CN102690679B - Catalytic cracking method for producing propylene - Google Patents
Catalytic cracking method for producing propylene Download PDFInfo
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- CN102690679B CN102690679B CN201110072767.1A CN201110072767A CN102690679B CN 102690679 B CN102690679 B CN 102690679B CN 201110072767 A CN201110072767 A CN 201110072767A CN 102690679 B CN102690679 B CN 102690679B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention discloses a catalytic cracking method for producing propylene. The catalytic cracking method comprises the following steps that one or more heavy raw materials and a first catalytic cracking catalyst comprising catalyst particles having main active ingredients of Y-type molecular sieves and catalyst particles having main active ingredients of beta-type molecular sieves undergo a contact reaction in a first riser reactor; after the contact reaction, the first catalytic cracking catalyst is subjected to steam stripping and regeneration and then is recycled; one or more light hydrocarbons and a second catalytic cracking catalyst comprising active ingredients of shape-selective molecular sieves having aperture sizes less than 0.7nm undergo a contact reaction in a second reactor; and after the contact reaction, the second catalytic cracking catalyst is subjected to steam stripping and regeneration and then is recycled. The catalytic cracking method provided by the invention has a high propylene yield and a high butene yield.
Description
Technical field
The present invention relates to a kind of catalyst cracking method producing propylene.
Background technology
Heavy oil catalytic pyrolysis prepares ethene, the important method of the small-numerator olefin such as propylene and butylene, the industrial heavy oil fluid catalytic cracking generally used produces the deep catalytic cracking technology (DCC of the method such as maximum production of propylene of low-carbon alkene, USP4980053 and USP5670037) and maximum produce the catalytic pyrolysis technology (CPP of ethene, USP6210562), these two kinds of technology adopt the structure of reactor of single riser reactor or single riser reactor combination dense phase fluidized bed to coordinate special-purpose catalyst to react under higher temperature conditions, the catalyzer used is all single catalyst systems that mesopore zeolite (as ZSM-5) containing MFI structure and/or large pore zeolite (as Y molecular sieve) isoreactivity constituent element are formed, higher small-numerator olefin productive rate is pursued on the certain heavy oil conversion basis of guarantee.But, because strengthening heavy oil conversion differs greatly with the catalytic active center improved required for small-numerator olefin, therefore, its catalyst formulation is difficult to sometimes combine in the reactor of dense phase fluidized bed at single riser reactor or single riser reactor the requirement simultaneously taking into account heavy oil conversion reaction and the reaction of voluminous small-numerator olefin.In addition, some catalytic cracking unit also increases voluminous small-numerator olefin productive rate by the auxiliary agent method of adding containing ZSM-5 zeolite at present.Although the method has good handiness, but the method is except increase small-numerator olefin productive rate amplitude is less, also there is the defect that other is difficult to overcome: one is, when add containing ZSM-5 zeolite auxiliary agent very little time be difficult to reach voluminous small-numerator olefin requirement; Two are, when adding the auxiliary agent containing ZSM-5 zeolite and being higher, main catalytic cracking catalyst is existed to the physical dilution effect of significant adverse, thus reduce whole catalyst system net effect, also there is the problem that between auxiliary agent with Primary Catalysts, performance is mated mutually, its productivity of propylene is difficult to further raising simultaneously.
CN100448954C discloses the catalysis conversion method of propylene enhancing.The method adopts two kinds of catalyst mixtures to participate in reaction, and a kind of is the catalyzer containing Y zeolite, and another kind of is the catalyzer containing ZSM-5 molecular sieve, transition metal additives and phosphorus additive.Reaction unit adopts double lifting leg design, mainly comprises main riser tube, subsidiary riser and public revivifier and gas-solid separation equipment.At main riser tube, heavy, macromolecular hydrocarbon oil crude material cracking are generated the products such as gasoline, diesel oil and liquefied gas; Isolate the liquefied gas intermediate product after propylene to be injected in auxiliary riser line reactor and to contact with two kinds of catalyst mixtures of heat, successively carry out alkene oligomerization, superimposed product cracking and dehydrating alkanes and react propylene enhancing product.The method cannot solve the side effect such as interference, dilution stated between two kinds of catalyzer, and productivity of propylene is not high; Reaction, regenerating unit structure is not related to yet.
CN101314724A discloses a kind of bio-oil and mineral oil combined catalytic conversion method.The method adopts catalyzer catalyzed conversion bio-oil and the mineral oil in riser tube and fluidized-bed compound reactor that modified beta zeolite and the zeolite with MFI structure are essential active to be used for producing the small-numerator olefins such as propylene.The method uses the single catalyst system containing various active constituent element, be difficult to take into account heavy oil conversion reaction and voluminous small-numerator olefin reacts the very large requirement of two kinds of response differences, the side effect such as interference, dilution between above-mentioned two kinds of zeolites cannot be solved well, productivity of propylene is not high, in addition, this patent does not also have particular requirement and regulation to reaction unit configuration aspects.
CN101134913A discloses a kind of hydrocarbons catalytic conversion method of preparing low-carbon olefins, and the method will obtain C2 ~ C4 alkene, gasoline, diesel oil, heavy oil and other low molecule saturated hydrocarbons after hydrocarbon material catalytic cracking; The catalyzer that the method uses, containing by phosphorus and the β zeolite of transition metal M modification and other kind zeolites of surplus.The method adopts the single catalyst system be made up of various active constituent element, and be difficult to take into account heavy oil conversion and the very large reaction of voluminous small-numerator olefin two species diversity, productivity of propylene is not high simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst cracking method producing propylene, and the method is used for heavy feed stock and transforms, and has higher productivity of propylene.
The invention provides a kind of catalyst cracking method producing propylene, comprising:
(1) heavy feed stock and the first catalytic cracking catalyst contact reacts in the first riser reactor is made, reacted oil gas is separated with the first catalytic cracking catalyst, oil gas introduces product separation system, first catalytic cracking catalyst introduces the first revivifier regeneration after the first stripper stripping, and the first catalytic cracking catalyst after regeneration is introduced the first reactor cycles and used; Wherein, described first catalytic cracking catalyst is mainly by active ingredient the granules of catalyst that the granules of catalyst of Y zeolite and active ingredient be mainly beta-molecular sieve and forms; First riser reactor temperature of reaction is 450 ~ 650 DEG C, and agent-oil ratio is 1 ~ 25, and the reaction times is 0.50 ~ 10 second;
(2) light hydrocarbon is made to be less than the second catalytic cracking catalyst of 0.7nm shape-selective molecular sieve in the second reactor contact reacts with containing aperture; The second described reactor comprises the second riser reactor and the fluidized-bed reactor of series connection, and the reacted oil gas of the second riser reactor and reacted second catalytic cracking catalyst are introduced the fluidized-bed reactor of connecting with the second riser reactor and reacted; Oil gas after fluidized-bed reaction introduces product separation system, and Second reactivator regeneration introduced by catalyzer after introducing the second stripper stripping, the second catalytic cracking catalyst after regeneration is introduced the second riser reactor and recycled; Described light hydrocarbon comprises gasoline fraction and/or C4 hydrocarbon; When described light hydrocarbon comprises gasoline fraction, the agent-oil ratio that gasoline fraction operates in the second riser reactor is 10 ~ 30, and the reaction times is 0.10 ~ 1.5 second; When described light hydrocarbon comprises C4 hydrocarbon, it is 12 ~ 40 that C4 hydrocarbon operates agent-oil ratio in the second riser tube, and the reaction times is 0.50 ~ 2.0 second; The temperature of reaction of fluidized-bed reactor is 500 ~ 650 DEG C, and weight hourly space velocity is 1 ~ 35 hour
-1.
