CN102690679A - Catalytic cracking method for producing propylene - Google Patents
Catalytic cracking method for producing propylene Download PDFInfo
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- CN102690679A CN102690679A CN2011100727671A CN201110072767A CN102690679A CN 102690679 A CN102690679 A CN 102690679A CN 2011100727671 A CN2011100727671 A CN 2011100727671A CN 201110072767 A CN201110072767 A CN 201110072767A CN 102690679 A CN102690679 A CN 102690679A
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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 of producing propylene.
Background technology
Heavy oil catalytic pyrolysis is the important method of small-numerator olefins such as preparation ethene, propylene and butylene; The method of the RFCC production low-carbon alkene that generally uses in the industry is the catalytic pyrolysis technology (DCC of maximum production of propylene for example; USP4980053 and USP5670037) and maximum produce the catalytic pyrolysis technology (CPP of ethene; USP6210562); These two kinds technology adopt the structure of reactor of single riser reactor or single riser reactor combination dense phase fluidized bed to cooperate special-purpose catalyst under higher temperature conditions, to react; Employed catalyzer all is single catalyst systems that the mesopore zeolite (like ZSM-5) that contains the MFI structure and/or large pore zeolite (like Y molecular sieve) isoreactivity constituent element constitute, and is guaranteeing to pursue higher small-numerator olefin productive rate on certain heavy oil conversion basis.But; Because strengthening heavy oil conversion differs greatly with the needed catalytic active center of raising small-numerator olefin; Therefore, be difficult in sometimes on its catalyst formulation and take into account the requirement that heavy oil conversion reaction and voluminous small-numerator olefin react in the reactor drum of single riser reactor or single riser reactor combination dense phase fluidized bed simultaneously.In addition, some CCU also increases voluminous small-numerator olefin productive rate through the auxiliary agent method that interpolation contains the ZSM-5 zeolite at present.Though this method has better flexibility; But this method is except increase small-numerator olefin productive rate amplitude is less; The defective that also exists other to be difficult to overcome: the one,, the auxiliary agent that contains the ZSM-5 zeolite when interpolation is difficult to reach voluminous small-numerator olefin requirement very little the time; The 2nd; When interpolation contains the auxiliary agent of ZSM-5 zeolite when higher; The physics diluting effect that the main catalytic cracking catalyst is existed significant adverse; Thereby reduce whole catalyst system net effect, also have the problem that performance is mated each other between auxiliary agent and Primary Catalysts simultaneously, its productivity of propylene is difficult to further raising.
CN100448954C discloses the catalysis conversion method of propylene enhancing.This method adopts two kinds of catalyst mixtures to participate in reaction, and a kind of is the catalyzer that contains Y zeolite, and is another kind of for containing the catalyzer of ZSM-5 molecular sieve, transition metal additives and phosphorus additive.Reaction unit adopts the 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 products such as gasoline, diesel oil and liquefied gas; Isolate liquefied gas intermediate product behind the propylene and be injected in the service hoisting pipe reactor and contact, successively carry out alkene oligomerization, superimposed product cracking and dehydrating alkanes and react the propylene enhancing product with two kinds of hot catalyst mixtures.This method can't solve states spinoffs such as two kinds of interference, dilution between catalyzer, and productivity of propylene is not high; Do not relate to reaction, regenerating unit structure yet.
CN101314724A discloses a kind of bio-oil and MO combined catalytic conversion method.It is that the catalyzer of essential active catalyzed conversion bio-oil and MO in riser tube and fluidized-bed compound reactor are used for producing small-numerator olefins such as propylene that this method adopts modified beta zeolite and the zeolite with MFI structure.This method is used the single catalyst system that contains the various active constituent element; Be difficult to take into account heavy oil conversion reaction and two kinds of requirements that response difference is very big of voluminous small-numerator olefin reaction; Can't solve spinoffs such as interference between above-mentioned two kinds of zeolites, dilution well; Productivity of propylene is not high, and in addition, this patent does not have particular requirement and regulation to the reaction unit structure aspects yet.
CN101134913A discloses a kind of hydrocarbons catalytic conversion method of producing low-carbon alkene, and this method obtains C2～C4 alkene, gasoline, diesel oil, heavy oil and other low molecule saturated hydrocarbons after with the hydrocarbon material catalytic cracking; The catalyzer that this method is used contains by the β zeolite of phosphorus and transition metal M modification and other kind zeolites of surplus.This method adopts the single catalyst system that is made up of the various active constituent element, is difficult to take into account simultaneously heavy oil conversion and the very big reaction of voluminous small-numerator olefin two species diversity, and productivity of propylene is not high.
Summary of the invention
The technical problem that the present invention will solve provides a kind of catalyst cracking method of producing propylene, and this method is used for heavy feed stock and transforms, and has higher productivity of propylene.
