CN1148865A - Process and preparation for producing light olefins - Google Patents
Process and preparation for producing light olefins Download PDFInfo
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- CN1148865A CN1148865A CN95193178A CN95193178A CN1148865A CN 1148865 A CN1148865 A CN 1148865A CN 95193178 A CN95193178 A CN 95193178A CN 95193178 A CN95193178 A CN 95193178A CN 1148865 A CN1148865 A CN 1148865A
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- revivifier
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/22—Higher olefins
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
A process and apparatus for catalytically converting hydrocarbons to light olefins with a short contact circulating fluidized bed reactor system. The process comprises the steps of feeding a hydrocarbon feedstock into a reaction zone (1) containing a solid catalyst, contacting the hydrocarbon feedstock in the reaction zone (1) with the catalyst under conditions which favour catalytic conversion of hydrocarbons into light olefins, separating the reaction products obtained from the reaction zone (1) after catalytic conversion, recovering the catalyst, and regenerating the deactivated catalyst in a regenerator (3). According to the invention, the hydrocarbon feedstock is contacted with the catalyst in a circulating fluidized bed reactor (1) at a residence time in the range of 0.1 to 3 seconds. The process is used for preparing propylene, butylenes and pentenes and high octane, low benzene gasoline fraction by catalytic conversion of LGO, HGO, VGO or naphta, using conventional or improved FCC catalysts. The process can also be used for preparing propylene, isobutylene or isoamylene rich products by catalytic dehydrogenation from propane, isobutane or naphta, respectively, using conventional or improved dehydrogenation catalysts for fluidized bed service.
Description
Background of invention
Invention field
The present invention relates to light-olefin production.In detail, the present invention relates to a kind of method according to the preamble of claim 1, it comprises that with the cause hydrocarbon raw material for example light gas oil, heavy gas oil and vacuum gas oil, petroleum naphtha, propane, butane or light condensation product are produced light olefin such as propylene, butylene and amylene.The invention still further relates to a kind of equipment according to the preamble of claim 17, it is suitable for producing light olefin by said hydrocarbon feed.Correlation technique is introduced
Several commercial methods of producing propylene, butylene or amylene have been known at present with the various petroleum base hydrocarbon feeds of cause.These methods comprise steam cracking, fluid catalystic cracking and dehydrogenation.These prior arts have some shortcomings of pointing out below:
Steam cracking: the main products of process for steam cracking is an ethene.Propylene and heavier alkene are most important byproducts, and their productive rate can not increase considerably by changing operational condition.Other byproduct comprises fuel gas, aromatic tar and coke, and they are harmful to and are worth the very low or basic value that there is not to this method.
Habitual fluid catalystic cracking (FCC): the low and main products composition of light olefin productive rate, FCC gasoline, with low quality, can not satisfy the needs of back, this is because its octane value is low, benzene and heavy olefin(e) centent height.In order to increase the generation of light olefin, need higher temperature and short residence time(SRT), this is unpractical in pre-existing reactors, will illustrate below this point.When improving temperature, the reactor heat absorption is more, and the temperature head between reactor and the revivifier reduces, and this is because regenerator temperature can not improve again, otherwise can damage catalyzer.In order to supply with needed whole energy, perhaps increase the ratio of catalyzer to oil, perhaps transmit part energy with certain alternate manner.
Catalytic dehydrogenation: dehydrogenation of hydrocarbons just can be carried out under quite high temperature.Dehydrogenation reaction is a strong endothermic reaction, requires heat a large amount of to the reaction zone input, careful control.Can make the design of reactor/regenerator complicated and expensive like this.
The type of reactor that has been used for hydrocarbon conversion processes is as follows:
Fixed-bed reactor and
2. fluidized-bed reactor.
Under very high fluidizing velocity, bed face is no longer obvious,, and replaced with the zone of highly slowly reducing by a solids content.Very thin as fruit granule, can cause the high speed fluidisation, wherein solid is carried secretly and is carried out so soon, so that high-velocity fluidized bed generally can only lean on and by cyclonic separator entrained solid carried out recirculation and keep.This system is called circulating fluidized bed, CFB.
One of most widely used reactor system is the FCC system, and its chief component is: operate in the riser tube of high speed fluidisation yield zone, operate in the large vol reactor and the revivifier that operates in fluidised bed zones of rare suspending phase.This reactor system has a high riser tube (30-40m) higher than revivifier usually, and revivifier is connected at a certain position between reactor top and riser tube bottom with riser tube-combination of reactors.Riser tube must be higher than the hydrodynamic force reactivity of revivifier with guarantee system significantly.This has just set the restricted condition that is caused by the residence time and equipment design for this method.When needing short contacting time and high solid concentration in the reactor, these restricted conditions are unfavorable especially.This has just limited the residence time and solids concn-very short duration of contact or high solids concn and can not reach with a kind of FCC system.