The catalyst cracking method of production propylene provided by the invention, at heavy feed stock catalytic conversion reaction, in reprocessing cycle system, the cracking catalyst used be with Y zeolite be chief active constituent element granules of catalyst and take beta-molecular sieve as the mixture of granules of catalyst composition of chief active constituent element, at light hydrocarbon oil catalytic conversion reaction, in reprocessing cycle system, the cracking catalyst used is less than 0.7nm shape-selective molecular sieve for chief active constituent element with mean pore size, can be abundant, easily strengthen heavy oil conversion, heavy feed stock is converted into the small-numerator olefin products such as propylene by highly selective, two reacted spent agents of reactive system enter respective breeding blanket coke burning regeneration, be easy to regulation and control, thus define the closed catalyst reaction of two independences, reprocessing cycle, while can improving heavy oil conversion rate, highly selective increases the yield of small-numerator olefin yield especially propylene, there is higher heavy oil conversion rate and productivity of propylene, surprisingly also there is higher butylene productive rate.
Accompanying drawing explanation
Fig. 1 is a kind of catalytic cracking unit schematic diagram provided by the invention.Wherein 1,2 is riser reactor, 3 is dense fluidized bed bioreactor, 4 is revivifier, 5 is stripping stage subregion dividing plate in settling vessel, 6 regenerate subregion dividing plate in revivifier, 7 is heavy hydrocarbon oil riser reactor outlet gas-solid fast subset, and 8 be the fast subset of outlet gas-solid of riser tube and fluidized-bed combined reactor, and 9 is the public settling vessel of riser reactor 1 and riser tube 2 and fluidized-bed 3 combined reactor.40 and 41 are respectively two strands of regenerated catalyst inclined tubes (by guiding valve aperture control catalyst flow wherein, do not mark in figure), 42 and 43 are respectively two strands of reclaimable catalyst inclined tubes (by guiding valve aperture control catalyst flow wherein, not marking in figure).51 and 52 are respectively stripping zone corresponding to two strands of catalyzer, and 61 and 62 are respectively breeding blanket corresponding to two strands of catalyzer, and 50 is water stripping steam, and 60 is regeneration air.As shown in Figure 1, riser tube 2 and fluidized-bed 3 are connected in series through settling vessel 9 and realize being arranged in juxtaposition with riser tube 1, and settling vessel 9 is coaxially arranged with the stripper height comprising stripping zone 51 and stripping zone 52.
Embodiment
The catalyst cracking method of production propylene provided by the invention, in the first riser reactor, heavy feed stock and the first catalytic cracking catalyst contact reacts, oil gas is separated with carbon deposited catalyst after reaction by riser tube end tripping device by the oil agent mixture generated, described tripping device is preferably fast separating device, in order to by reaction oil gas and carbon deposited catalyst sharp separation, can adopt existing fast separating device, preferred fast packing is set to slightly revolves a point separator.By heavy feed stock catalyzed conversion riser reactor end fast separating device, oil gas is separated rapidly with carbon deposited catalyst after reaction, can dry gas yied be reduced, suppress low-carbon alkene especially propylene transforming again after generating.Oil gas is separated through follow-up product separation system and obtains the products such as cracked gas, pyrolysis gasoline, cracking light oil and cracking masout; Spent agent enters the first follow-up stripper, and the spent agent after stripping returns the first riser reactor after importing the first revivifier regeneration by line of pipes and recycles.Operational condition in first riser reactor comprises: temperature of reaction is 450 ~ 650 DEG C, is preferably 480 ~ 600 DEG C; Agent-oil ratio (weight ratio of the first catalytic cracking catalyst and heavy feed stock) is 1 ~ 25, is preferably 5 ~ 20; Reaction times is 0.50 ~ 10 second, is preferably 1 ~ 10; Reactor pressure (absolute pressure) 0.1 ~ 0.4MPa, is preferably 0.15 ~ 0.35MPa.
Described heavy feed stock is heavy hydrocarbon and/or the various animals and plants oils raw materials being rich in hydrocarbon polymer, and described heavy hydrocarbon is selected from one or more the mixture in petroleum hydrocarbon, mineral oil and synthetic oil.Petroleum hydrocarbon is conventionally known to one of skill in the art, such as, can be the hydrocarbon ils that decompressed wax oil, long residuum, decompressed wax oil blending part reduced pressure residual oil or other secondary processing obtain.The hydrocarbon ils that described other secondary processing obtains as wax tailings, deasphalted oil, furfural treatment raffinate oil in one or more.Mineral oil is selected from one or more the mixture in liquefied coal coil, tar sand oil and shale oil.Synthetic oil is that coal, Sweet natural gas or pitch synthesize the distillate obtained through F-T.Be rich in various animals and plants oils raw materials such as animal grease, the Vegetable oil lipoprotein of hydrocarbon polymer.
The catalyst cracking method of production propylene provided by the invention, make the combined reactor contact reacts that light hydrocarbon and the second catalytic cracking catalyst are being composed in series by the second riser reactor and fluidized-bed reactor, light hydrocarbon is transformed, oil gas and the catalyst separating of the second reactor is left after reaction, catalyzer regenerates after entering stripper stripping, and the catalyzer after regeneration is introduced the second riser reactor and recycled.In the combined reactor that the second riser reactor and fluidized-bed reactor form, light hydrocarbon and the second catalytic cracking catalyst are in the second riser reactor after contact reacts, the oil agent mixture obtained is introduced in the fluidized-bed reactor be connected with the second riser reactor end and is continued to react, reacted hydrocarbon product enters the gas-solid separation equipment of settling vessel then through being connected with settling vessel and enters subsequent product separation system, obtain cracked gas, pyrolysis gasoline, cracking light oil and cracking masout, the spent agent that gas-solid separation equipment is separated enters fluidized bed reaction zone, the post catalyst reaction leaving fluidized bed reaction zone enters the second stripper, return the second riser reactor to introduce in Second reactivator regeneration after stripping after to recycle.The described gas-solid separation equipment be connected with settling vessel such as cyclonic separator.