The present invention provides a kind of catalyst cracking method of producing propylene, comprising:
(1) makes the heavy feed stock and first catalytic cracking catalyst contact reacts in first riser reactor; Reacted oil gas is separated with first catalytic cracking catalyst; Oil gas is introduced the product separation system; First catalytic cracking catalyst is introduced the regeneration of first revivifier behind the first stripper stripping, first catalytic cracking catalyst after the regeneration is introduced first reactor cycles and used; Wherein, said first catalytic cracking catalyst is mainly the granules of catalyst of Y zeolite by active ingredient and granules of catalyst that active ingredient is mainly beta-molecular sieve is formed; The first riser reactor temperature of reaction is 450～650 ℃, and agent-oil ratio is 1～25, and the reaction times is 0.50～10 second;
(2) make light hydrocarbon with contain the aperture less than second catalytic cracking catalyst of 0.7nm shape-selective molecular sieve in the second reactor drum contact reacts; Described second reactor drum comprises placed in-line second riser reactor and fluidized-bed reactor, and reacted oil gas of second riser reactor and reacted second catalytic cracking catalyst are introduced and the placed in-line fluidized-bed reactor reaction of second riser reactor; Oil gas behind the fluidized-bed reaction is introduced the product separation system, and catalyzer is introduced the regeneration of second revivifier after introducing the second stripper stripping, and second catalytic cracking catalyst after the regeneration is introduced second riser reactor and recycled; Said light hydrocarbon comprises gasoline fraction and/or C4 hydrocarbon; When said light hydrocarbon comprised gasoline fraction, the agent-oil ratio that gasoline fraction is operated in second riser reactor was 10～30, and the reaction times is 0.10～1.5 second; When said light hydrocarbon comprised the C4 hydrocarbon, the C4 hydrocarbon is operated agent-oil ratio in second riser tube be 12～40, and the reaction times is 0.50～2.0 second; The temperature of reaction of fluidized-bed reactor is 500～650 ℃, and weight hourly space velocity is 1～35 hour
-1
The catalyst cracking method of production propylene provided by the invention; In heavy feed stock catalytic conversion reaction, reprocessing cycle system; The cracking catalyst of using is for being the granules of catalyst of main active component with Y zeolite and being the mixture that the granules of catalyst of main active component is formed with beta-molecular sieve that in light hydrocarbon oil catalytic conversion reaction, reprocessing cycle system, the cracking catalyst of use is main active component with mean pore size less than the 0.7nm shape-selective molecular sieve; Can fully, easily strengthen heavy oil conversion; Highly selective is converted into heavy feed stock small-numerator olefin products such as propylene, and two reacted spent agents of reactive system get into breeding blanket coke burning regeneration separately, is easy to regulation and control; Thereby two independent closed catalyst reaction, reprocessing cycle have been formed; Highly selective increases the especially yield of propylene of small-numerator olefin yield when can improve the heavy oil conversion rate, has higher heavy oil conversion rate and productivity of propylene, is also to have higher butylene productive rate unexpectedly.
Description of drawings
Fig. 1 is a kind of CCU synoptic diagram provided by the invention.Wherein 1,2 is riser reactor; 3 is the dense, fluidized bed bioreactor, and 4 is revivifier, and 5 is stripping stage subregion dividing plate in the settling vessel; 6 is regeneration subregion dividing plate in the revivifier; 7 are the fast subset of heavy hydrocarbon oil riser reactor outlet gas-solid, and 8 is the fast subset of outlet gas-solid of riser tube and fluidized-bed combined reactor, and 9 is riser reactor 1 and riser tube 2 and the public settling vessel of fluidized-bed 3 combined reactors.40 and 41 are respectively two strands of regenerated catalyst inclined tubes (by guiding valve aperture control catalyst flow wherein, not marking among the figure), and 42 and 43 are respectively two strands of reclaimable catalyst inclined tubes (by guiding valve aperture control catalyst flow wherein, not marking among the figure).51 and 52 are respectively the corresponding stripping zone of two strands of catalyzer, and 61 and 62 are respectively the corresponding breeding blanket of two strands of catalyzer, and 50 is the water stripping steam, and 60 is regeneration air.As shown in Figure 1, riser tube 2 is connected with fluidized-bed 3 and is realized being arranged in juxtaposition through settling vessel 9 and riser tube 1, settling vessel 9 and the stripper height coaxial arrangement that comprises stripping zone 51 and stripping zone 52.
Embodiment
The catalyst cracking method of production propylene provided by the invention; In first riser reactor, the heavy feed stock and the first catalytic cracking catalyst contact reacts, the finish mixture of generation separates oil gas through the terminal tripping device of riser tube with reaction back carbon deposited catalyst; Described tripping device is preferably fast minute device; In order to reaction oil gas and carbon deposited catalyst sharp separation, can adopt the existing fast device that divides, preferred fast packing is changed to slightly revolves the branch separator.Through the terminal fast device that divides of heavy feed stock catalyzed conversion riser reactor oil gas is separated rapidly with reaction back carbon deposited catalyst, can reduce dry gas yied, suppress the especially again conversion of propylene after generating of low-carbon alkene.Oil gas obtains products such as cracked gas, pyrolysis gasoline, cracking light oil and cracking heavy oil through follow-up product separation system separation; Spent agent gets into the first follow-up stripper, and the spent agent behind the stripping imports through line of pipes and returns first riser reactor after the regeneration of first revivifier and recycle.Operational condition in first riser reactor comprises: temperature of reaction is 450～650 ℃, is preferably 480～600 ℃; Agent-oil ratio (weight ratio of 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.
Said heavy feed stock is heavy hydrocarbon and/or the various plant-animal oils raw materials that are rich in hydrocarbon polymer, and said heavy hydrocarbon is selected from one or more the mixture in petroleum hydrocarbon, MO and the synthetic oil.Petroleum hydrocarbon is conventionally known to one of skill in the art, for example, can be the hydrocarbon ils that decompressed wax oil, long residuum, decompressed wax oil blending part vacuum residuum or other secondary processing obtain.During hydrocarbon ils that said other secondary processing obtains such as wax tailings, deasphalted oil, furfural treatment are raffinated oil one or more.MO is selected from one or more the mixture in liquefied coal coil, tar sand oil and the shale oil.Synthetic oil is that coal, Sweet natural gas or pitch are through the synthetic distillate that obtains of F-T.The various plant-animal oils raw materials that are rich in hydrocarbon polymer are animal oil and fat, Vegetable oil lipoprotein for example.
The catalyst cracking method of production propylene provided by the invention; Make the light hydrocarbon and second catalytic cracking catalyst in the combined reactor contact reacts that is composed in series by second riser reactor and fluidized-bed reactor; Light hydrocarbon is transformed; Leave the oil gas and the catalyst separating of second reactor drum after the reaction, catalyzer is regenerated after getting into the stripper stripping, and the catalyzer after the regeneration is introduced second riser reactor and recycled.In the combined reactor of second riser reactor and fluidized-bed reactor composition; The light hydrocarbon and second catalytic cracking catalyst are in second riser reactor after the contact reacts; The finish mixture that obtains is introduced in the fluidized-bed reactor that links to each other with second riser reactor end and is continued reaction; Reacted hydrocarbon product gets into the settling vessel gas-solid separation equipment entering subsequent product separation system that links to each other with settling vessel of warp then; Obtain cracked gas, pyrolysis gasoline, cracking light oil and cracking heavy oil; The isolating spent agent of gas-solid separation equipment gets into fluidized bed reaction zone, and the post catalyst reaction that leaves fluidized bed reaction zone gets into second stripper, behind stripping, returns second riser reactor after the regeneration in introducing second revivifier and recycles.The described gas-solid separation equipment that links to each other with settling vessel is cyclonic separator for example.