US patent specification No.4980053 has described with heavy hydrocarbon fraction such as vacuum gas oil and has made raw material, than FCC harshness, and than the test of carrying out under the condition of steam cracking gentleness, propylene that obtains and butylene productivity ratio ethene height.Be referred to as this method of deep catalytic cracking method (DCC), pilot plant and a commerce, study on the improved FCC apparatus.This device is actually a FCC apparatus, has just used different operating parameterss and a kind of improved catalyzer.
Announced among the european patent application No.395345 a kind of stable hydrocarbon to be converted into light olefin, the method for propylene particularly, it uses a kind of zeolite catalyst, and temperature of reaction is between 500 to 700 ℃, and hydrocarbon partial pressure is very low.In the embodiment of said reference, react with fixed-bed reactor, can keep short residence time(SRT).But this method also can be carried out in the fluidized-bed system.It is said that this prior art is than habitual steam cracking reduced investment, to propylene and butylene selectivity height.
But reactor system above-mentioned has a serious limitation, and has limited in the method that needs short residence time(SRT) and high solid concentration in their application, particularly reactor.In this method, riser tube should be lower than revivifier.If between revivifier and riser tube, also have very big pressure reduction, problem even more serious simultaneously.Under the sort of situation, revivifier can't be connected with the cyclonic separator of riser tube.Need replace complicated system with recycling catalyst.In fact, reactor riser must be designed to unrealistic ground height, and in this case, it is too high that gas flow rate can become, and the volume fraction of catalyzer is too low in the riser tube, is difficult to reach optimum process condition.The limitation of FCC system is that under the condition that does not influence other processing parameter, the volume fraction of catalyzer can not arbitrarily be controlled.
Summary of the invention
Therefore, an object of the present invention is to overcome the above-mentioned defective of prior art, and a kind of novel method and reactor system that is prepared light olefin by hydrocarbon feed is provided.
Design of the present invention is based on the catalyzed conversion that carries out hydrocarbon feed in a circulating fluidized bed (CFB) reactor with short residence time(SRT).Preferably, spent catalyst is also regenerated in a circulating fluidized bed (CFB) revivifier, and endothermic conversion is reacted required whole heat energy and provided by the catalyst particle of cyclic regeneration.
More particularly, the characteristics of the inventive method characteristic as claimed in claim 1 is said.
Reactor system according to the present invention comprises that at least one is used to carry out the ciculation fluidized bed unit (reactor) of hydro carbons catalyzed conversion, and hydrocarbon feed is housed for it and the reinforced of recycling catalyst particle chews.The CFB reactor also is equipped with a cyclonic separator or similar separator, and in order to spent catalyst is separated with product flow, said cyclonic separator has the products export of a light olefin and the solid outlet of an isolated catalyst particle.In addition, reactor system comprises that also at least one carries out the ciculation fluidized bed unit of catalyst regeneration with combustion method, it is equipped with that regenerated spent catalyst material is chewed and a cyclonic separator or similar separator, in order to the regenerated catalyzer is separated with the stack gas of combustion processes.The material of regenerator unit is chewed with the solid outlet of reactor unit cyclonic separator and is connected.
More particularly, the characteristic of the principal character of this reactor system such as claim 17 is said.
Brief Description Of Drawings
Accompanying drawing is represented the process design of the simplification of the present invention's one preferred embodiment in a schematic way.
The detailed Description Of The Invention definition
Within the scope of the present invention, term " spent catalyst " and " decaying catalyst " but mutual alternative has deposited the granules of catalyst of coke or other impurity in order to expression, coke or impurity have reduced the catalytic activity of catalyzer.
Abbreviation " CFB " a kind of in order to represent " circulating fluidized bed ", wherein solid is vertically carried by high velocity air in a vertical ducting.This CFB preferably is equipped with a cyclonic separator so that with solid and pneumatic separation.Usually also have a return pipe to link to each other with cyclonic separator so that make solid carry out recirculation.This return pipe has been represented a kind of preferred embodiment according to CFB of the present invention, but following CFB device does not have return pipe can operate yet.Typical performance gas velocity is between about 2 to about 10m/s among the CFB.Under such gas speed, the logistics flux of solid (catalyst particle) is very big, makes required reactor diameter reduce to minimum.Superficial gas velocity in the CFB revivifier is also not really important, but because catalyzer recirculation is to reach the desired residence time of catalyst regeneration.
" light olefin " is meant the alkene that contains 1 to 6 carbon atom, optimal ethylene, propylene, butylene and amylene.
