CN102051213B - Catalytic cracking method - Google Patents
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- CN102051213B CN102051213B CN200910210330.2A CN200910210330A CN102051213B CN 102051213 B CN102051213 B CN 102051213B CN 200910210330 A CN200910210330 A CN 200910210330A CN 102051213 B CN102051213 B CN 102051213B
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Abstract
The invention relates to a catalytic cracking method which comprises the following steps: a heavy raw material is in contact with a catalyst containing shape-adaptive zeolite with the average pore size of less than 0.7nm in a first riser reactor with at least two reaction zones to perform cracking reaction; and a light raw material and cracked heavy oil are in contact with the catalyst containing shape-adaptive zeolite with the average pore size of less than 0.7nm in a second riser reactor and a fluidized bed reactor to perform cracking reaction. The method is used for the catalytic cracking of heavy oil; and the conversion rate of heavy oil and the yield of propylene are higher, and the yields of dry gas and coke are low.
Description
Technical field
The present invention relates to a kind of catalyst cracking method.
Background technology
The small-numerator olefins such as ethene, propylene and butylene are the most basic organic synthesis raw materials.At present the production of small-numerator olefin mainly adopts steam cracking method in the world, but due to the easy coking of high-temperature cracking furnace, so the method is only applicable to process lightweight material oil, as Sweet natural gas, petroleum naphtha and solar oil etc.Because the crude oil of China is heavier, the light oil yields such as petroleum naphtha are lower, and the raw material imbalance between supply and demand of steam cracking and catalytic reforming is day by day serious.Since middle 1980s, Research Institute of Petro-Chemical Engineering of China Petrochemical Corp. just takes to the research of the catalytic pyrolysis family technology of Producing Low Molecular Olefins from Heavy Oil, and successfully developed the catalytic pyrolysis (DCC of maximum production of propylene, USP4980053 and USP5670037) technology and maximum produce catalytic pyrolysis (CPP, the USP6210562) technology of ethene.Up to now, above-mentioned two kinds of technology are mainly used the structure of reactor of single riser reactor or single riser reactor combination dense phase fluidized bed, and dry gas and coke yield are high.
In recent years, the technology that adopts two riser reactors to carry out heavy oit pyrolysis production propylene is subject to greater attention.CN101074392A discloses a kind of method of utilizing two-stage catalytic cracking to produce propylene and high-quality petrol and diesel oil, the method is mainly to utilize two-stage riser Catalytic processes, the catalyzer of shape-selective molecular sieve is rich in employing, the various animals and plants oils of take heavy crude hydro carbons or being rich in hydrocarbon polymer are raw material, for reaction mass of different nature, carry out the optimum combination of feeding manner, control the suitable reaction conditions of different material, to reach, improve propene yield, take into account the object that light oil yield and quality, inhibition dry gas and coke generate.Its concrete proposition first paragraph riser tube charging is fresh heavy raw oil, and light hydrocarbons raw material can be entered in its underpart or bottom; Gasoline and turning oil that the charging of second segment riser tube is high olefin content, can stratified feeding or parallel feeding, and other light hydrocarbons raw material can be entered in its underpart or bottom.This invention is used two to promote reactor, yet the method productivity of propylene is not high, and heavy oil conversion performance is low, and dry gas yied is still higher.
CN101293806A discloses a kind of catalysis conversion method that improves productivity of low carbon olefin hydrocarbon, the method hydrocarbon oil crude material through raw material nozzles injecting lift pipe or/and in fluidized-bed reactor, contact and react with the shape-selective zeolite catalysts that contains mean pore size and be less than 0.7 nanometer, the gas inject reactor of hydrogen will be rich in, by reaction oil gas and the catalyst separating of reacting rear carbon deposit, wherein reaction oil gas is isolated to the object product that contains ethene, propylene, and the catalyzer of carbon deposit Returning reactor after stripping, regeneration recycles.The means that the method is rich in hydrogen gas by injection in reactor suppress the again conversion reaction of low-carbon alkene after generating, to improve the particularly productive rate of propylene of low-carbon alkene, but little to the effect of reduction dry gas yied, raising heavy oil conversion.