The catalyst cracking method of production propylene provided by the invention, said light hydrocarbon are gasoline fraction and/or C4 hydrocarbon, preferably include gasoline fraction and/or C4 hydrocarbon that the inventive method product separation system obtains.The operational condition of second riser reactor is: when said light hydrocarbon comprises gasoline fraction; Gasoline fraction is operated agent-oil ratio (introducing second catalytic cracking catalyst of second riser reactor and the weight ratio of gasoline fraction) in second riser tube be 10～30, and the reaction times is 0.10～1.5 second; When said lightweight material comprised the C4 hydrocarbon, the C4 hydrocarbon is operated agent-oil ratio (introducing the weight ratio of second catalytic cracking catalyst and the C4 hydrocarbon of second riser reactor) in second riser tube be 12～40, and the reaction times is 0.50～2.0 second; The temperature of reaction of fluidized-bed reactor is 500～650 ℃, 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 second riser reactor: gasoline fraction is operated agent-oil ratio and is preferably 15～25 in second riser tube; Reaction times is preferably 0.30～0.8 second; Gasoline fraction atomized water steam accounts for the gasoline fraction inlet amount and is preferably 10～20 weight %.The operation condition of C 4 fraction: the C4 hydrocarbon is operated agent-oil ratio (introducing the weight ratio of second catalytic cracking catalyst with the C4 hydrocarbon of introducing second riser reactor of second riser reactor) preferred 17～30 in second riser reactor; Be rich in alkene C4 preferred 0.8～1.5 second in the second riser tube internal reaction time; Atomized water steam accounts for preferred 15～25 weight % of ratio of C4 inlet amount.
In the 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; The fluidized-bed reaction temperature is about 500～650 ℃, is preferably 510～580 ℃; The weight hourly space velocity of fluidized-bed (charging of fluid bedreactors THC) 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 of introducing in second riser reactor is gasoline fraction and/or C4 hydrocarbon, is preferably the gasoline fraction and/or the C4 hydrocarbon that are rich in alkene.The said gasoline fraction raw material that is rich in alkene comprises that the gasoline fraction of apparatus of the present invention production (promptly from according to the invention product separation system) and/or other device produce gasoline fraction; The mixture of one or more in the gasoline fraction that the optional catalytic cracking raw gasline of other device production gasoline fraction, catalytic cracking stable gasoline, coker gasoline, viscosity breaking gasoline and other oil refining or chemical process are produced, the gasoline fraction of preferentially selecting for use this device to produce.Said gasoline stocks can be the gasoline fraction of full range, final boiling point be no more than 204 ℃ for example boiling range be 40～204 ℃, also can be narrow fraction wherein, the gasoline fraction of boiling range between 40～85 ℃ for example.The gasoline fraction of injection light hydrocarbon oil riser reactor is 0.05～0.20: 1 with the weight ratio of the heavy feed stock that injects first riser reactor, preferred 0.08～0.15: 1.Said gasoline stocks is preferably the gasoline fraction that is rich in alkene, and its olefin(e) centent is 20～95 weight %, and preferred 35～90 heavy % are preferably in more than the 50 weight %.
Said C4 hydro carbons is meant with the C 4 fraction to be the low-molecular-weight hydrocarbon that exists with gas form under the normal temperature, normal pressure of staple, comprises that carbonatoms in the molecule is 4 alkane, alkene and alkynes.It comprises the gaseous hydrocarbon products that is rich in C 4 fraction that apparatus of the present invention are produced, and also can comprise the hydrocarbon gas that is rich in C 4 fraction that other device process is produced, the C 4 fraction that wherein preferred apparatus of the present invention are produced.Said C4 hydro carbons is preferably the C 4 fraction that is rich in alkene, and wherein the content of C4 alkene is preferably greater than 60 heavy %, preferably more than 70 weight % greater than 50 heavy %.Preferred said light hydrocarbon comprises gasoline fraction, contains or do not contain the C4 hydrocarbon, and the weight ratio of C4 hydrocarbon and gasoline fraction is 0～2: 1, preferred 0～1.2: 1, most preferably 0～0.8: 1.
Preferably; The cracking heavy oil that also product separation of the present invention system is obtained is introduced and is reacted in second riser reactor and/or introduce fluidized-bed reactor and react; This helps reducing dry gas yied and coke yield, and improves especially productivity of propylene of low-carbon alkene.When cracking heavy oil was introduced second riser reactor, the introducing optimum seeking site of said cracking heavy oil was in the part of 1/2nd places to the riser tube outlet of the second riser reactor length, and promptly said introducing optimum seeking site is in the middle and lower reaches of second riser reactor.Preferably, said cracking heavy oil is introduced in the fluidized-bed reactor and is reacted, and more preferably introduces the bottom of said fluidized-bed reactor.The cracking heavy oil that described cracking heavy oil obtains for product separation system of the present invention; The crackate that promptly gets into product separation system is isolated remaining most of product liquid behind gas, gasoline and the diesel oil; Its normal pressure boiling range is between 330～550 ℃, and preferably its normal pressure boiling range is 350～530 ℃.The cracking heavy oil that injects second riser tube and fluidized-bed reactor is 0.05～0.30: 1 with the weight ratio of the heavy feed stock that injects first riser reactor, preferred 0.10～0.25: 1.
The catalyst cracking method of production propylene provided by the invention, the terminal tripping device of first riser reactor separates reaction oil gas with carbon deposited catalyst, and the oil gas product is introduced product separation system and is separated; The reacted oil gas of the combined reactor of forming from second reactor drum and fluidized-bed reactor successively gets into settling vessel and gas-solid separation equipment isolate the catalyzer that wherein carries after, get into follow-up product separation system.The oil gas product of first riser reactor and the oil gas product of fluidized-bed reactor are introduced the product separation system and are separated, and preferably two strands of oil gas are mixed the back and introduce the separation of product separation system.In the product separation system, the oil gas product obtains cracked gas, pyrolysis gasoline, cracking light oil and cracking heavy oil through separation.Described product separation system is a 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 the equal diameter riser tube, etc. linear speed riser tube and become a kind of or wherein two kinds the combination in the diameter riser tube, wherein the heavy hydrocarbon oil riser reactor can adopt identical pattern also can adopt different patterns with the light hydrocarbon oil riser reactor.That described fluidized-bed reactor is selected from is fixed fluidized bed, one or more the combination in dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, Transport Bed and the dense bed reactor drum.