When being used to address the contact of raw material-catalyzer, term " short contact " the expression residence time is between 0.1 to 3 second.The residence time is shorter than 2 seconds or is shorter than 1 second, particularly even to be shorter than 0.5 second be possible.Method is introduced
The method that hydro carbons is catalytically conveted to light olefin comprises the habitual step that a kind of hydrocarbon feed is dosed in the reaction zone that contains a kind of solid catalyst.At this reaction zone, hydro carbons contacts with catalyzer under its condition that is catalytically conveted to light olefin helping.After the reaction, the light olefin of production separates with catalyst particle with unreacted raw material.To lost efficacy, the catalyzer of inactivation reclaims and in a revivifier method with carbon deposit on the burning-off catalyst particle make it to regenerate.
According to the present invention, hydrocarbon feed contacts with catalyzer in a circulating fluidized bed (CFB reactor), and the residence time is between 0.1 to 3 second.Difference with habitual FCC system is according to CFB system of the present invention: 1) large vol reactor a riser tube that an outside whirly separator is housed replaces and only reacts and carry out in this riser tube; 2) the ebullated bed revivifier is replaced by a CFB revivifier.These 2 improvement can be promoted the control of the residence time and improve the structure of reactor.
So far, circulating fluid bed reactor (CFBR) is mainly used in the on-catalytic method.But a kind of circulating fluid bed reactor (CFB) is also known in the present technique field, also once plans to produce maleic anhydride [Pugsley based on the catalyzed oxidation of butane, T.et al., industrial engineering chemistry research (Ind.Eng, Chem.Res.) 31 (1992), 2652-2660].As a shortcoming of this known CFB structure, should be mentioned that the catalyst volume mark of this reactor can't carry out free adjustment under the condition that does not influence other process parameter.And, there is not available same equipment to carry out the suggestion of cracking reaction or preparation light olefin in the prior art.
According to the present invention, spent catalyst one with external cyclone that the CFB reactor is connected in separate with hydrocarbon feed with product.Revivifier preferably includes an equipment that is similar to reactor, so that the regeneration of spent catalyst can be carried out in one second circulating fluidized bed.But the revivifier of other type also can use.
According to the present invention, can arrange two (or more) reactor units to contact, make the raw material of subsequent reactor with the product stream of front reactor.The reactor of this embodiment can be operated under different temperature and pressures, can make this method adapt to various hydrocarbon feed like this.
According to a particularly preferred embodiment, wherein reactor system comprises a CFB reactor and a CFB revivifier, and the isolating decaying catalyst of at least a portion is imported into revivifier by first pipe (" spent catalyst pipe ") that is connected in the revivifier bottom.The most handy one is connected in the decaying catalyst feed that valve control that the pipeline material chews enters revivifier, and its mode wants to make the catalyzer that has a minimum in the pipeline at least to guarantee that pipeline is bubble-tight basically." stopper " that catalyzer forms in pipeline can avoid any gas of reaction zone to enter revivifier.This has just been avoided the danger of blast.
Within the scope of the present invention, whole isolating decaying catalysts can be imported revivifier and do not carry out any internal reactor circulation.
Decaying catalyst preferably in second circulating fluidized bed, accumulates in its surperficial coke 650 to 800 ℃ of temperature range burnings and regenerates, and preferred method is with warm air, and optional approach is that the stack gas that will be obtained by traditional fuel is introduced revivifier.As mentioned above, the also revivifier of available other type is as the revivifier of habitual ebullated bed type.
A main advantages of this reactor assembly (following will illustrating in greater detail) is that the concentration of catalyst reactor can maintain high level, and this just guarantees that its available big catalytic surface contacts with the hydrocarbon reaction thing.Therefore, according to reactor system of the present invention second pipe (" catalyst recirculation pipe ") is housed preferably, in order to the isolated catalyst recirculation of cyclonic separator is back to reactor.
Go the two-part throughput ratio of regenerated and round-robin to depend on hydrocarbon feed, input speed, catalyst system therefor and processing condition in the spent catalyst.
The same with CFB reactor situation, preferably a part of catalyst recirculation is got back to the CFB revivifier by a circulation tube, remaining catalyzer then flows in the CFB reactor by the catalyst recirculation pipe that links to each other with the CFB reactor bottom.
The present invention both can be under dehydrogenation condition, also can be under cracking conditions in order to being light olefin with the hydrocarbon conversion.The hydrocarbon feed that is used for catalytic cracking among the present invention can comprise light gas oil (LGO), heavy gas oil (HGO), vacuum gas oil (VGO) or petroleum naphtha.Steam or other gas can be used as thinner.The light olefin of producing comprises ethene, propylene, butylene, amylene and a kind of high-octane rating, low benzoline fraction.(FCC) cracking catalyst and the improved cracking catalyst of habitually practising are used as solid catalyst.Catalyst type can be following the example explanation: natural and synthetic aluminium silicate, zeolite, clay etc.Habitual zeolite can comprise X and y-type zeolite, and their available rare earth metals are stablized.As follows according to catalytic cracking process condition in the reactor system of the present invention: temperature of reaction: 520 to 700 ℃; Pressure: 105 to 500kPa; The residence time: 0.1 to 3 second, particularly 0.2 to 1 second.The residence time also may be less than 0.5 second (for example 0.2-0.49 second).
