor of gasoline upgrading, to be incorporated into from the regenerated catalyst of revivifier and carry out heat exchange with heat transferring medium in this water cooler and be cooled, be admitted to auxiliary fluidizing reactor through cooled regenerated catalyst.
12, a kind of device of realizing described heavy oil fluid catalytic cracking of claim 1 and gasoline upgrading cross complaint method comprises the heavy oil riser reactor and the revivifier that have the auxiliary fluidizing reactor of gasoline upgrading, wherein,
Be provided with a catalyzer circulation mixing tank in described heavy oil riser reactor bottom, the top of this mixing tank all is connected with the heavy oil riser tube with the bottom, the auxiliary fluidizing reactor of gasoline upgrading is respectively arranged with the reclaimable catalyst transfer lime that is connected and is connected with revivifier with this catalyzer circulation mixing tank, and revivifier is connected by the riser reactor of first regenerated catalyst with described catalyzer circulation mixing tank bottom;
Described device also comprises a regenerated catalyst water cooler, and revivifier is communicated with this water cooler catalyst inlet by second regenerated catalyst, and the catalyst outlet of water cooler is communicated with auxiliary fluidizing reactor.
13, device according to claim 12, wherein, described catalyzer circulation mixing apparatus has a cylindrical outer cylinder body, is provided with a co-axial cylindrical inner core in it, forms outer annular space between the inside and outside cylindrical shell; Outer cylinder body top and bottom are communicated with the heavy oil riser reactor respectively, are communicated with the outer cylinder body side from the reclaimable catalyst transfer lime of the stripping stage of auxiliary fluidizing reactor; The ratio of described inner diameter of steel flue and urceolus diameter is 1:5-3:5, and the ratio of inner core height and urceolus height is 1:4-3:4; Described outer annular space bottom is provided with the water vapor distribution pipe.
14, a kind of device of realizing described heavy oil fluid catalytic cracking of claim 1 and gasoline upgrading cross complaint comprises the heavy oil riser reactor and the revivifier that have the auxiliary fluidizing reactor of gasoline upgrading, wherein,
Described heavy oil riser reactor bottom is provided with a catalyzer circulation mixing tank, this catalyzer circulation mixing tank top is connected with the heavy oil riser reactor, the bottom is an end socket, the auxiliary fluidizing reactor of gasoline upgrading is respectively arranged with the reclaimable catalyst transfer lime that is connected and is connected with revivifier with this catalyzer circulation mixing tank, and revivifier is connected with described catalyzer circulation mixing tank bottom by first regenerated catalyst;
Described device also comprises a regenerated catalyst water cooler, and revivifier is communicated with this water cooler catalyst inlet by second regenerated catalyst, and the catalyst outlet of water cooler is communicated with auxiliary fluidizing reactor.
15, device according to claim 14, wherein, described catalyzer circulation mixing apparatus has a cylindrical outer cylinder body, is provided with a co-axial cylindrical inner core in it, forms outer annular space between the inside and outside cylindrical shell; The outer cylinder body top is communicated with the heavy oil riser reactor, is communicated with the outer cylinder body side from the reclaimable catalyst transfer lime of the stripping stage of auxiliary fluidizing reactor; The ratio of described inner diameter of steel flue and urceolus diameter is 1:5-3:5, and the ratio of inner core height and urceolus height is 1:4-3:4; Described outer annular space bottom is provided with the water vapor distribution pipe.
16, a kind of device of realizing described heavy oil fluid catalytic cracking of claim 1 and gasoline upgrading cross complaint comprises the heavy oil riser reactor and the revivifier that have the auxiliary fluidizing reactor of gasoline upgrading, wherein,
Described heavy oil riser reactor next door is provided with a catalyzer circulation mixing tank, this mixing tank top is connected with revivifier by the 4th regenerated catalyst, the bottom is connected with the heavy oil riser reactor by the mixed catalyst transfer lime, the auxiliary fluidizing reactor of gasoline upgrading is respectively arranged with the reclaimable catalyst transfer lime that is connected and is connected with revivifier with this catalyzer circulation mixing tank, and revivifier is connected with described catalyzer circulation mixing tank bottom by first regenerated catalyst;
Described device also comprises a regenerated catalyst water cooler, and revivifier is communicated with this water cooler catalyst inlet by second regenerated catalyst, and the catalyst outlet of water cooler is communicated with auxiliary fluidizing reactor.
17, device according to claim 16, wherein, described catalyzer circulation mixing apparatus has a cylindrical outer cylinder body, is provided with a co-axial cylindrical inner core in it, forms outer annular space between the inside and outside cylindrical shell; Outer cylinder body top and bottom are communicated with revivifier and heavy oil riser reactor respectively, are communicated with the outer cylinder body side from the reclaimable catalyst transfer lime of the stripping stage of auxiliary fluidizing reactor; The ratio of described inner diameter of steel flue and urceolus diameter is 1:5-3:5, and the ratio of inner core height and urceolus height is 1:4-3:4; Described outer annular space bottom is provided with the water vapor distribution pipe.
18, according to claim 12,14 or 16 described devices, wherein, described regenerated catalyst water cooler is arranged at the revivifier next door, the catalyst outlet of water cooler is communicated with auxiliary fluidizing reactor by the 3rd regenerated catalyst, also is provided with the regenerated catalyst loop between water cooler and the revivifier.
19, according to claim 12,14 or 16 described devices, wherein, described regenerated catalyst water cooler is arranged at the bottom of the auxiliary fluidizing reactor of gasoline upgrading, and the top of regenerated catalyst water cooler is a catalyst outlet, and be connected with auxiliary fluidizing reactor, the bottom is an end socket.
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| CN101993712B (en) * | 2009-08-17 | 2013-03-06 | 中国石油大学(北京) | Method for flexibly adjusting catalytic cracking reaction-regeneration system heat balance |
| CN102212390B (en) * | 2010-04-02 | 2013-07-10 | 中国石油化工集团公司 | Double riser catalytic cracking method and device |
| RU2563637C2 (en) | 2010-09-27 | 2015-09-20 | Чайна Петролеум Энд Кемикал Корпорейшн | Method of catalytic conversion for improvement of composition of target product |
| AR119323A1 (en) * | 2019-07-02 | 2021-12-09 | Lummus Technology Inc | FLUID CATALYTIC CRACKING PROCESSES AND APPARATUS |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104379702A (en) * | 2012-06-29 | 2015-02-25 | 环球油品公司 | Apparatus for mixing two streams of catalyst with an insert having aligned openings |
| CN104379702B (en) * | 2012-06-29 | 2016-10-19 | 环球油品公司 | Utilize the equipment of insert two strands of catalyst streams of mixing of the opening with alignment |
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