CN101314724A discloses a kind of bio-oil and mineral oil combined catalytic conversion method, comprises bio-oil and mineral oil to contact with catalyzer containing modified beta zeolite in compound reactor to carry out catalytic cracking reaction and obtain low-carbon alkene and gasoline, diesel oil, heavy oil.The method dry gas yied is higher, and heavy oil conversion rate is not high.
CN1298812C discloses double lift pipe catalytic cracking method and the device of a kind of modifying inferior patrol in petroleum refining process, mainly solves content of olefin in gasoline or the little problem of sulphur content fall.This device is set up two riser reactors (heavy oil riser tube and gasoline rising pipe) and corresponding gas-solid separation equipment and settling vessel, a public revivifier separately side by side.On gasoline rising pipe reactor top, be provided with the bed reactor of hole enlargement structure, from the settling vessel extension spent agent of gasoline reactor, be blended into above-mentioned bed reaction participation reaction, for reducing olefin(e) centent and the sulphur content of inferior patrol simultaneously.
CN101191068A discloses a riser reactor that comprises a plurality of reaction zones, and the riser reactor of the plurality of reaction zone comprises at least one central reaction zone and at least one reaction zone, top, and reaction zone, top is positioned on central reaction zone.In central reaction zone, introduce inferior heavy oil raw material and half regenerated catalyst contact reacts; In reaction zone, top, introduce heavy feed stock and regenerated catalyst contact reacts.In addition, in above-mentioned riser reactor bottom, can be provided with lower reaction zone, lightweight material improves lightweight material character at this reaction zone and spent agent or half regenerator contact reacts, increases productivity of propylene.At least one in the content of the carbon residue of inferior heavy oil raw material, metallic nickel and vanadium, asphalt content and basic n content higher than described heavy feed stock.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of heavy feed stock catalytic pyrolysis, and the method can improve heavy oil conversion rate and propene yield.
The invention provides a kind of catalytic cracking method, comprising:
By heavy feed stock and containing mean pore size, be less than cracking catalyst contact reacts in the reaction zone I of the first riser reactor that at least comprises two reaction zones that 0.7nm selects type zeolite, then reactant flow is introduced in the reaction zone II of the first riser reactor and with introduce reaction zone II containing mean pore size, be less than the cracking catalyst contact reacts that 0.7nm selects type zeolite, the tripping device exporting by this riser reactor is separated with carbon deposited catalyst after reaction by oil gas, oil gas obtains cracked gas through follow-up product separation system separation, pyrolysis gasoline, cracking light oil and cracking masout, the temperature of reaction of reaction zone I is 500～700 ℃, and agent-oil ratio is 5～20, and the reaction times is 0.4～10 second, the temperature of reaction of reaction zone II is 480～600 ℃, and agent-oil ratio is 7～20, and the reaction times is 0.5～8 second, introducing reaction zone I is 1: 0.05～0.5 with the ratio of the cracking catalyst of reaction zone II, described heavy feed stock is heavy hydrocarbon and/or the various animals and plants oils that are rich in hydrocarbon polymer,
By lightweight material with contain mean pore size and be less than catalyzer that 0.7 nanometer selects type zeolite in the second riser reactor contact reacts, then introduce the fluidized-bed reactor of connecting with the second riser reactor and continue reaction, meanwhile, cracking masout is introduced to the second riser reactor and/or fluidized-bed reactor bottom; In fluidized-bed reactor, reacted oil gas is introduced settling vessel and is isolated solid wherein, and hydrocarbon product is introduced subsequent products separation system and obtained cracked gas, pyrolysis gasoline, cracking light oil and cracking masout; Wherein, described lightweight material is gasoline fraction and/or C4 hydrocarbon; The temperature of reaction of the second riser reactor is 520～580 ℃; When lightweight material comprises gasoline fraction, described gasoline fraction (gasoline stocks) is 10～30 at the agent-oil ratio of the second lifting inner reaction tube, and the reaction times is 0.1～1.5 second; When lightweight material comprises C4 hydrocarbon, described C4 hydrocarbon is 12～40 at the agent-oil ratio of the second lifting inner reaction tube, and the reaction times is 0.5～2 second; The temperature of reaction of fluidized-bed reactor is 500～580 ℃, and the weight hourly space velocity of fluidized-bed is 1～35 hour
-1.