In described second riser reactor and the fluidized-bed reactor combined reactor, riser tube outlet preferred lower pressure outlet sparger, its pressure drop is less than 10KPa.Described low tension outlet sparger is the arch sparger for example.
The catalyst cracking method of production propylene provided by the invention, heavy feed stock and light hydrocarbon adopt different catalyst and reaction-regeneration system.Wherein first catalytic cracking catalyst is mainly the catalyst cracking particles of Y zeolite by active ingredient and catalyst cracking particles that active ingredient is mainly beta-molecular sieve is formed.Said active ingredient is mainly the catalyst cracking particles of Y zeolite; Butt weight with this granules of catalyst is benchmark; At least the Y zeolite that comprises 10 weight contains or does not contain other molecular sieve except that Y zeolite, and the content of other molecular sieve is no more than 5 weight %; Preferably, comprise the Y zeolite of 10～70 weight %, the clay of 0～60 weight %, the inorganic oxide binder of 15～60 weight %; More preferably form by the Y zeolite of 25～50 weight %, the clay of 25～50 weight %, the inorganic oxide binder of 25～50 weight %.Said active component is mainly the catalytic cracking catalyst of beta-molecular sieve, comprises the beta molecular sieve of at least 10 weight, contains or do not contain other molecular sieve beyond the beta-molecular sieve, and the content of other molecular sieve is no more than 5 weight %; Preferably include the beta molecular sieve of 10～70 weight %, the clay of 0～60 weight %, the inorganic oxide binder of 15～60 weight %; More preferably comprise the beta molecular sieve of 25～50 weight %, the clay of 25～50 weight %, the inorganic oxide binder of 25～50 weight %.
In described first catalytic cracking catalyst; Active ingredient mainly is that the catalyst cracking particles of Y zeolite and the mass ratio of the catalyst cracking particles that active ingredient mainly is beta-molecular sieve are 4～1: 1～4, is preferably 1.5～3.5: 3.5～1.5.Said Y zeolite is the various Y zeolites that generally adopt in the prior art, the for example mixture of one or more in rare earth Y type molecular sieve (REY), rare earth hydrogen Y zeolite (REHY), super-stable Y molecular sieves (USY), the rare earth superstable Y-type molecular sieve (REUSY).Said beta molecular sieve is the beta-molecular sieve of the various modifications generally adopted in the prior art, the for example beta-molecular sieve of Hydrogen beta-molecular sieve, phosphorus and transition metal modification.The concrete preparation of beta molecular sieve can be referring to CN1035668C and CN1041616C.
The catalyst cracking method of production propylene provided by the invention; In light hydrocarbon oil catalytic conversion reaction, reprocessing cycle system; Adopt active ingredient to be mainly second catalytic cracking catalyst of mean pore size, in second riser tube and fluidized-bed reactor, react less than 0.7nm shape-selective molecular sieve (like the ZSM-5 molecular sieve).Mean pore size is at least 10 weight % less than the content of 0.7nm shape-selective molecular sieve in said second catalytic cracking catalyst; Contain or do not contain except that mean pore size less than other molecular sieve the 0.7nm shape-selective molecular sieve; The content of said other molecular sieve is no more than 5 weight %; Preferably in said second catalytic cracking catalyst by butt weight; Said second catalytic cracking catalyst comprises the mean pore size of 10～65 weight % less than the shape-selective molecular sieve of 0.7 nanometer, the clay of 0～60 weight % and the inorganic oxide binder of 15～60 weight %, and the average all apertures that more preferably comprise 20～50 weight % are less than the shape-selective molecular sieve of 0.7 nanometer, the clay of 10～45 weight % and the inorganic oxide binder of 25～50 weight %.The said mean pore size that contains can be one or more the combination that is provided by prior art less than the shape-selective molecular sieve catalyzer of 0.7 nanometer, can be purchased or according to existing method preparation.
Said mean pore size is selected from ZSM series zeolite, ferrierite, chabazite, dachiardite, erionite, A zeolite, epistilbite, lomontite less than the shape-selective molecular sieve of 0.7 nanometer, and one or more the mixture among the zeolite that after physics and/or chemical process are handled, obtains 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 the ZRP molecular sieve.Preferred mean pore size is in ZSM-5 molecular sieve, ZRP molecular sieve, element modified ZSM-5 or the element modified ZRP molecular sieve one or more less than the shape-selective molecular sieve of 0.7 nanometer, and element modified ZSM-5 molecular sieve is the ZSP molecular sieve for example.The more detailed description of relevant ZSM-5 molecular sieve is referring to USP3702886, and the more detailed description of relevant ZRP is referring to USP5232675, CN1211470A, CN1611299A.
Said inorganic oxide can be selected from silicon-dioxide (SiO as caking agent
2) and/or aluminium sesquioxide (Al
2O
3).Said clay is as matrix, and promptly carrier can be selected from kaolin and/or halloysite.
The operating method of the described revivifier of the inventive method and operational condition can be with reference to conventional catalytic cracking regenerators.
A kind of CCU that is used for the present invention's use comprises reactor drum part, stripper part, revivifier part and product separation system at least.Preferably; Reactor drum adopts double lifting leg and fluidized-bed to form the combined reactor configuration; One of them riser tube and fluidized-bed reactor series connection back is arranged in juxtaposition with another riser tube mutually, and described riser tube and fluidized-bed reactor cascaded structure further with the stripper arranged in series.At above-mentioned stripper one dividing plate is set it is divided into two independent stripping zones, reaction, stripping route that the combined reactor that one of them stripping zone and riser tube and fluidized-bed constitute forms, it is used for the light hydrocarbon catalyzed conversion; Another stripping zone then forms corresponding another road reaction, stripping route with another riser tube, and it is used for the heavy feed stock catalyzed conversion.Settle a dividing plate that it is divided into two breeding blankets in the said revivifier and be connected with corresponding stripping zone respectively, thereby form two strands of independently catalyst reaction, reprocessing cycle routes.