The present invention also can be used for the dehydrogenation of hydrocarbon feed such as propane, Trimethylmethane and light condensation product so that this raw material is separately converted to propylene, iso-butylene and mixed butene.Typical temperature of reaction is between 580～750 ℃.The available residence time as hereinbefore.The known dehydrogenation catalyst of available art technology such as chromium/aluminum oxide.
According to the present invention, air can be added reactor with accelerated reaction, the air feeding coal is 0 to 50%, if to reactor feeding additional air, its preferable amount be hydrocarbon weight about 0.1 to about 50%, 10-40% particularly.
Compare with currently known methods, the most important benefit of the present invention is:
Do not use complicated mechanical or pneumatic transmission system that catalyzer is delivered to another unit by a unit, just can keep short residence time(SRT) and high catalyst volume fraction.
The required net quantity of heat of hydrocarbon feed catalyzed conversion is provided by regenerated recycling catalyst in the circulating fluidized bed revivifier, provides some heats unless also inject the oxidation of air and raw material that causes thus and reaction product in reactor to reactor.
The volume fraction of catalyzer in reactor can have nothing to do with other flow in the process with the internal activator cycle sets at desired value.
The pressure height of reactor and revivifier can be controlled independently of one another.This also can provide unites the possibility of using many reactors, and their each personal optimal processing parameters and raw material are operated, a shared revivifier.
Compare with habitual cracking method, the inventive method provides high light olefin productive rate, premium fraction, high conversion and simple, cheap reactor design.
Compare with existing method of dehydrogenating, the invention provides a kind of very simple, cheap reactor/regenerator design.
Compare with FCC type device, revivifier is little and loaded catalyst is few.This just might be by suitably design, avoids existing heavy fire-resistant assembly and uses easy maintenance, light-duty, simple, cheap external insulation structure.
Use air to make pre-fluidized gas, need not improve reactor inlet temperature and just can improve average cracking temperature along the CFB reactor, the light olefin productive rate also improves as a result, and this is owing in reaction zone and heat absorption cracking simultaneously, the heat release burning has taken place.
Accompanying drawing is represented a preferred embodiment of the present invention.Obtain the processing condition of needs with a short contact reaction/regeneration system.
(Einco Oy has narrated the ultimate principle of controlling two CFB unit interphase interactions in Finland) to Finnish Patent Application 924438 in more detail.
According to the present invention, a kind of hydrocarbon feed with the catalyst mix that heats carries out cracking 520 to 700 ℃ temperature range in a short contact CFB reactor 1.Hydro carbons is chewed (24) by a material and is fed in raw material.The working pressure of reactor is 105 to 500kPa (a), and the residence time is by 0.1 to 3 second, preferably 0.2 to 2 second.Catalyzer can change between 1 to 120 the ratio of oil.Preferably 10 to 50, hydrocarbon feed partial pressure can not be the prerequisite of present method operation but use diluent gas by adding steam or other diluent gas as reducing from this unitary circulation gas.Raw material is entered by pipeline 17 and pre-fluidizing agent injects by pipeline 18.
After the cracking reaction, spent catalyst separates at a cyclonic separator 2 that is arranged in outside the fluidized-bed reactor with product.The hydro carbons that adsorbs in the used catalyst or stay wherein and burn in revivifier 3 if it is reasonable economically perhaps to carry out elution, then comes out its elution with logistics 21 in the elution district of cyclonic separator bottom.Product flows out by pipeline 19.Part spent catalyst is delivered to revivifier 3 by cyclonic separator 2 by spent catalyst pipeline 16, and the flow of catalyst particle is regulated by valve 8, this valve is positioned at the material that is connected with revivifier 3 bottoms chews 8 ' near pipeline on.Part spent catalyst can be used as internal recycling and gets back to reactor by the control valve on the catalyst recirculation pipe 12 6.Get final product the volume fraction and the temperature cross section of catalyzer in the conditioned reaction device with valve 6 control catalyst speed of circulation.For avoiding reactor and regenerator gases to mix, make pipeline 16 always be filled with catalyzer with the flow of valve 8 control catalyst particles.Control with L indication surface height.