The catalyst cracking method of production propylene provided by the invention, described light hydrocarbon is gasoline fraction and/or C4 hydrocarbon, preferably includes gasoline fraction and/or C4 hydrocarbon that the inventive method product separation system obtains.The operational condition of the second riser reactor is: when described light hydrocarbon comprises gasoline fraction, it is 10 ~ 30 that gasoline fraction operates agent-oil ratio (introducing the second catalytic cracking catalyst of the second riser reactor and the weight ratio of gasoline fraction) in the second riser tube, and the reaction times is 0.10 ~ 1.5 second; When described lightweight material comprises C4 hydrocarbon, it is 12 ~ 40 that C4 hydrocarbon operates agent-oil ratio (introducing the second catalytic cracking catalyst of the second riser reactor and the weight ratio of C4 hydrocarbon) in the second riser tube, and the reaction times is 0.50 ~ 2.0 second; The temperature of reaction of fluidized-bed reactor is 500 ~ 650 DEG C, and weight hourly space velocity is 1 ~ 35 hour
-1, reactor pressure 0.1 ~ 0.4MPa (absolute pressure).Preferably, the operation condition of gasoline fraction in the second riser reactor: gasoline fraction operates agent-oil ratio and is preferably 15 ~ 25 in the second riser tube; Reaction times is preferably 0.30 ~ 0.8 second; Gasoline fraction atomized water steam accounts for gasoline fraction inlet amount and is preferably 10 ~ 20 % by weight.The operation condition of C 4 fraction: C4 hydrocarbon operates agent-oil ratio (the second catalytic cracking catalyst introducing the second riser reactor and the weight ratio of C4 hydrocarbon introducing the second riser reactor) preferably 17 ~ 30 in the second riser reactor; Be rich in alkene C4 preferably 0.8 ~ 1.5 second reaction times in the second riser tube; The ratio that atomized water steam accounts for C4 inlet amount preferably 15 ~ 25 % by weight.
In catalyst cracking method provided by the invention, the operation condition of fluidized-bed reactor comprises: reaction pressure (settling vessel top hole pressure, absolute pressure) is 0.1 ~ 0.4MPa, is preferably 0.15 ~ 0.35MPa; Fluidized-bed reaction temperature is about 500 ~ 650 DEG C, is preferably 510 ~ 580 DEG C; The weight hourly space velocity (charging of fluid bedreactors THC) of fluidized-bed is 1 ~ 35 hour
-1, be preferably 3 ~ 30 hours
-1.
In the catalyst cracking method of production propylene provided by the invention, the light hydrocarbon introduced in the second riser reactor is gasoline fraction and/or C4 hydrocarbon, is preferably rich in gasoline fraction and/or the C4 hydrocarbon of alkene.The described gasoline fraction raw material being rich in alkene comprises gasoline fraction and/or other device production gasoline fraction that apparatus of the present invention produce (namely from product separation system of the present invention); One or more mixture in the gasoline fraction that the optional catalytic cracking raw gasline of other device production gasoline fraction, catalytic cracking stable gasoline, coker gasoline, visbreaker gasoil and other oil refining or chemical process are produced, preferentially selects the gasoline fraction that this device is produced.Described gasoline stocks can be the gasoline fraction of full range, and it is 40 ~ 204 DEG C that final boiling point is no more than 204 DEG C of such as boiling ranges, also can be narrow fraction wherein, the gasoline fraction of such as boiling range between 40 ~ 85 DEG C.The gasoline fraction injecting light hydrocarbon oil riser reactor is 0.05 ~ 0.20: 1 with the weight ratio of the heavy feed stock injecting the first riser reactor, preferably 0.08 ~ 0.15: 1.Described gasoline stocks is preferably rich in the gasoline fraction of alkene, and its olefin(e) centent is 20 ~ 95 % by weight, preferably 35 ~ 90 heavy %, preferably more than 50 % by weight.
The low-molecular-weight hydrocarbon that described C4 hydro carbons refers to C 4 fraction to be the normal temperature of main component, exist in gaseous form under normal pressure, comprises alkane, alkene and alkynes that carbonatoms in molecule is 4.It comprises the gaseous hydrocarbon products being rich in C 4 fraction that apparatus of the present invention are produced, and also can comprise the hydrocarbon gas being rich in C 4 fraction that other device process is produced, the C 4 fraction of wherein preferably apparatus of the present invention production.Described C4 hydro carbons is preferably rich in the C 4 fraction of alkene, and wherein the content of C4 alkene is greater than 50 heavy %, is preferably greater than 60 heavy %, preferably more than 70 % by weight.Preferred described light hydrocarbon comprises gasoline fraction, containing or not containing C4 hydrocarbon, the weight ratio of C4 hydrocarbon and gasoline fraction is 0 ~ 2: 1, preferably 0 ~ 1.2: 1, most preferably 0 ~ 0.8: 1.
Preferably, also the cracking masout that product separation system of the present invention obtains is introduced in the second riser reactor and carry out reacting and/or introduce fluidized-bed reactor and react, this is conducive to reducing dry gas yied and coke yield, and improves low-carbon alkene especially productivity of propylene.When cracking masout introduces the second riser reactor, the introducing position of described cracking masout preferably at 1/2nd places of the second riser reactor length to the part of leg outlet, namely described introducing position is preferably in the middle and lower reaches of the second riser reactor.Preferably, described cracking masout is introduced in fluidized-bed reactor and is reacted, and more preferably introduces the bottom of described fluidized-bed reactor.Described cracking masout is the cracking masout that product separation system of the present invention obtains, namely most of product liquid that the crackate entering product separation system is remaining after isolating gas, gasoline and diesel oil, its normal pressure boiling range is between 330 ~ 550 DEG C, and preferably its normal pressure boiling range is 350 ~ 530 DEG C.The cracking masout injecting the second riser tube and fluidized-bed reactor is 0.05 ~ 0.30: 1 with the weight ratio of the heavy feed stock injecting the first riser reactor, preferably 0.10 ~ 0.25: 1.
The catalyst cracking method of production propylene provided by the invention, reaction oil gas is separated with carbon deposited catalyst by the tripping device of the first riser reactor end, and oil gas product is introduced product separation system and is separated; Successively enter after settling vessel and gas-solid separation equipment isolate the catalyzer wherein carried from the reacted oil gas of the combined reactor of the second reactor and fluidized-bed reactor composition, enter follow-up product separation system.The oil gas product of the first riser reactor and the oil gas product of fluidized-bed reactor are introduced product separation system and are separated, and are preferably separated introducing product separation system after two strands of air-fuel mixtures.In product separation system, oil gas product is isolated to cracked gas, pyrolysis gasoline, cracking light oil and cracking masout.Described product separation system is prior art, and the present invention does not have particular requirement.
In the catalyst cracking method of production propylene provided by the invention, described riser reactor be selected from equal diameter riser tube, etc. a kind of in linear speed riser tube and variable diameters riser tube or the wherein combination of two kinds, wherein heavy hydrocarbon oil riser reactor and light hydrocarbon oil riser reactor can adopt identical pattern also can adopt different patterns.Described fluidized-bed reactor is selected from the combination of one or more in fixed fluidized bed, dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying bed and dense bed reactor.