A kind of CCU that the present invention uses; As shown in Figure 1, said CCU comprises gas-solid separation equipment 8, settling vessel 9, the stripper dividing plate 5 of riser reactor 1, the gas-solid separation equipment 7 that is communicated with the outlet of riser reactor 1, riser reactor 2 and placed in-line with it fluidized-bed reactor 3, fluidized-bed reactor and first stripping zone 51 and second stripping zone 52 that is separated by dividing plate 5; The catalyst outlet of gas-solid separation equipment 7 is communicated with first stripping zone 51, and the top of 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 inlet of gas-solid separation equipment 8 is communicated with settling vessel 9; The catalyst outlet position of gas-solid separation equipment 8 makes catalyzer wherein can get into stripping zone 52 or fluidized-bed reactor 3,, can be in fluidized-bed reactor top, the fluidized-bed reactor or in second stripping zone 52 for this reason; After linking to each other, the oil gas vent of gas-solid separation equipment 7 and gas-solid separation equipment 8 is communicated with oil and gas separating system.Described revivifier can be two independent revivifiers; Also can be as shown in Figure 1 a revivifier to be divided into two breeding blankets; The dividing plate of wherein settling in the revivifier 46 is divided into two independent breeding blankets 61 and 62 with revivifier 4, is connected with stripping zone 51 and 52 respectively.For freshening cracking heavy oil, described riser reactor 2 and/or fluidized-bed reactor 3 also comprise cracking heavy oil inlet.Stripper dividing plate 5 preferably also extends in the settling vessel; The bottom of settling vessel is divided into two zones that do not communicate; Be used separately as riser reactor 2 and the settling vessel of the combined reactor of fluidized-bed reactor 3 compositions and the settling vessel of riser reactor 1; Preferred two negative areas are communicated with the headspace of public settling vessel 9 at the top of settling vessel 5.
The above-mentioned catalytic cracking conversion system that is used for the inventive method; Can realize different cut employing different catalyst is carried out selective conversion and catalyst system therefor is distinguished stripping and regeneration; Simply, effectively accomplish and form two strands of relatively independent catalyst reactions, reprocessing cycle route; Compact construction and easy to implement, device operation be simple relatively, flexibly, the fine solution eliminated two kinds of disadvantageous phase mutual interference of catalyst system on the engineering.Riser tube and fluidized-bed combined reactor and the second stripping zone arranged in series; Can realize water stripping steam introducing fluidized-bed reactor; Discharge reactor drum after making it pass fluidized-bed reactor, both can effectively reduce the oil gas dividing potential drop, shorten oil gas in the settling section residence time; Thereby help propylene enhancing, reduce dry gas, coke yield.
Below in conjunction with accompanying drawing the present invention is further explained:
In method as shown in Figure 1; First catalytic cracking catalyst of being derived by first breeding blanket 61 of revivifier 4 gets into riser reactor 1 bottom through regenerator inclined tube 40; Second catalytic cracking catalyst of being derived by breeding blanket 62 flows to riser reactor 2 bottoms through regenerator inclined tube 41, and correspondingly two strands of catalyzer quicken upwards to flow respectively under the preparatory lifting medium effect of being injected by pipeline 22 and 23.Heavy feed stock after the preheating (heavy hydrocarbon or be rich in the various plant-animal oils of hydrocarbon polymer) through pipeline 20 with after atomizing steam from pipeline 21 mixes by a certain percentage; Injecting lift pipe reactor 1, reaction oil gas and catalyst mixture separate carbon deposited catalyst after oil gas and the reaction through the terminal fast minute device 7 of riser tube 1; The light hydrocarbon (for example being rich in the gasoline fraction and/or the C4 hydrocarbon of alkene) of preheating simultaneously or not preheating through pipeline 24 with after atomizing steam from pipeline 25 mixes by a certain percentage; Injecting lift pipe reactor 2; Thereafter during reaction oil gas and catalyst mixture make progress flowing-path along riser tube 2; Reaction oil gas and catalyst mixture get into the reaction of fluidized-bed reactor 3 continued through the outlet sparger (not marking among the figure) of riser tube 2, get into settling vessel 9 at last after gas-solid separation equipment 8 carries out separating of oil gas and catalyzer.All hydrocarbon ils products comprise the oil gas of riser tube 1 outlet and all draw reactor drum through settling vessel top cyclone separation system (not marking the figure) collection through pipeline 26 from fluidized-bed reactor 3 effusive oil gas getting into subsequent product separation system (not marking among the figure).The catalytic pyrolysis product is separated into hydrocarbon gas, pyrolysis gasoline, cracking light oil, cracking heavy oil and cracking slurry oil in the product separation system.Cracked gaseous hydrocarbons separates at subsequent product, can obtain the polymerization-grade propylene product after refining and be rich in the C 4 fraction of alkene, but the C 4 fraction Returning reactor that wherein is rich in alkene transforms the production propylene again, and the C 4 fraction that preferably will be rich in alkene returns riser tube 2 and transforms.Pyrolysis gasoline partly or entirely Returning reacting system transforms again; Also can be earlier with gasoline be cut into gently, the 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 fast minute device 7 isolated carbon deposited catalysts terminal through riser tube 1 get into stripping zones 51, and the spent agent after separating device 8 separates contacts the laggard fluidized-bed reactor 3 of going into the finish mixture that riser tube 2 is drawn, get into independent stripping zone 52 then; Stripped vapor injects stripper through pipeline 50; With the carbon deposited catalyst counter current contact; Stripping is clean as much as possible for the reaction oil gas that carbon deposited catalyst is entrained; The stripped vapor of stripping zone 51 directly gets into settling vessel 9, gets into stripper 9 then and the stripped vapor of stripping zone 52 is introduced into fluidized-bed reactor 3, after gas-solid separation equipment 8 separates, draws reactor drum by pipeline 26 with other oil gas.The stripping zone 51 behind the stripping and the catalyzer of stripping zone 52 are sent into two independent breeding blankets 61 through spent agent inclined tube 42 and 43 respectively and are carried out coke burning regeneration with breeding blanket 62.Public space mixes and draws through pipeline 63 regenerated flue gas that oxygen-containing gas such as air inject 4, two breeding blankets of revivifiers through pipeline 60 at the top of revivifier 4.Catalyzer after the regeneration returns riser reactor 1 and 2 respectively through regenerator inclined tube 40 and 41 and recycles.