The present invention is based on the combined reactor that double lifting leg and fluidized-bed form, by the optimization of process program, be equipped with suitable catalyzer, realization is carried out selective conversion to different feeds in corresponding reaction zone, effectively improve heavy oil conversion, significantly increase productivity of propylene, suppress dry gas and coke simultaneously and generate, reduce the productive rate of dry gas and coke, and improve pyrolysis gasoline and light oil character.Wherein, flow direction along reaction mass in the first riser reactor at least arranges two reaction zones (reaction zone I and reaction zone II), and to reaction zone II, filling into high temperature regeneration agent regulates and controls the operating severity of reaction zone II (comprising temperature of reaction and agent-oil ratio), strengthening heavy hydrocarbon oil is effectively converted into the ability of propylene and high olefin content gasoline fraction in the first riser reactor, by the fast separating device of riser tube end, oil gas is separated with carbon deposited catalyst after reaction, when can make heavy hydrocarbon oil effectively be converted into propylene and high olefin content gasoline fraction, suppress the especially again conversion reaction of propylene after generating of low-carbon alkene, reduce dry gas yied, improve cracking light oil character.Cracking masout is incorporated into second riser reactor or the participation conversion of fluidized-bed reactor bottom, realize on the one hand the heavy oil conversion degree of depth that heavy oil twice transformation improves whole device, utilize cracking masout cut propylene enhancing, to being rich in the gasoline fraction of alkene and/or the Quench of C4 hydrocarbon reaction, stop simultaneously, suppress low-carbon alkene, especially propylene generates conversion reaction more afterwards, thereby effectively keeps high productivity of propylene.The inventive method is introduced fluidized-bed reactor by water stripping steam, discharges reactor after making it pass fluidized-bed reactor, can effectively reduce oil gas dividing potential drop, shortens oil gas in the settling section residence time, is conducive to increase productivity of propylene, reduces dry gas, coke yield.
Accompanying drawing explanation
Fig. 1 is a kind of schematic flow sheet of catalytic cracking method provided by the invention.In figure, 1,2 send out and answer device for riser tube, 3 is stripper, 4 is fluidized-bed reactor, 5 is reacting-settler, 6 is product separation device, 7 is revivifier, 8 is that reclaimable catalyst inclined tube (is controlled catalyst flow wherein by guiding valve aperture, in figure, do not mark), 9,10 and 11 is that regenerated catalyst inclined tube (is controlled catalyst flow wherein by guiding valve aperture, in figure, do not mark), riser tube 2 is realized and being arranged in juxtaposition with riser tube 1 by settling vessel 5 with coaxial series connection of fluidized-bed 4, is connected with the coaxial coupling of stripper 3 height simultaneously.
Embodiment
In catalytic cracking method provided by the invention, heavy feed stock is carried out in the first riser reactor to cracking reaction, then pass through the tripping device of the first riser reactor end by crackate and catalyst separating.The first described riser reactor at least comprises reaction zone I and reaction zone II, in the II of reaction zone, introduce the cracking catalyst of regeneration, the position that regenerated catalyst is introduced makes the residence time of hydrocarbon ils in the I of reaction zone be not less than 0.5s, and the residence time in preferred reaction district I is not less than 1 second.By introducing high temperature regeneration agent to reaction zone II, realization, to the regulation and control of (comprising temperature of reaction and agent-oil ratio etc.) of the operating severity of reaction zone II, can be strengthened the ability that heavy hydrocarbon oil is effectively converted into propylene and high olefin content gasoline fraction in the first riser reactor.Described tripping device is fast separating device, in order to by reaction oil gas and carbon deposited catalyst sharp separation, can adopt existing fast separating device, and preferred fast packing is set to slightly revolves a minute separator.The oil gas product that separation obtains enters product separation system separation; The carbon deposited catalyst that separation obtains is introduced air lift device or is introduced fluidized-bed reactor and then introduce air lift device.