In the second described riser reactor and fluidized-bed reactor combined reactor, leg outlet preferred lower pressure outlet distributor, its pressure drop is less than 10KPa.Described low tension outlet sparger such as arch sparger.
The catalyst cracking method of production propylene provided by the invention, heavy feed stock and light hydrocarbon adopt different catalyzer and reaction-regeneration system.Wherein the first catalytic cracking catalyst is mainly by active ingredient the catalyst cracking particles that the catalyst cracking particles of Y zeolite and active ingredient be mainly beta-molecular sieve and forms.Described active ingredient is mainly the catalyst cracking particles of Y zeolite, with the butt weight of this granules of catalyst for benchmark, at least comprise the Y zeolite of 10 weight, contain or do not contain other molecular sieve except Y zeolite, the content of other molecular sieve is no more than 5 % by weight; Preferably, the Y zeolite of 10 ~ 70 % by weight, the clay of 0 ~ 60 % by weight, the inorganic oxide binder of 15 ~ 60 % by weight is comprised; More preferably be made up of Y zeolite, the clay of 25 ~ 50 % by weight, the inorganic oxide binder of 25 ~ 50 % by weight of 25 ~ 50 % by weight.Described active component is mainly the catalytic cracking catalyst of beta-molecular sieve, comprises the beta molecular sieve of at least 10 weight, and contain or do not contain other molecular sieve beyond beta-molecular sieve, the content of other molecular sieve is no more than 5 % by weight; Preferably include the beta molecular sieve of 10 ~ 70 % by weight, the clay of 0 ~ 60 % by weight, the inorganic oxide binder of 15 ~ 60 % by weight; More preferably the beta molecular sieve of 25 ~ 50 % by weight, the clay of 25 ~ 50 % by weight, the inorganic oxide binder of 25 ~ 50 % by weight is comprised.
In the first described catalytic cracking catalyst, the mass ratio of the active ingredient mainly catalyst cracking particles of Y zeolite and the active ingredient mainly catalyst cracking particles of beta-molecular sieve is 4 ~ 1: 1 ~ 4, is preferably 1.5 ~ 3.5: 3.5 ~ 1.5.Described Y zeolite is the various Y zeolites generally adopted in prior art, such as, one or more mixture in rare earth Y type molecular sieve (REY), rare earth hydrogen Y zeolite (REHY), super-stable Y molecular sieves (USY), rare earth superstable Y-type molecular sieve (REUSY).Described beta molecular sieve is the beta-molecular sieve of the various modifications generally adopted in prior art, the beta-molecular sieve of such as Hydrogen beta-molecular sieve, phosphorus and transition metal modification.The concrete preparation of beta molecular sieve can see CN1035668C and CN1041616C.
The catalyst cracking method of production propylene provided by the invention, in light hydrocarbon oil catalytic conversion reaction, reprocessing cycle system, employing active ingredient is mainly the second catalytic cracking catalyst that mean pore size is less than 0.7nm shape-selective molecular sieve (as ZSM-5 molecular sieve), reacts in the second riser tube and fluidized-bed reactor.The content that in described second catalytic cracking catalyst, mean pore size is less than 0.7nm shape-selective molecular sieve is at least 10 % by weight, contain or do not contain other molecular sieve except mean pore size is less than 0.7nm shape-selective molecular sieve, the content of other molecular sieve described is no more than 5 % by weight, preferably press dry basis with described second catalytic cracking catalyst, the mean pore size that described second catalytic cracking catalyst comprises 10 ~ 65 % by weight is less than the shape-selective molecular sieve of 0.7 nanometer, the inorganic oxide binder of clay and 15 ~ 60 % by weight of 0 ~ 60 % by weight, more preferably the average all apertures comprising 20 ~ 50 % by weight are less than the shape-selective molecular sieve of 0.7 nanometer, the inorganic oxide binder of clay and 25 ~ 50 % by weight of 10 ~ 45 % by weight.The described shape-selective molecular sieve catalyzer being less than 0.7 nanometer containing mean pore size can be the combination of one or more provided by prior art, can be purchased or prepare according to existing method.
The shape-selective molecular sieve that described mean pore size is less than 0.7 nanometer is selected from ZSM series zeolite, ferrierite, chabazite, dachiardite, erionite, A zeolite, epistilbite, lomontite, and one or more the mixture among the zeolite that obtains after physics and/or chemical process process of above-mentioned zeolite.Described ZSM series zeolite is selected from one or more the mixture in ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38ZSM-48 and ZRP molecular sieve.The shape-selective molecular sieve that preferred mean pore size is less than 0.7 nanometer is one or more in ZSM-5 molecular sieve, ZRP molecular sieve, element modified ZSM-5 or element modified ZRP molecular sieve, and element modified ZSM-5 molecular sieve is ZSP molecular sieve such as.About the more detailed description of ZSM-5 molecular sieve is see USP3702886, about the more detailed description of ZRP is see USP5232675, CN1211470A, CN1611299A.
Described inorganic oxide, as caking agent, can be selected from silicon-dioxide (SiO
2) and/or aluminium sesquioxide (Al
2o
3).Described clay is as matrix, i.e. carrier, can be selected from kaolin and/or halloysite.
The operating method of the revivifier described in the inventive method and operational condition can refer to Conventional catalytic cracking revivifier.
For the catalytic cracking unit that the present invention uses, at least comprise reactor part, stripper section, regenerator section and product separation system.Preferably, reactor adopts double lifting leg and fluidized-bed to form combined reactor configuration, one of them riser tube connect with fluidized-bed reactor after and another riser tube be arranged in juxtaposition mutually, and described riser tube and fluidized-bed reactor cascaded structure further with stripper arranged in series.Arrange a dividing plate at above-mentioned stripper and be divided into two independent stripping zones, the reaction that the combined reactor that one of them stripping zone and riser tube and fluidized-bed are formed is formed, stripping route, it is for light hydrocarbon catalyzed conversion; Another stripping zone then forms to another riser tube that another road corresponding is reacted, stripping route, and it is for heavy feed stock catalyzed conversion.Settle a dividing plate to be divided into two breeding blankets in described revivifier to be connected with corresponding stripping zone respectively, thus form two strands of independently catalyst reaction, reprocessing cycle routes.