In above-mentioned embodiment process, introduce lifting medium in advance to riser tube 1 and riser tube 2 respectively through pipeline 22 and 23.Said preparatory lifting medium is known for those skilled in the art, can be selected from water vapour, C1～C4 hydro carbons or the conventional catalytic cracked dry gas one or more, the preferably water steam.
Following embodiment will further specify the present invention.
Employed raw material comprises raw material A, raw material B, raw material C and raw material D in embodiment and the Comparative Examples; Wherein raw material A is two kinds of different heavy oil fractions with B; Raw material C and raw material D are respectively the pyrolysis gasoline and conventional full cut catalytic cracking product gasoline that is rich in alkene, and specific nature is seen table 1.The catalyzer that is adopted is respectively the CHP of Sinopec catalyzer Shandong branch office production and plants four kinds of catalyzer that the prepared in laboratory name is called Y, B and BY.Four kinds of catalyzer specific natures are seen table 2, all carry out 790 ℃ * 100%H before the use
2The aging pre-treatment of the water vapour of O * 14 hour (promptly in 790 ℃, 100% steam atmosphere aging 14 hours down); Wherein Y activity of such catalysts component is the USY molecular sieve; B activity of such catalysts component is a beta molecular sieve; BY catalyst activity component is USY molecular sieve and beta-molecular sieve, and CHP activity of such catalysts component is the ZRP molecular sieve, and to account for the ratio of catalyzer total amount suitable basically for active component in three kinds of catalyzer.
Y catalyzer, B catalyzer and BY catalyzer prepare according to existing method; Its preparation process is following: (1) adds into the glue jar successively with water, kaolin, pseudo-boehmite and hydrochloric acid; Wherein to make the solid content of the slurries that obtain be 30 weight % to the consumption of water; Hydrochloric acid (in HCl) is 0.18: 1 with the mol ratio of pseudo-boehmite (in aluminum oxide), stirs; (2) the gained slurries are warming up to 65 ℃, stop to stir static aging 1h; (3) be cooled to 50 ℃, add aluminium colloidal sol and molecular sieve pulp (content of molecular sieve is 30 weight % in the molecular sieve pulp) successively, continue to stir; (4) the spray-dried moulding of slurries, washing, oven dry make catalyst sample.The composition of Y catalyzer, B catalyzer and BY catalyzer is: contain molecular sieve 35 weight %, kaolin 35 weight %, pseudo-boehmite (in aluminum oxide) 26 weight %, aluminium colloidal sol (in aluminum oxide) 4 weight %.Wherein, the mass ratio of two kinds of molecular sieves is a Y zeolite in the BY catalyzer: beta molecular sieve=2: 3, and promptly the content of Y zeolite is 14 weight %, the content of beta molecular sieve is 21 weight %.The B catalyzer contains beta-molecular sieve 35 weight %, kaolin 35 weight %, pseudo-boehmite (in aluminum oxide) 26 weight %, aluminium colloidal sol (in aluminum oxide) 4 weight %.Wherein, beta-molecular sieve silica alumina ratio (SiO
2/ Al
2O
3Mol ratio) is 30, is Hydrogen; The USY molecular sieve, its content of rare earth 2 weight %, silica alumina ratio (SiO
2/ Al
2O
3Mol ratio) be 5.2; USY, beta-molecular sieve are catalyzer Shandong company of China Petrochemical Industry and produce.
Comparative Examples 1
Experiment is carried out at small fixed flowing bed (FFB) CCU.This device is designed to interval type, single-pass operation pattern.Raw material is heavy oil A, and catalyzer is BY.
Heavy oil A as shown in table 2 gets into interior the contact with the BY catalyzer of fluidized-bed reactor and carries out catalyzed reaction, and reaction conditions is: temperature of reaction is 520 ℃, agent-oil ratio 6, weight hourly space velocity 15h
-1, the water filling vapor volume is 5 weight %.Reaction product, steam and spent agent separate in settling vessel, and reaction product isolated obtains gaseous product and product liquid, and the spent agent catalyzer is gone out the hydrocarbon product that adsorbs on the spent agent by the water vapor stripping.Spent agent behind the stripping contacts with the warm air that heated regenerates, and the catalyzer after the regeneration carries out new catalytic conversion reaction again.Test conditions and main result are seen table 3.
Comparative Examples 2
Experimentizing on the FFB device described in the Comparative Examples 1.Raw material and reaction conditions and Comparative Examples 1 are identical; Different is that catalyzer is the mechanical mixture of B and two kinds of catalyzer of Y; Wherein the mixed weight ratio of Y catalyzer and B catalyzer is respectively 40 weight % and 60 weight %; The content of Y molecular sieve and beta-molecular sieve is respectively 14 weight % and 21 weight % in the formation catalyst mixture, and is identical with two kinds of molecular sieve content in the BY catalyzer.The main operational condition and the result of experiment list in table 3.
Comparative Examples 3
Experimentizing on the FFB device described in the Comparative Examples 1.Raw material and reaction conditions and Comparative Examples 1 are identical, and different is that catalyzer is Y, and the main operational condition and the result of experiment list in table 3.
Comparative Examples 4
Experiment is carried out at small fixed flowing bed (FFB) CCU.Raw material is heavy oil B, and catalyzer is CHP.
Heavy oil B as shown in table 2 gets into interior the contact with the CHP catalyzer of fluidized-bed reactor and carries out catalyzed reaction, and reaction conditions is: temperature of reaction is 580 ℃, agent-oil ratio 5, weight hourly space velocity 1h
-1, the water filling vapor volume is 30 weight %.Reaction product, steam and spent agent separate in settling vessel, and reaction product isolated obtains gaseous product and product liquid, and the spent agent catalyzer is gone out the hydrocarbon product that adsorbs on the spent agent by the water vapor stripping.Spent agent behind the stripping contacts with the warm air that heated regenerates, and the catalyzer after the regeneration carries out new catalytic conversion reaction again.Test conditions and main result are seen table 3.