In catalytic cracking method provided by the invention, the operation condition of the reaction zone I of described the first riser reactor comprises: temperature of reaction is 500～700 ℃ (temperature outs), agent-oil ratio is 5～20, and the reaction times is 0.4～10 second, and atomized water steam accounts for 2～50 % by weight of inlet amount; The operation condition of reaction zone II comprises: temperature of reaction is 480～600 ℃, agent-oil ratio is 7～20, and the reaction times is 0.5～8 second, and atomized water steam accounts for the 2-50 % by weight of inlet amount, reaction pressure (absolute pressure, top hole pressure) is 0.15～0.35MPa.Preferably, the operational condition of the first riser reactor reaction zone I: temperature of reaction is 520～650 ℃, agent-oil ratio is 7～12, and the reaction times is 0.5～1.5 second, and atomized water steam accounts for 5～15 % by weight of inlet amount, and reaction pressure is 0.2～0.25MPa; The operational condition of the first riser reactor reaction zone II: temperature of reaction 500-580 ℃, agent-oil ratio is 8～15, the reaction times is that 1～2 second reaction pressure is 0.2～0.25MPa.The ratio of introducing the cracking catalyst of reaction zone I and the cracking catalyst weight of reaction zone II is 1: 0.05～0.5, be preferably 1: 0.15～and 0.30.
In catalytic cracking method provided by the invention, lightweight material is introduced to the second riser reactor reaction, described lightweight material is preferably the C4 hydrocarbon that is rich in the gasoline fraction of alkene and/or is rich in alkene, the second riser reactor temperature (temperature out) is about 520～580 ℃, is preferably 520～560 ℃.The lightweight material of introducing the second riser reactor is 0.05～0.20: 1 with the weight ratio of introducing the heavy feed stock of the first riser reactor, preferably 0.08～0.15: 1.When described lightweight material comprises gasoline fraction, the operation condition of gasoline fraction described in the second riser reactor (the present invention claims again gasoline stocks): gasoline stocks is 10～30 at the agent-oil ratio of the second riser reactor reaction, is preferably 15～25; Gasoline stocks reaction times in the second riser tube is 0.10～1.5 second, preferably 0.30～0.8 second; Atomized water steam accounts for 5～30 % by weight (the atomized water vapor ratio of gasoline) of gasoline feeding amount, preferably 10～20 % by weight.When described lightweight material comprises C4 hydrocarbon, described in the second riser reactor, the operation condition of C4 hydrocarbon comprises: agent-oil ratio (weight ratio of catalyzer and C4 hydrocarbon) is 12～40, preferably 17～30; Described C4 hydrocarbon reaction times in the second riser tube is 0.50～2.0 second, preferably 0.8～1.5 second; The atomized water steam of described C4 hydrocarbon accounts for 10～40 % by weight (C4 hydrocarbon atomized water vapor ratio) of C4 hydrocarbon feed amount, preferably 15～25 % by weight.The operation condition of fluidized-bed reactor: reaction pressure (settling vessel top hole pressure, absolute pressure) is 0.15～0.3MPa, is preferably 0.2～0.25MPa; Fluidized-bed reaction temperature is about 500～580 ℃, is preferably 510～560 ℃; The weight hourly space velocity of fluidized-bed (combined feed total feed of fluid bedreactors) is 1～35 hour
-1, be preferably 3～30 hours
-1.In the cracking masout of being introduced, be 1～30 with the agent-oil ratio of separating heavy oil and catalyzer in fluidized-bed, preferably 5～20; Cracking masout weight hourly space velocity in fluidized-bed is 1～20 hour
-1, preferably 3～15 hours
-1; Atomized water steam accounts for 5～20 % by weight (the atomized water vapor ratio of cracking masout) of cracking masout inlet amount, preferably 10～15 % by weight.