A kind of catalytic cracking unit that the present invention uses, as shown in Figure 1, described catalytic cracking unit the first stripping zone 51 and the second stripping zone 52 of comprising riser reactor 1, gas-solid separation equipment 7, riser reactor 2 and the fluidized-bed reactor 3 of connecting with it with the outlet of riser reactor 1, the gas-solid separation equipment 8 of fluidized-bed reactor, settling vessel 9, stripper dividing plate 5 and being separated by dividing plate 5; The catalyst outlet of gas-solid separation equipment 7 is communicated with the first stripping zone 51, and the top of the first stripping zone is communicated with settling vessel 9; The top of fluidized-bed reactor 3 is communicated with settling vessel 9, and the bottom of fluidized-bed reactor 3 is communicated with stripping zone 52, and the entrance of gas-solid separation equipment 8 is communicated with settling vessel 9; The catalyst outlet position of gas-solid separation equipment 8 enables catalyzer wherein enter stripping zone 52 or fluidized-bed reactor 3, can be in above fluidized-bed reactor, in fluidized-bed reactor or in the second stripping zone 52 for this reason; Be communicated with oil and gas separating system after gas-solid separation equipment 7 is connected with the oil gas vent of gas-solid separation equipment 8.Described revivifier can be two independent revivifiers, also can be as shown in Figure 1 a revivifier is divided into two breeding blankets, the dividing plate 6 wherein settled in revivifier 4, is divided into two independent breeding blankets 61 and 62, is connected respectively with stripping zone 51 with 52 by revivifier 4.In order to freshening cracking masout, described riser reactor 2 and/or fluidized-bed reactor 3 also comprise cracking masout entrance.Stripper dividing plate 5 preferably also extends in settling vessel, the bottom of settling vessel is divided into two regions do not communicated, be used separately as the settling vessel of combined reactor and the settling vessel of riser reactor 1 that riser reactor 2 and fluidized-bed reactor 3 form, preferably two negative areas are communicated with at the top of settling vessel 5, the headspace of public settling vessel 9.
The above-mentioned catalytic cracking conversion system for the inventive method, can realize adopting different catalyzer to carry out selective conversion to different cuts and distinguishing stripping and regeneration to used catalyst, simply, formation two strands of relatively independent catalyst reactions, reprocessing cycle route is effectively completed, compact construction and easy to implement, device operation is relatively simple, flexible, solves the disadvantageous mutual interference of elimination two kinds of catalyst systems engineering very well.Riser tube and fluidized-bed combined reactor and the second stripping zone arranged in series, water stripping steam can be realized and introduce fluidized-bed reactor, reactor is discharged after making it pass fluidized-bed reactor, both oil gas dividing potential drop can effectively be reduced, shorten oil gas in the settling section residence time, thus be conducive to propylene enhancing, reduce dry gas, coke yield.
Below in conjunction with accompanying drawing, the present invention is further described:
In method as shown in Figure 1, first catalytic cracking catalyst of being derived by the first breeding blanket 61 of revivifier 4 enters bottom riser reactor 1 through regenerator inclined tube 40, second catalytic cracking catalyst of being derived by breeding blanket 62 flows to bottom riser reactor 2 through regenerator inclined tube 41, and correspondingly two strands of catalyzer accelerate upwards to flow respectively under the pre-lift medium effect of being injected by pipeline 22 and 23.Heavy feed stock after preheating (heavy hydrocarbon or be rich in the various animals and plants oils of hydrocarbon polymer) is after pipeline 20 mixes by a certain percentage with the atomizing steam from pipeline 21, injecting lift pipe reactor 1, oil gas carbon deposited catalyst after reaction is separated with the fast separating device 7 of catalyst mixture through riser tube 1 end by reaction oil gas; The light hydrocarbon (being such as rich in gasoline fraction and/or the C4 hydrocarbon of alkene) of preheating simultaneously or not preheating is after pipeline 24 mixes by a certain percentage with the atomizing steam from pipeline 25, injecting lift pipe reactor 2, thereafter reaction oil gas and catalyst mixture are along in riser tube 2 upwards flowing-path, reaction oil gas and catalyst mixture continue reaction after the outlet distributor (not marking in figure) of riser tube 2 enters fluidized-bed reactor 3, carry out being separated of oil gas and catalyzer after finally entering settling vessel 9 through gas-solid separation equipment 8.All hydrocarbon oil product, are comprised oil gas that riser tube 1 exports and are all collected by settling vessel top cyclone separation system (not marking figure) from the oil gas that fluidized-bed reactor 3 flows out and draw reactor by pipeline 26 and enter subsequent product separation system (not marking in figure).In product separation system, catalytic pyrolysis product separation is hydrocarbon gas, pyrolysis gasoline, cracking light oil, cracking masout and cracking slurry oil.Cracked gaseous hydrocarbons is separated at subsequent product, refining after can obtain polymerization-grade propylene product and be rich in the C 4 fraction of alkene, the C 4 fraction being wherein rich in alkene can transform production propylene by Returning reactor again, preferably the C 4 fraction being rich in alkene is returned riser tube 2 and transforms.Pyrolysis gasoline can partly or entirely transform by Returning reacting system again; Also can first gasoline be cut into gently, heavy naphtha section, the part or all of Returning reacting system of petroleum naphtha transforms again, preferably petroleum naphtha is returned riser tube 2 and transforms.
The isolated carbon deposited catalyst of fast separating device 7 through riser tube 1 end enters stripping zone 51, the spent agent after separating device 8 is separated to contact with the oil agent mixture that riser tube 2 is drawn laggard enter fluidized-bed reactor 3, then enter independent stripping zone 52; Stripped vapor injects stripper through pipeline 50, with carbon deposited catalyst counter current contact, by the reaction oil gas entrained by carbon deposited catalyst, stripping is clean as much as possible, the stripped vapor of stripping zone 51 directly enters settling vessel 9, and the stripped vapor of stripping zone 52 is introduced into fluidized-bed reactor 3 then enters stripper 9, after gas-solid separation equipment 8 is separated, draw reactor by pipeline 26 together with other oil gas.Stripping zone 51 after stripping and the catalyzer of stripping zone 52 send into two independent breeding blankets 61 respectively by spent agent inclined tube 42 and 43 and coke burning regeneration is carried out in breeding blanket 62.Oxygen-containing gas such as air injects revivifier 4 through pipeline 60, and the regenerated flue gas of two breeding blankets is drawn through pipeline 63 in the top public space mixing of revivifier 4.Catalyzer after regeneration returns riser reactor 1 and 2 respectively through regenerator inclined tube 40 and 41 and recycles.
In above-mentioned embodiment process, introduce pre-lift medium by pipeline 22 and 23 respectively to riser tube 1 and riser tube 2.Described pre-lift medium is known for those skilled in the art, can be selected from one or more in water vapour, C1 ~ C4 hydro carbons or Conventional catalytic cracking dry gas, preferably water steam.
The following examples will be further described the present invention.