Comparative Examples 5
Experimentizing on the FFB device described in the Comparative Examples 4.Catalyzer and reaction conditions and Comparative Examples 4 are identical, and different is that raw oil becomes raw material D.
Comparative Examples 6
Experimentizing on the FFB device described in the Comparative Examples 5.Reaction conditions is identical with Comparative Examples 4 with Comparative Examples 5 with catalyzer, is not both raw material and changes, and the main operational condition and the result of experiment list in table 3.
Embodiment 1
Experiment is carried out at kitty cracker.This device comprises two cover reaction-regeneration systems: first riser reactor, internal diameter are 16 millimeters, and length is 3800 millimeters, and used catalyzer is made up of the B catalyzer of 40 weight %Y catalyzer and 60 weight %, and the raw material A shown in the his-and-hers watches 1 is carried out cracking; Oil gas after the conversion and catalyst separating, catalyzer get into the regeneration of first revivifier after getting into first stripper, and the catalyzer after the regeneration returns first riser reactor and recycles; Oil gas is introduced the product separation system and is separated.Warp is 16mm in second riser reactor; Length is 3200mm, series fluidized bed reactor behind second riser reactor, and the diameter of fluidized-bed reactor is 64 millimeters for (internal diameter); 600 millimeters of length; Gasoline fraction (boiling range is 30～85 ℃) to from the product separation system transforms, and used catalyzer is CHP, oil gas after the conversion and catalyst separating; Catalyzer gets into the regeneration of second revivifier after getting into second stripper, and the catalyzer after the regeneration returns second riser reactor and recycles; Oil gas is introduced the product separation system and is separated.The oil gas that obtains after the oil gas that obtains after first riser reactor reaction and the fluidized-bed reactor reaction mixes and then separates in the identical product separation system.Oil gas behind the second stripper stripping passes fluidized-bed reactor and gets into corresponding settling vessel.Its reaction and operational condition and reaction result are seen table 4.
Comparative Examples 7
Experiment is carried out at kitty cracker, and riser tube adds fluidized-bed reaction.
Warp is 16mm in the riser reactor; Length is 3200mm, series fluidized bed reactor behind the riser reactor, and the diameter of fluidized-bed reactor is 64 millimeters for (internal diameter); 600 millimeters of height; Raw material A shown in the his-and-hers watches 1 transforms, and used catalyzer is MMC-2 (catalyzer Shandong branch office of China Petrochemical Industry product contains USY type molecular sieve and ZRP molecular sieve).Oil gas after the conversion and catalyst separating, catalyzer get into revivifier regeneration after getting into stripper, and the catalyzer after the regeneration returns riser reactor and recycles; The oil gas product is introduced the product separation system and is separated.Oil gas behind the stripper stripping passes fluidized-bed reactor and gets into corresponding settling vessel.Its reaction and operational condition and reaction result are seen table 4.
Embodiment 2
With reference to embodiment 1; Different is in second riser reactor, to introduce cracking heavy oil (boiling range of cracking heavy oil is 350～500 ℃) at 1.5 meters of distance second riser reactor outlet, and the introducing amount of said cracking heavy oil and the weight ratio of raw material A are 0.05: 1.
Embodiment 3
According to the method for embodiment 2, different is that cracking heavy oil is introduced the fluidized-bed reactor bottom, does 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 outlets connect fluidized-bed reactor 3, the xsect semicircular in shape of this fluidized-bed reactor, and it is 64 millimeters circular area that its cross-sectional area equals diameter, 600 millimeters of length.Settling vessel 9 length are 1520mm; Diameter is 250mm; Wherein stripper dividing plate 5 is straight plate, and stripper is divided into two portions, and the sectional area that forms round-robin stripping zone 51 with riser reactor 1 accounts for 85% of whole stripping stage sectional area; And stripper dividing plate 5 extends to settling vessel, and the dividing plate upper edge is 500mm apart from the settling vessel top.Test adopts the freshening mode to operate.Raw material B is introduced first riser reactor with the catalyst mixture of being made up of the B catalyzer of 40 weight %Y catalyzer and 60 weight % to react; Reacted oil gas advances fast minute device to be separated; Catalyzer after the separation gets into stripping zone 51, introduces breeding blanket 61 regeneration behind the stripping, and oil gas gets into the product separation system with the oil gas mixing back of fluidized-bed reactor to be separated; Separate the gasoline fraction (boiling range is 30～85 ℃) that obtains and introduce riser reactor 2; Its amount is 0.15: 1 with the weight ratio of raw material B, contacts with introducing CHP catalyzer wherein and reacts, and gets into fluidized-bed reactor 3 then and reacts; Oil gas behind the fluidized-bed reaction gets into settling vessel and isolates through gas-solid separator 8 behind the catalyzer that wherein carries and to mix back entering product separation system with the oil gas of first reactor drum; Catalyzer in the fluidized-bed reactor leaves from its bottom and gets into stripping zone 52, gets into breeding blanket 62 regeneration behind the stripping, and the oil gas behind stripper 52 strippings passes fluidized-bed reactor 3 and gets into settling vessel.Its operational condition and reaction result are seen table 4.
Visible by table 4; The inventive method can improve heavy oil conversion performance, reduces dry gas and coke yield in the time of the gain in yield of propylene and butylene, with cracking heavy oil freshening to riser tube and fluidized-bed combined reactor; Can further reduce the heavy oil productive rate, increase the productive rate of propylene and iso-butylene.The new texture device that uses the present invention to propose can reduce the heavy oil productive rate, increases the productive rate of propylene and iso-butylene, improves the yield of high-value product, has a significant effect.