Revivifier 3 comes down to a circulating fluid bed reactor.Revivifier is as two purposes: supply with heat that the heat absorption cracking reaction needs and burn the coke that is deposited on the spent catalyst particle to reactor with the catalyzer that heats in the revivifier.The regeneration of catalyzer is carried out 650 to 800 ℃ of temperature ranges, and method is to blast preheated air and inject additional fuel by pipeline 23 by gas inlet pipe 22 to the revivifier lower end.Perhaps also can therefrom hot flue gases be introduced regenerator bottoms by pipeline 22 with additional fuel in an independent combustion chambers burn.The regenerated thermocatalyst separates with burning gas and gets back to reactor 1 by regenerated catalyst pipe 15, its flow is by control valve 9 controls, burning gas flows out by the outlet pipe in the revivifier cyclonic separator 4 20, and remaining regenerated catalyst is got back to revivifier as internal recycle by catalyst recirculation pipe 14.
Under stable condition, catalyzer equates by the flow velocity of pipeline 15 and 16.Catalyzer is added system by valve 5, is controlled by the pressure difference of revivifier top and bottom.
The polyphone form of many reactors with hydrocarbon material can be configured, also can be with they parallel connections, every reactor has the raw material of oneself.
A FCC product recovery system available standard or improved will be in reactor cyclone further be processed into the intermediates fraction with the product of catalyst separating.
As the example of embodiment of the present invention, provided the pilot-plant test result that gas oil is converted into alkene below.Embodiment 1
Without the inner catalyst circulation, major parameter is as follows: reactor in System is made up of a CFB reactor and a CFB revivifier.The regenerated catalyst that enters reactor carries out pre-fluidisation with nitrogen.Light gas oil (LGO) the is chewed reinforced to reactor with the low discharge air distribution through a material. test: the pre-fluidisation pipe of height 1.85m diameter 0.030m oil quality flow velocity 1.13g/s external catalyst catalystoil ratio 27g/g internal accelerator/oil ratio 0% catalyst volume mark, 2 to 7% pre-fluidisation pipe height 0.25m diameter 0.018m regenerator: the 3.1m diameter 0.08m O that works off one's feeling vent one's spleen highly2Concentration 4 to 5% catalyst volume marks 4% embodiment 2
Identical among structure of reactor and raw material and the embodiment 1, exception be that interior and outer catalyst/oil ratio all is approximately 15.The inner catalyst loop head is just on oiling point top on the reactor.Embodiment 3
Identical among structure of reactor and raw material and the embodiment 2, exception be that air useless distributes raw material and inner catalyst/oil ratio to be about 8.Embodiment 4
Structure of reactor is identical with embodiment 1 with raw material, exception be to carry out pre-fluidisation with air, but do not have product distribution gas.Riser diameter is 0.042m in this test.
Table 1. embodiment 1 to 4 test-results
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 mass balance raw materials, g oil 4,073 3,802 4,248 8,780 nitrogen 3,323 2,620 2,618 0 air 593 428 02,962 amount to 7,989 6,850 6,866 11,742 products, g gas 5,593 4,563 4,406 7,164 condensation products 2,132 1,594 2,234 3,555 coke 407 380 425 1,300 amount to 8,132 6,537 7,065 10, poor-2% 5%-3%-2% process yield of 719 poor-143 313-199-277 raw materials, wt-%C
1To C
4Alkane 5.8 6.4 5.9 13.8C
2 =To C
4 =26.2 24.2 21.2 26.0 gasoline, 28.3 30.8 37.1 30.4 gas oils, 23.9 23.1 20.3 12.5 bottomss, 4.3 4.0 3.7 0.4 coke, 10.7 9.9 11.5 14.3CO
2, H
2, H
2O 0.8 0.8 0.2 2.5 amounts to 100.0 99.8 99.7 99.9 transformation efficiencys, wt-% temperature of reactor ℃ 588 587 585 591 regenerator temperature ℃ 760 755 786 762 inner catalysts/oil ratio 0 15 80 outer catalyst/oil are than 27 15 15 22 residence time, and seconds 0.25 0.31 0.32 0.83
Claims (17)
1. one kind is catalytically conveted to the method for light olefin with hydro carbons, and it may further comprise the steps:
-a kind of hydrocarbon feed is fed in the reaction zone (1) that contains a kind of solid catalyst,
-helping allowing hydrocarbon feed at reaction zone under the condition that hydro carbons is catalytically conveted to light olefin
(1) contact with catalyzer in,
Behind-the catalyzed conversion by isolating the reaction product that obtains in the reaction zone (1),
-reclaim catalyzer and
-the catalyzer of regeneration of deactivated in revivifier (3) is characterized in that:
-allow hydrocarbon feed and catalyzer in a circulating fluid bed reactor (1) with 0.1 to 3 second
The residence time contacts.