In catalytic cracking method provided by the invention, the lightweight material of introducing the second riser reactor is preferably gasoline fraction and/or the C4 hydrocarbon that is rich in alkene, described in be rich in alkene gasoline fraction raw material be selected from the gasoline fraction that gasoline fraction that the present invention produces and/or other device are produced.The mixture of one or more in the gasoline fraction that the optional catalytic cracking raw gasline of gasoline fraction, catalytic cracking stable gasoline, coker gasoline, viscosity breaking gasoline and other oil refining that other device is produced or chemical process are produced, preferentially selects this to install self-produced gasoline fraction.The described olefin(e) centent that is rich in the gasoline stocks of alkene is 20～95 % by weight, preferably 35～90 weighs %, more than being preferably in 50 % by weight.The described gasoline stocks final boiling point that is rich in alkene is no more than 204 ℃, can be for example that boiling range is the full range gasoline fraction of 35～204 ℃, also can be narrow fraction wherein, for example final boiling point be no more than the gasoline fraction of 85 ℃, preferably the gasoline fraction of boiling range between 40～85 ℃.The described hydrocarbon that is rich in the C 4 fraction of alkene refers to take the low-molecular-weight hydrocarbon existing with gas form under normal temperature that C 4 fraction is main component, normal pressure, comprise alkane, alkene and alkynes that in molecule, carbonatoms is 4, it can be the self-produced gaseous hydrocarbon products that is rich in C 4 fraction of the present invention, also can be the hydrocarbon gas that is rich in C 4 fraction that other device process is produced, wherein preferably this installs self-produced C 4 fraction.In the described C4 hydrocarbon that is rich in alkene, the content of C4 alkene is greater than 50 heavy %, is preferably greater than 60 heavy %, preferably more than 70 % by weight.In lightweight material, be rich in the C4 hydro carbons of alkene and the weight ratio of gasoline stocks is 0～2: 1, preferably 0～1.2: 1, most preferably 0～0.8: 1; The highly olefinic gasoline cut of introducing the second riser reactor is 0.05～0.20: 1 with the weight ratio of introducing the heavy feed stock of the first riser reactor, preferably 0.10～0.15: 1.
In catalytic cracking method provided by the invention, lightweight material is injected to the second riser reactor, after the second riser reactor reaction, introduce fluidized-bed reactor and continue reaction, and the cracking masout that product separation system of the present invention is obtained is introduced in the second riser reactor and/or introduces fluidized-bed reactor and react.When cracking masout is introduced the second riser reactor, the introducing location optimization of described cracking masout at 1/2nd places of riser reactor length (the second riser reactor gasoline entrance is to the length of this reactor outlet) to the part of leg outlet.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, the crackate that enters product separation system is isolated remaining most of product liquid after gas, gasoline and diesel oil, its normal pressure boiling range, between 330～550 ℃, is preferably between 350～530 ℃.The cracking masout of introducing the second riser tube and fluidized-bed reactor is 0.05～0.30: 1 with the weight ratio of injecting the heavy feed stock of the first riser reactor, preferably 0.10～0.25: 1, the cracking masout amount of its actual freshening depends on the reaction depth of the first riser tube, and reaction depth more cracking masout freshening amount is lower.While preferably injecting described cracking masout, the coke content on catalyst reactor is no more than 0.5 % by weight, is preferably 0.1～0.3 % by weight.Cracking masout is introduced in the second riser reactor middle and lower reaches or fluidized-bed reactor, when can reduce coke and dry gas yied, improved the selectivity that generates propylene.