Table 1
Table 2
| The catalyzer title | Y | BY | B | CHP | MMC-2 |
| Main active component | USY | USY+β | β | ZRP | USY+ZRP |
| Chemical property, 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, weight % | 69 | 66 | 64 | 52 | 64 |
Table 3
Table 4
Claims (13)
1. catalyst cracking method of producing propylene comprises:
(1) makes the heavy feed stock and first catalytic cracking catalyst contact reacts in first riser reactor; Reacted oil gas is separated with first catalytic cracking catalyst; Oil gas is introduced the product separation system; First catalytic cracking catalyst is introduced the regeneration of first revivifier behind the first stripper stripping, first catalytic cracking catalyst after the regeneration is introduced first reactor cycles and used; Wherein, said first catalytic cracking catalyst is mainly the granules of catalyst of Y zeolite by active ingredient and granules of catalyst that active ingredient is mainly beta-molecular sieve is formed; The first riser reactor temperature of reaction is 450～650 ℃, and agent-oil ratio is 1～25, and the reaction times is 0.5～10 second;
(2) make light hydrocarbon with contain the aperture less than second catalytic cracking catalyst of 0.7nm shape-selective molecular sieve in the second reactor drum contact reacts; Described second reactor drum comprises placed in-line second riser reactor and fluidized-bed reactor, and reacted oil gas of second riser reactor and reacted second catalytic cracking catalyst are introduced and the placed in-line fluidized-bed reactor reaction of second riser reactor; Oil gas behind the fluidized-bed reaction is introduced the product separation system; Second catalytic cracking catalyst behind the fluidized-bed reaction is introduced the regeneration of second revivifier after introducing the second stripper stripping, and second catalytic cracking catalyst after the regeneration is introduced second riser reactor and recycled; Said light hydrocarbon comprises gasoline fraction and/or C4 hydrocarbon; When said light hydrocarbon comprised gasoline fraction, the agent-oil ratio that gasoline fraction is operated in second riser reactor was 10～30, and the reaction times is 0.10～1.5 second; When said light hydrocarbon comprised the C4 hydrocarbon, the C4 hydrocarbon is operated agent-oil ratio in second riser tube be 12～40, and the reaction times is 0.50～2.0 second; The temperature of reaction of fluidized-bed reactor is 500～650 ℃, and weight hourly space velocity is 1～35 hour
-1
2. according to the described method of claim 1; It is characterized in that; The butt weight that is mainly the granules of catalyst of Y zeolite with active ingredient is benchmark, and the granules of catalyst that said active ingredient is mainly Y zeolite comprises 10～70 weight %Y type molecular sieves, the clay of 0～60 weight %, the inorganic oxide binder of 15～60 weight %; The butt weight that is 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 the clay of 10～70 weight % beta molecular sieves, 0～60 weight %, the inorganic oxide binder of 15～60 weight %; Described active ingredient is mainly the granules of catalyst of Y zeolite and the weight ratio of the granules of catalyst that described active ingredient is mainly beta-molecular sieve is 4～1: 1～4.
3. according to the described method of claim 2, it is characterized in that the granules of catalyst that said active ingredient is mainly Y zeolite comprises the Y zeolite of 25～50 weight %, the clay of 25～50 weight % and the inorganic oxide binder of 25～50 weight %; The particle that described active ingredient is mainly beta molecular sieve comprises the beta molecular sieve of 25～50 weight %, the clay of 25～50 weight % and the inorganic oxide binder of 25～50 weight %.
4. according to the described method of claim 1; It is characterized in that; With the second catalytic cracking catalyst butt weight is benchmark, and described second catalytic cracking catalyst comprises that the aperture of 10～65 weight % is less than the clay of 0.7nm shape-selective molecular sieve, 0～60 weight % and the inorganic oxide binder of 15～60 weight %.
5. according to the described method of claim 4, it is characterized in that described second catalytic cracking catalyst comprises that the aperture of 20～50 weight % is less than the clay of 0.7nm shape-selective molecular sieve, 10～45 weight %, the inorganic oxide binder of 25～50 weight %.
6. according to the described method of claim 1, it is characterized in that the operational condition of first riser reactor: temperature of reaction is 480～600 ℃; Agent-oil ratio is 5～20; Reaction times is 1～10 second; Reaction pressure is 0.15～0.35MPa.
7. according to the described method of claim 1, it is characterized in that when described light hydrocarbon comprised gasoline fraction, said gasoline fraction is operated agent-oil ratio in second riser tube be 15～25, the reaction times is 0.30～0.8 second.
8. according to claim 1 or 7 described methods, it is characterized in that when described light hydrocarbon comprised the C4 hydrocarbon, the C4 hydrocarbon is operated agent-oil ratio in second riser reactor be 17～30, the reaction times is 0.8～1.5 second.
9. according to the described catalyst cracking method of claim 1; It is characterized in that; Described heavy feed stock is heavy hydrocarbon and/or the various plant-animal oils raw materials that are rich in hydrocarbon polymer, and said heavy hydrocarbon is selected from one or more the mixture in petroleum hydrocarbon, MO and the synthetic oil.
10. according to the described catalyst cracking method of claim 1, it is characterized in that said light hydrocarbon comprises gasoline fraction and/or the C4 hydrocarbon from said product separation system.
11., it is characterized in that the cracking heavy oil that the product separation system obtains is introduced the middle and lower reaches of second reactor drum and/or the bottom of introducing fluidized-bed reactor according to the described method of claim 1.
12. according to the described method of claim 1; It is characterized in that; The employed CCU of this method, comprise riser reactor (1), the gas-solid separation equipment (7) that is communicated with the outlet of riser reactor (1), riser reactor (2), with the placed in-line fluidized-bed reactor of riser reactor (2) (3), gas-solid separation equipment (8), settling vessel (9), stripper dividing plate (5) and first stripping zone (51) and second stripping zone (52) that separate by dividing plate (5); The catalyzer that the catalyst outlet position of gas-solid separation equipment (7) obtains its separation gets into first stripping zone (51), and the top of first stripping zone is communicated with settling vessel (9); The inlet 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) obtains its separation can get into second stripping zone (52) or fluidized-bed reactor (3); After linking to each other, the oil gas vent of gas-solid separation equipment (7) and gas-solid separation equipment (8) is communicated with oil and gas separating system; 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., it is characterized in that riser tube pipe reactor (2) and/or fluidized-bed reactor (3) also comprise cracking heavy oil inlet according to the described method of claim 12.
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| CN110317628A (en) * | 2019-04-17 | 2019-10-11 | 中国石油大学(北京) | A kind of catalyst sections integrated catalytic cracking method and device |
| CN110317630A (en) * | 2019-04-17 | 2019-10-11 | 中国石油大学(北京) | A kind of catalyst sections catalyst 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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