The raw material used in embodiment and comparative example comprises raw material A, raw material B, raw material C and raw material D, wherein raw material A and B are two kinds of different heavy oil fractions, raw material C and raw material D is respectively the pyrolysis gasoline and routine full cut catalytic cracking product gasoline that are rich in alkene, and specific nature is in table 1.The catalyzer adopted is respectively CHP that Sinopec catalyzer asphalt in Shenli Refinery produces and plants laboratory prepares four kinds of catalyzer that name is called Y, B and BY.Four kinds of catalyzer specific natures, in table 2, all carry out 790 DEG C × 100%H before using
2the aging pre-treatment of water vapour of O × 14 hour (namely in 790 DEG C, under 100% steam atmosphere aging 14 hours), wherein the active ingredient of Y catalyzer is USY molecular sieve, the active ingredient of B catalyzer is beta molecular sieve, BY catalyst activity component is USY molecular sieve and beta-molecular sieve, the active ingredient of CHP catalyzer is ZRP molecular sieve, and in three kinds of catalyzer, to account for the ratio of catalyzer total amount substantially suitable for active component.
Y catalyzer, B catalyzer and BY catalyzer are prepared according to existing method, its preparation process is as follows: water, kaolin, pseudo-boehmite and hydrochloric acid are added plastic cans by (1) successively, wherein the consumption of water makes the solid content of the slurries obtained be 30 % by weight, hydrochloric acid (in HCl) is 0.18: 1 with the mol ratio of pseudo-boehmite (in aluminum oxide), stirs; (2) gained slurries are warming up to 65 DEG C, stop stirring, static aging 1h; (3) be cooled to 50 DEG C, add Alumina gel and molecular sieve pulp (content of molecular sieve pulp Middle molecule sieve is 30 % by weight) successively, continue to stir; (4) slurries are spray-dried shaping, washing, the obtained catalyst sample of oven dry.The composition of Y catalyzer, B catalyzer and BY catalyzer is: containing molecular sieve 35 % by weight, kaolin 35 % by weight, pseudo-boehmite (in aluminum oxide) 26 % by weight, Alumina gel (in aluminum oxide) 4 % by weight.Wherein, in BY catalyzer, the mass ratio of two kinds of molecular sieves is Y zeolite: beta molecular sieve=2: 3, and namely the content of Y zeolite is 14 % by weight, and the content of beta molecular sieve is 21 % by weight.B catalyzer contains beta-molecular sieve 35 % by weight, kaolin 35 % by weight, pseudo-boehmite (in aluminum oxide) 26 % by weight, Alumina gel (in aluminum oxide) 4 % by weight.Wherein, beta-molecular sieve silica alumina ratio (SiO
2/ Al
2o
3mol ratio) be 30, be Hydrogen; USY molecular sieve, its content of rare earth 2 % by weight, silica alumina ratio (SiO
2/ Al
2o
3mol ratio) be 5.2; USY, beta-molecular sieve are China Petrochemical Industry's catalyzer Shandong company and produce.
Comparative example 1
Experiment is carried out in small fixed flowing bed (FFB) catalytic cracking unit.This apparatus design is interval type, single-pass operation pattern.Raw material is heavy oil A, and catalyzer is BY.
Heavy oil A as shown in table 2 enters in fluidized-bed reactor and carries out catalyzed reaction with BY catalyst exposure, and reaction conditions is: temperature of reaction is 520 DEG C, agent-oil ratio 6, weight hourly space velocity 15h
-1, water filling vapor volume is 5 % by weight.Reaction product, steam are separated in settling vessel with spent agent, and reaction product isolated obtains gaseous product and product liquid, and spent agent catalyzer is gone out the hydrocarbon product that spent agent adsorbs by water vapor stripping.Spent agent after stripping and heated hot air regenerate, and the catalyzer after regeneration carries out new catalytic conversion reaction again.Test conditions and main result are in table 3.
Comparative example 2
FFB device described in comparative example 1 is tested.Raw material is identical with comparative example 1 with reaction conditions, unlike the mechanical mixture that catalyzer is B and Y two kinds of catalyzer, wherein the mixed weight ratio of Y catalyzer and B catalyzer is respectively 40 % by weight and 60 % by weight, the content forming Y molecular sieve and beta-molecular sieve in catalyst mixture is respectively 14 % by weight and 21 % by weight, identical with two kinds of molecular sieve content in BY catalyzer.Experiment prevailing operating conditions and the results are shown in table 3.
Comparative example 3
FFB device described in comparative example 1 is tested.Raw material is identical with comparative example 1 with reaction conditions, is Y unlike catalyzer, the prevailing operating conditions of experiment and the results are shown in table 3.
Comparative example 4
Experiment is carried out in small fixed flowing bed (FFB) catalytic cracking unit.Raw material is heavy oil B, and catalyzer is CHP.
Heavy oil B as shown in table 2 enters in fluidized-bed reactor and carries out catalyzed reaction with CHP catalyst exposure, and reaction conditions is: temperature of reaction is 580 DEG C, agent-oil ratio 5, weight hourly space velocity 1h
-1, water filling vapor volume is 30 % by weight.Reaction product, steam are separated in settling vessel with spent agent, and reaction product isolated obtains gaseous product and product liquid, and spent agent catalyzer is gone out the hydrocarbon product that spent agent adsorbs by water vapor stripping.Spent agent after stripping and heated hot air regenerate, and the catalyzer after regeneration carries out new catalytic conversion reaction again.Test conditions and main result are in table 3.
Comparative example 5
FFB device described in comparative example 4 is tested.Catalyzer is identical with comparative example 4 with reaction conditions, becomes raw material D unlike stock oil.
Comparative example 6
FFB device described in comparative example 5 is tested.Reaction conditions is identical with comparative example 4 with comparative example 5 with catalyzer, is not both raw material and changes, the prevailing operating conditions of experiment and the results are shown in table 3.
Embodiment 1
Experiment is carried out at kitty cracker.This device comprises two cover reaction-regeneration systems: the first riser reactor, and internal diameter is 16 millimeters, and length is 3800 millimeters, and catalyzer used is made up of the B catalyzer of 40 % by weight Y catalyzer and 60 % by weight, and the raw material A shown in his-and-hers watches 1 carries out cracking; Oil gas after conversion and catalyst separating, catalyzer enters the first revivifier regeneration after entering the first stripper, the catalyzer after regeneration returns the first riser reactor and recycles; Oil gas is introduced product separation system and is separated.In second riser reactor, warp is 16mm, length is 3200mm, series fluidized bed reactor after second riser reactor, the diameter of fluidized-bed reactor is 64 millimeters for (internal diameter), length 600 millimeters, gasoline fraction (boiling range is 30 ~ 85 DEG C) from product separation system is transformed, catalyzer used is CHP, oil gas after conversion and catalyst separating, catalyzer enters Second reactivator regeneration after entering the second stripper, the catalyzer after regeneration returns the second riser reactor and recycles; Oil gas is introduced product separation system and is separated.The oil gas obtained after first riser reactor reaction is separated in identical product separation system with after the air-fuel mixture obtained after fluidized-bed reactor reaction.Oil gas after second stripper stripping enters corresponding settling vessel through fluidized-bed reactor.Its reaction and operational condition and reaction result are in table 4.
Comparative example 7
Experiment is carried out at kitty cracker, and riser tube adds fluidized-bed reaction.