2. according to the process of claim 1 wherein that revivifier comprises a circulating fluidized bed (3), this method is further comprising the steps of:
-from circulating fluid bed reactor (1), take out a part of spent catalyst at least and with it
Be fed into circulating fluidized bed revivifier (3) so as with combustion method regeneration and
-with the regenerated catalyst recirculation to circulating fluid bed reactor (1), by this in fact
The net quantity of heat that the hydrocarbon feed catalyzed conversion needs is by in circulating fluidized bed revivifier (3)
The regenerated recycling catalyst provides.
3. according to the method for claim 2, wherein all spent catalysts in the circulating fluid bed reactor (1) are taken out and be fed into revivifier (3) so that regenerate with combustion method.
4. according to the arbitrary method of claim 1 to 3, wherein spent catalyst is separated in by circulating fluid bed reactor (1) in an outer whirlwind separator (2) that links to each other with reactor, and at least a portion catalyzer is introduced into revivifier (3) by the spent catalyst pipeline (16) that is connected in circulating fluidized bed revivifier (3) bottom.
5. according to the method for claim 4, wherein separative catalyzer is introduced into revivifier (3).
6。Method according to claim 4 or 5, wherein flow into the used catalyst flow of revivifier (3) through used catalyst pipeline (16), controlled with the valve (8) that is contained on the spent catalyst pipeline (16) so that spent catalyst pipeline (16) thus in always be filled with catalyzer and guarantee that reactor and regenerator gases do not mix mutually.
7. according to the method for claim 3 to 6, the concentration in the reactor and controlled through catalyst recirculation pipe (12) to the catalyst circulation rate of reactor by regulating wherein along the temperature cross section of reactor (1).
8. according to arbitrary method in the above claim, wherein in the cyclonic separator (4) of regenerated catalyst outside revivifier (3) by separating in the circulating fluidized bed revivifier (3), part catalyzer cycles back to circulating fluidized bed revivifier (3) through catalyst recirculation pipe (14), and remaining catalyzer is directed to reactor (1) bottom through regenerated catalyst pipe (15).
9. according to the method for claim 1, wherein with a kind of hydrocarbon feed such as light gas oil, heavy gas oil, vacuum gas oil or petroleum naphtha, under catalytic cracking condition, do not use diluent gas or handle as thinner with steam or other gas, this hydrocarbon feed is converted into light rare hydrocarbon such as propylene, butylene, amylene and high-octane rating, low benzoline.
10. according to the method for claim 9, wherein used solid catalyst or habitual cracking catalyst, or improved cracking catalyst.
11. according to arbitrary method in the above claim, wherein raw material and catalyzer are in circulating fluid bed reactor (1), 520 to 700 ℃ of temperature ranges, 105 to 500kPa pressure contacted with 0.1 to 3 second residence time.
12., under dehydrogenation condition, handle, so that hydrocarbon feed is converted into propylene, butylene or amylene according to the process of claim 1 wherein a kind of hydrocarbon feed such as propane, Trimethylmethane or light condensation product in the presence of a kind of dehydrogenation catalyst.
13. according to the method for claim 12, wherein raw material and catalyzer 580 to 750 ℃ of temperature ranges, contacted with 0.1 to 3.0 second residence time in circulating fluid bed reactor (1).
14. according to arbitrary method in the above claim, wherein 0.1 to 50% the air charge that will calculate with hydrocarbon feed weight is to reactor (1).
15. according to arbitrary method in the above claim, wherein decaying catalyst is used in the method for burning the surface deposition coke in the circulating fluidized bed revivifier (3) and regenerates, temperature range is 650 to 800 ℃, but with warm air and also additional fuel.
16. according to the process of claim 1 wherein that the residence time is 0.2 to 2 second, best 0.2 to 1 second.