In riser reactor, warp is 16mm, length is 3200mm, series fluidized bed reactor after riser reactor, the diameter of fluidized-bed reactor is 64 millimeters for (internal diameter), height 600 millimeters, raw material A shown in his-and-hers watches 1 transforms, and catalyzer used is MMC-2 (catalyzer asphalt in Shenli Refinery of China Petrochemical Industry product, containing USY type molecular sieve and ZRP molecular sieve).Oil gas after conversion and catalyst separating, catalyzer enters revivifier regeneration after entering stripper, the catalyzer after regeneration returns riser reactor and recycles; Oil gas product is introduced product separation system and is separated.Oil gas after stripper stripping enters corresponding settling vessel through fluidized-bed reactor.Its reaction and operational condition and reaction result are in table 4.
Embodiment 2
With reference to embodiment 1, in the second riser reactor, introduce cracking masout (boiling range of cracking masout is 350 ~ 500 DEG C) unlike exporting 1.5 meters of at distance the second riser reactor, the introduction volume of described cracking masout and the weight ratio of raw material A are 0.05: 1.
Embodiment 3
According to the method for embodiment 2, introduce bottom fluidized-bed reactor unlike cracking masout, do not introduce riser reactor 2.
Embodiment 4
Use reaction unit provided by the invention.As shown in Figure 1, this middle-scale device riser reactor 1 internal diameter is 16 millimeters, and length is 3800 millimeters, and the internal diameter of riser reactor 2 is 16 millimeters, and length is 3200 millimeters, and adopts external riser tube pattern to arrange.Riser reactor 2 exports and connects fluidized-bed reactor 3, and the cross section semicircular in shape of this fluidized-bed reactor, it is 64 millimeters of circular area that its cross-sectional area equals diameter, length 600 millimeters.Settling vessel 9 length is 1520mm, diameter is 250mm, wherein stripper dividing plate 5 is straight plate, stripper is divided into two portions, the sectional area forming the stripping zone 51 of circulating with riser reactor 1 accounts for 85% of whole stripping stage sectional area, and stripper dividing plate 5 extends to settling vessel, along distance settling vessel top 500mm on dividing plate.Test adopts freshening mode to operate.Raw material B is introduced the first riser reactor with the catalyst mixture that forms of B catalyzer by 40 % by weight Y catalyzer and 60 % by weight react, reacted oil gas enters fast separating device and is separated, catalyzer after separation enters stripping zone 51, introduce breeding blanket 61 after stripping to regenerate, oil gas with enter product separation system after the air-fuel mixture of fluidized-bed reactor and be separated, be separated the gasoline fraction (boiling range is 30 ~ 85 DEG C) obtained and introduce riser reactor 2, its amount is 0.15: 1 with the weight ratio of raw material B, react with the CHP catalyst exposure introduced wherein, then enter fluidized-bed reactor 3 to react, oil gas after fluidized-bed reaction enter settling vessel isolated the catalyzer wherein carried by gas-solid separator 8 after with the air-fuel mixture of the first reactor after enter product separation system, catalyzer in fluidized-bed reactor enters stripping zone 52 from leaving bottom it, enter breeding blanket 62 after stripping to regenerate, oil gas after stripper 52 stripping enters settling vessel through fluidized-bed reactor 3.Its operational condition and reaction result are in table 4.
From table 4, the inventive method can improve heavy oil conversion performance, reduces dry gas and coke yield, by cracking masout freshening to riser tube and fluidized-bed combined reactor while the gain in yield of propylene and butylene, heavy oil yield can be reduced further, increase the productive rate of propylene and iso-butylene.The net-structure apparatus using the present invention to propose, can reduce heavy oil yield, increases the productive rate of propylene and iso-butylene, improves the yield of high-value product, has a significant effect.
Table 1
Table 2
| Catalyzer title | Y | BY | B | CHP | MMC-2 |
| Chief active constituent element | USY | USY+β | β | ZRP | USY+ZRP |
| Chemical property, % by weight | |||||
| Al 2O 3 | 53.1 | 50.6 | 48.9 | 51 | 52.3 |
| Na 2O | / | / | / | 0.066 | 0.072 |
| RE 2O 3 | 0.67 | / | / | / | / |
| Physical properties | |||||
| Total pore volume, ml/g | 0.196 | 0.165 | 0.144 | 0.22 | 0.164 |
| Specific surface, m 2/g | 144 | 129 | 120 | 105 | 113 |
| Micro-activity, % by weight | 69 | 66 | 64 | 52 | 64 |
Table 3
Table 4
Claims (13)
1. produce a catalyst cracking method for propylene, comprising:
(1) heavy feed stock and the first catalytic cracking catalyst contact reacts in the first riser reactor is made, reacted oil gas is separated with the first catalytic cracking catalyst, oil gas introduces product separation system, first catalytic cracking catalyst introduces the first revivifier regeneration after the first stripper stripping, and the first catalytic cracking catalyst after regeneration is introduced the first riser reactor and recycled; Wherein, described first catalytic cracking catalyst is mainly by active ingredient the granules of catalyst that the granules of catalyst of Y zeolite and active ingredient be mainly beta-molecular sieve and forms; First riser reactor temperature of reaction is 450 ~ 650 DEG C, and agent-oil ratio is 1 ~ 25, and the reaction times is 0.5 ~ 10 second;
(2) light hydrocarbon is made to be less than the second catalytic cracking catalyst of 0.7nm shape-selective molecular sieve in the second reactor contact reacts with containing aperture; The second described reactor comprises the second riser reactor and the fluidized-bed reactor of series connection, and the reacted oil gas of the second riser reactor and reacted second catalytic cracking catalyst are introduced the fluidized-bed reactor of connecting with the second riser reactor and reacted; Oil gas after fluidized-bed reaction introduces product separation system, the second catalytic cracking catalyst after fluidized-bed reaction introduces Second reactivator regeneration after introducing the second stripper stripping, the second catalytic cracking catalyst after regeneration is introduced the second riser reactor and recycled; Described light hydrocarbon comprises gasoline fraction and/or C4 hydrocarbon; When described light hydrocarbon comprises gasoline fraction, the agent-oil ratio that gasoline fraction operates in the second riser reactor is 10 ~ 30, and the reaction times is 0.10 ~ 1.5 second; When described light hydrocarbon comprises C4 hydrocarbon, it is 12 ~ 40 that C4 hydrocarbon operates agent-oil ratio in the second riser tube, and the reaction times is 0.50 ~ 2.0 second; The temperature of reaction of fluidized-bed reactor is 500 ~ 650 DEG C, and weight hourly space velocity is 1 ~ 35 hour
-1.