17. one kind with the equipment that hydro carbons is catalytically conveted to light olefin, it comprises following unitary combination:
-at least one circulating fluid bed reactor (1),
-hydrocarbon feed and recycling catalyst are dosed to the material of circulating fluid bed reactor (1) bottom
Chew (24) and (6 '),
The cyclonic separator of-one separating catalyst (2), it is contained in fluidized-bed reactor (1)
The outside is in order to separate spent catalyst said cyclonic separation with the reactor product logistics
Device has a product outlet (19) and catalyzer to solidify outlet (12,16),
-one circulating fluidized bed regeneration unit device (3), in order to regenerated catalyst,
-go regenerated spent catalyst material to chew (6 '), at the second circulating fluidized bed revivifier (3)
The bottom and
The cyclonic separator of-one separating catalyst (4) is in order to regenerated catalyst and regeneration
Device stack gas is separated.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI941528 | 1994-03-31 | ||
| FI941528A FI98529C (en) | 1994-03-31 | 1994-03-31 | Method and apparatus for the preparation of light olefins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1148865A true CN1148865A (en) | 1997-04-30 |
| CN1124330C CN1124330C (en) | 2003-10-15 |
Family
ID=8540434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95193178A Expired - Fee Related CN1124330C (en) | 1994-03-31 | 1995-03-31 | Process and preparation for producing light olefins |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0753037B1 (en) |
| JP (1) | JPH09511535A (en) |
| KR (1) | KR100281750B1 (en) |
| CN (1) | CN1124330C (en) |
| AU (1) | AU2139695A (en) |
| CA (1) | CA2186744C (en) |
| DE (1) | DE69518407T2 (en) |
| ES (1) | ES2149976T3 (en) |
| FI (1) | FI98529C (en) |
| RU (1) | RU2125079C1 (en) |
| WO (1) | WO1995027019A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448948C (en) * | 2002-09-30 | 2009-01-07 | 埃克森美孚化学专利公司 | Catalyst regenerator linked with a plurality of reactors |
| CN101001938B (en) * | 2004-08-10 | 2012-01-11 | 国际壳牌研究有限公司 | Method and apparatus for making a middle distillate product and lower olefins from a hydrocarbon feedstock |
| CN101495222B (en) * | 2006-07-28 | 2012-03-21 | 巴斯夫欧洲公司 | Process for the long-term operation of a continuously operated heterogeneously catalyzed partial dehydrogenation of a hydrocarbon to be dehydrogenated |
| CN101233213B (en) * | 2005-10-07 | 2012-05-23 | Sk新技术株式会社 | Process for production of light olefins from hydrocarbon feedstock |
| CN101568379B (en) * | 2006-12-28 | 2013-02-13 | 环球油品公司 | Fluidized bed reactor with back-mixing for dehydrogenation of light paraffins |
| CN101688131B (en) * | 2007-07-13 | 2013-08-07 | Sk润滑油株式会社 | Process for manufacturing naphthenic base oils from effluences of fluidized catalytic cracking unit |
| CN103566838A (en) * | 2012-08-02 | 2014-02-12 | 宁波科元塑胶有限公司 | Acrylonitrile fluidized reaction system and acrylonitrile fluidized bed production method |
| CN110678437A (en) * | 2017-06-07 | 2020-01-10 | Sk燃气株式会社 | Olefin production process including reduction pretreatment |
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| FI101133B (en) | 1996-08-30 | 1998-04-30 | Fortum Oil Oy | Equipment for chemical and physical processes |
| US6538169B1 (en) | 2000-11-13 | 2003-03-25 | Uop Llc | FCC process with improved yield of light olefins |
| KR100473986B1 (en) * | 2001-11-01 | 2005-03-07 | 서곤 | Preparation of catalysts from used fcc catalysts for the liquid-phase degradation of waste polymer, and catalytic degradation process using the same |
| US7442739B1 (en) | 2003-11-12 | 2008-10-28 | Henkel Corporation | Hot melt pressure sensitive adhesives |
| KR100651418B1 (en) | 2006-03-17 | 2006-11-30 | 에스케이 주식회사 | Catalytic cracking process using fast fluidization for the production of light olefins from hydrocarbon feedstock |
| KR100898816B1 (en) * | 2007-02-12 | 2009-05-22 | 한국에너지기술연구원 | Carbon deoxide capturing device including water vapor pretreatment apparatus |
| JP5124407B2 (en) * | 2008-09-26 | 2013-01-23 | ジェイパワー・エンテック株式会社 | Conveyor system for dry exhaust gas treatment equipment |
| US7935314B2 (en) | 2008-09-30 | 2011-05-03 | Uop Llc | Apparatus for mixing regenerated and carbonized catalyst |
| US8323477B2 (en) | 2008-09-30 | 2012-12-04 | Uop Llc | Process for mixing regenerated and carbonized catalyst |
| US8293670B2 (en) * | 2009-12-09 | 2012-10-23 | Uop Llc | Process for the production of propylene |
| JP2013141659A (en) * | 2012-01-12 | 2013-07-22 | Sumitomo Chemical Co Ltd | REACTION APPARATUS AND METHOD FOR PRODUCING ε-CAPROLACTAM |
| WO2019018569A2 (en) | 2017-07-18 | 2019-01-24 | Lummus Technology Llc | Integrated thermal and catalytic cracking for olefin production |
| FI130603B (en) | 2018-08-03 | 2023-12-08 | Neste Oyj | Method to produce bio-renewable propylene from oils and fats |
| US20220356405A1 (en) * | 2019-07-31 | 2022-11-10 | Sabic Global Technologies B.V. | High-density fluidized bed systems heat balance |
| CN116218561A (en) * | 2021-12-03 | 2023-06-06 | 中国石油化工股份有限公司 | Catalytic cracking reactor, catalytic cracking system and method |
| KR20240054505A (en) * | 2022-10-19 | 2024-04-26 | 한국화학연구원 | Olefin production method through dehydrogenation-cracking reaction of saturated hydrocarbons |
| WO2024118432A1 (en) * | 2022-11-29 | 2024-06-06 | Dow Global Technologies Llc | Methods for forming light olefins with catalyst recycle |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4724065A (en) * | 1985-12-05 | 1988-02-09 | Engelhard Corporation | Hydrocarbon conversion with hot and cooled regenerated catalyst in series |
| US5234578A (en) * | 1988-08-26 | 1993-08-10 | Uop | Fluidized catalytic cracking process utilizing a high temperature reactor |
| US5009769A (en) * | 1989-02-06 | 1991-04-23 | Stone & Webster Engineering Corporation | Process for catalytic cracking of hydrocarbons |
| US4917790A (en) * | 1989-04-10 | 1990-04-17 | Mobil Oil Corporation | Heavy oil catalytic cracking process and apparatus |
| US5019239A (en) * | 1989-11-21 | 1991-05-28 | Mobil Oil Corp. | Inverted fractionation apparatus and use in a heavy oil catalytic cracking process |
-
1994
- 1994-03-31 FI FI941528A patent/FI98529C/en active
-
1995
- 1995-03-31 EP EP95914373A patent/EP0753037B1/en not_active Expired - Lifetime
- 1995-03-31 ES ES95914373T patent/ES2149976T3/en not_active Expired - Lifetime
- 1995-03-31 CN CN95193178A patent/CN1124330C/en not_active Expired - Fee Related
- 1995-03-31 WO PCT/FI1995/000177 patent/WO1995027019A1/en active IP Right Grant
- 1995-03-31 KR KR1019960705409A patent/KR100281750B1/en not_active IP Right Cessation
- 1995-03-31 DE DE69518407T patent/DE69518407T2/en not_active Expired - Fee Related
- 1995-03-31 RU RU96119940A patent/RU2125079C1/en active
- 1995-03-31 AU AU21396/95A patent/AU2139695A/en not_active Abandoned
- 1995-03-31 JP JP7525430A patent/JPH09511535A/en not_active Ceased
- 1995-03-31 CA CA002186744A patent/CA2186744C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448948C (en) * | 2002-09-30 | 2009-01-07 | 埃克森美孚化学专利公司 | Catalyst regenerator linked with a plurality of reactors |
| CN101001938B (en) * | 2004-08-10 | 2012-01-11 | 国际壳牌研究有限公司 | Method and apparatus for making a middle distillate product and lower olefins from a hydrocarbon feedstock |
| CN101233213B (en) * | 2005-10-07 | 2012-05-23 | Sk新技术株式会社 | Process for production of light olefins from hydrocarbon feedstock |
| CN101495222B (en) * | 2006-07-28 | 2012-03-21 | 巴斯夫欧洲公司 | Process for the long-term operation of a continuously operated heterogeneously catalyzed partial dehydrogenation of a hydrocarbon to be dehydrogenated |
| CN101568379B (en) * | 2006-12-28 | 2013-02-13 | 环球油品公司 | Fluidized bed reactor with back-mixing for dehydrogenation of light paraffins |
| CN101688131B (en) * | 2007-07-13 | 2013-08-07 | Sk润滑油株式会社 | Process for manufacturing naphthenic base oils from effluences of fluidized catalytic cracking unit |
| CN103566838A (en) * | 2012-08-02 | 2014-02-12 | 宁波科元塑胶有限公司 | Acrylonitrile fluidized reaction system and acrylonitrile fluidized bed production method |
| CN110678437A (en) * | 2017-06-07 | 2020-01-10 | Sk燃气株式会社 | Olefin production process including reduction pretreatment |
Also Published As
| Publication number | Publication date |
|---|---|
| FI941528A (en) | 1995-10-01 |
| KR100281750B1 (en) | 2001-03-02 |
| EP0753037B1 (en) | 2000-08-16 |
| AU2139695A (en) | 1995-10-23 |
| RU2125079C1 (en) | 1999-01-20 |
| FI98529B (en) | 1997-03-27 |
| CN1124330C (en) | 2003-10-15 |
| FI941528A0 (en) | 1994-03-31 |
| ES2149976T3 (en) | 2000-11-16 |
| DE69518407T2 (en) | 2001-03-22 |
| JPH09511535A (en) | 1997-11-18 |
| FI98529C (en) | 1997-07-10 |
| DE69518407D1 (en) | 2000-09-21 |
| EP0753037A1 (en) | 1997-01-15 |
| CA2186744A1 (en) | 1995-10-12 |
| KR970702349A (en) | 1997-05-13 |
| WO1995027019A1 (en) | 1995-10-12 |
| CA2186744C (en) | 2003-06-24 |
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