2. in accordance with the method for claim 1, it is characterized in that, the butt weight being mainly the granules of catalyst of Y zeolite with active ingredient is benchmark, and the granules of catalyst that described active ingredient is mainly Y zeolite comprises 10 ~ 70 % by weight Y zeolites, the clay of 0 ~ 60 % by weight, the inorganic oxide binder of 15 ~ 60 % by weight; The butt weight being mainly the granules of catalyst of beta-molecular sieve with active ingredient is benchmark, and the granules of catalyst that described active ingredient is mainly beta-molecular sieve comprises 10 ~ 70 % by weight beta molecular sieves, the clay of 0 ~ 60 % by weight, the inorganic oxide binder of 15 ~ 60 % by weight; It is 4 ~ 1: 1 ~ 4 that described active ingredient is mainly the weight ratio that the granules of catalyst of Y zeolite and described active ingredient be mainly the granules of catalyst of beta-molecular sieve.
3. in accordance with the method for claim 2, it is characterized in that, the granules of catalyst that described active ingredient is mainly Y zeolite comprises the inorganic oxide binder of the Y zeolite of 25 ~ 50 % by weight, clay and 25 ~ 50 % by weight of 25 ~ 50 % by weight; The particle that described active ingredient is mainly beta molecular sieve comprises the inorganic oxide binder of the beta molecular sieve of 25 ~ 50 % by weight, clay and 25 ~ 50 % by weight of 25 ~ 50 % by weight.
4. in accordance with the method for claim 1, it is characterized in that, with the second catalytic cracking catalyst butt weight for benchmark, the aperture that the second described catalytic cracking catalyst comprises 10 ~ 65 % by weight be less than 0.7nm shape-selective molecular sieve, 0 ~ 60 % by weight the inorganic oxide binder of clay and 15 ~ 60 % by weight.
5. in accordance with the method for claim 4, it is characterized in that, the aperture that the second described catalytic cracking catalyst comprises 20 ~ 50 % by weight is less than 0.7nm shape-selective molecular sieve, the clay of 10 ~ 45 % by weight, the inorganic oxide binder of 25 ~ 50 % by weight.
6. in accordance with the method for claim 1, it is characterized in that, the operational condition of the first riser reactor: temperature of reaction is 480 ~ 600 DEG C; Agent-oil ratio is 5 ~ 20; Reaction times is 1 ~ 10 second; Reaction pressure is 0.15 ~ 0.35MPa.
7. in accordance with the method for claim 1, it is characterized in that, when described light hydrocarbon comprises gasoline fraction, it is 15 ~ 25 that described gasoline fraction operates agent-oil ratio in the second riser tube, and the reaction times is 0.30 ~ 0.8 second.
8. according to the method described in claim 1 or 7, it is characterized in that, when described light hydrocarbon comprises C4 hydrocarbon, it is 17 ~ 30 that C4 hydrocarbon operates agent-oil ratio in the second riser reactor, and the reaction times is 0.8 ~ 1.5 second.
9. according to catalyst cracking method according to claim 1, it is characterized in that, described heavy feed stock is heavy hydrocarbon and/or the various animals and plants oils raw materials being rich in hydrocarbon polymer, and described heavy hydrocarbon is selected from one or more the mixture in petroleum hydrocarbon, mineral oil and synthetic oil.
10. according to catalyst cracking method according to claim 1, it is characterized in that, described light hydrocarbon comprises gasoline fraction from described product separation system and/or C4 hydrocarbon.
11. in accordance with the method for claim 1, it is characterized in that, the cracking masout that product separation system obtains is introduced the middle and lower reaches of the second riser reactor and/or introduced the bottom of fluidized-bed reactor.
12. in accordance with the method for claim 1, it is characterized in that, the catalytic cracking unit that the method uses, comprises riser reactor (1), gas-solid separation equipment (7) with the outlet of riser reactor (1), riser reactor (2), the fluidized-bed reactor (3) of connecting with riser reactor (2), the gas-solid separation equipment (8) of fluidized-bed reactor, settling vessel (9), stripper dividing plate (5) and the first stripping zone (51) separated by dividing plate (5) and the second stripping zone (52); The catalyzer that the catalyst outlet position of gas-solid separation equipment (7) makes it be separated and obtains enters the first stripping zone (51), and the top of the first stripping zone is communicated with settling vessel (9); The entrance of gas-solid separation equipment (8) is communicated with settling vessel (9), and the catalyzer that the catalyst outlet position of gas-solid separation equipment (8) enables it be separated and obtains enters the second stripping zone (52) or fluidized-bed reactor (3); Be communicated with oil and gas separating system after gas-solid separation equipment (7) is connected with the oil gas vent of gas-solid separation equipment (8); The top of fluidized-bed reactor (3) is communicated with settling vessel (9), and the bottom of fluidized-bed reactor (3) is communicated with stripping zone (52).
13. in accordance with the method for claim 12, it is characterized in that, riser reactor (2) and/or fluidized-bed reactor (3) also comprise cracking masout entrance.
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| CN104232148B (en) * | 2014-09-22 | 2016-06-01 | 中国石油大学(华东) | The two-stage riser fluid catalytic cracking settling vessel of a kind of slow down coking |
| CN106147832B (en) * | 2015-04-20 | 2017-11-14 | 中国石化工程建设有限公司 | A kind of catalytic cracking selective reaction regeneration technology |
| CN106893609A (en) * | 2015-12-21 | 2017-06-27 | 中国石油天然气集团公司 | Produce the device and method of propylene content cracked gas high and gasoline with low olefine content |
| CN107964419B (en) * | 2016-10-19 | 2020-12-04 | 中国石油化工股份有限公司 | Processing technology of biological oil |
| CN109705905B (en) * | 2017-10-25 | 2021-04-06 | 中国石油化工股份有限公司 | Method and device for producing more low-carbon olefins |
| CN109704904B (en) * | 2017-10-25 | 2021-07-09 | 中国石油化工股份有限公司 | Method for increasing yield of low-carbon olefin and light aromatic hydrocarbon |
| CN109704903B (en) * | 2017-10-25 | 2021-09-07 | 中国石油化工股份有限公司 | Method for producing more propylene and light aromatic hydrocarbon |
| CN109722289B (en) * | 2017-10-30 | 2021-05-14 | 中国石油化工股份有限公司 | Catalytic cracking process for reducing dry gas and coke yields |
| CN110317629B (en) * | 2019-04-17 | 2020-10-27 | 中国石油大学(北京) | Double-catalyst zone catalytic cracking method and device |
| CN110317630B (en) * | 2019-04-17 | 2020-10-27 | 中国石油大学(北京) | Catalyst zoned catalytic cracking method and device |
| CN110317628B (en) * | 2019-04-17 | 2021-01-15 | 中国石油大学(北京) | Catalyst partition comprehensive catalytic cracking method and device |
| CN115725326A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Catalytic conversion method and device for producing ethylene, propylene and light aromatic hydrocarbon |
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| CN101062885A (en) * | 2006-04-28 | 2007-10-31 | 中国石油化工股份有限公司 | Catalytic conversion method for increasing propylene production |
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| US3856659A (en) * | 1972-12-19 | 1974-12-24 | Mobil Oil Corp | Multiple reactor fcc system relying upon a dual cracking catalyst composition |
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