In catalytic cracking method provided by the invention, the reacted catalyzer of the first riser reactor and fluidized-bed reactor shares stripper.The cracking catalyst of fluidized-bed reactor is introduced stripper and is carried out stripping; The carbon deposited catalyst that the first riser reactor separation obtains can directly be introduced stripping system and carry out stripping, also can first introduce fluidized-bed reactor, after catalyst mix in fluidized-bed reactor, enter again stripping system and carry out stripping, preferably first introduce and introduce stripper after fluidized-bed reactor again and carry out stripping, this is conducive to reduce dry gas yied and improves propene yield.The reaction oil gas that leaves fluidized-bed reactor enters settling vessel, and after the settlement separate catalyzer that goes out wherein to carry, oil gas product is introduced follow-up product separation system.In product separation system, oil gas product is isolated to cracked gas, pyrolysis gasoline, cracking light oil and cracking masout.Preferably the oil gas product of the first riser reactor and the oil gas product of fluidized-bed reactor share product separation system, now, will after two strands of air-fuel mixtures, introduce separation system separation.Described product separation system is prior art, and the present invention does not have particular requirement.
In catalytic cracking method provided by the invention, the oil gas that water stripping steam and stripping go out, the bottom of introducing fluidized-bed reactor, through after fluidized-bed, discharge reactor, can reduce oil gas dividing potential drop, shorten oil gas in the settling section residence time, propylene enhancing reduces dry gas, coke yield simultaneously.
In catalytic cracking method provided by the invention, described heavy feed stock is heavy hydrocarbon or the various animals and plants oils raw materials that are 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 can be the hydrocarbon ils that decompressed wax oil, long residuum, decompressed wax oil blending part vacuum residuum or other secondary processing obtain, and the hydrocarbon ils that described secondary processing obtains is as one or more in raffinating oil of wax tailings, deasphalted oil, furfural treatment.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 are through the synthetic distillate obtaining of F-T.The described various animals and plants oils that are rich in hydrocarbon polymer are various animal-plant oil for example.
In catalytic cracking method provided by the invention, described riser reactor be selected from equal diameter riser tube, etc. linear speed riser tube and straighten a kind of or wherein combination of two kinds in the riser tube of footpath, wherein the first riser reactor and the second riser reactor can adopt identical pattern also can adopt different patterns.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, conveying bed and dense bed reactor.
In catalytic cracking method provided by the invention, preferred used cat-cracker at least comprises reactor part, revivifier part and product separation system.Reactor adopts double lifting leg and fluidized-bed to form combined reactor configuration, one of them riser tube and fluidized-bed reaction are coaxial connect after and another root riser tube be arranged in juxtaposition mutually, and a described riser tube and the coaxial cascaded structure of fluidized-bed reaction further with the coaxial coupled arrangement of stripper.
Described riser tube exports sparger with the leg outlet preferred lower pressure in the coaxial series combination of fluidized-bed reaction, and its pressure drop is less than 10KPa, and described low tension outlet sparger can adopt for example arch sparger of existing sparger.
In catalytic cracking method provided by the invention, the type of the selecting zeolite that described mean pore size is less than 0.7 nanometer is selected from ZSM series zeolite, ZRP zeolite, ferrierite, chabazite, dachiardite, erionite, A zeolite, epistilbite, lomontite, and one or more the mixture among the above-mentioned zeolite obtaining after physics and/or chemical process are processed.ZSM series zeolite is selected from one or more the mixture in the zeolite of ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38ZSM-48 and other similar structures.The more detailed description of relevant ZSM-5 is referring to USP3702886, and the more detailed description of relevant ZRP is referring to USP5232675, CN1211470A, CN1611299A.
Describedly contain one or more the combination that the type of selecting zeolite catalyst that mean pore size is less than 0.7 nanometer can be the catalyzer that provided by prior art, can be purchased or this prepares according to existing method.Described catalyzer contains zeolite, inorganic oxide and optional clay, wherein contain: 5～50 % by weight zeolites, 5～95 % by weight inorganic oxides, 0～70 % by weight clay, described zeolite comprises that mean pore size is less than the type of the selecting zeolite of 0.7 nanometer and optional large pore zeolite, the type of the selecting zeolite that mean pore size is less than 0.7 nanometer accounts for 25～100 % by weight of active ingredient, preferred 50～100 % by weight, large pore zeolite accounts for 0～75 % by weight of active ingredient, preferably 0～50 % by weight.
Described large pore zeolite is the zeolite with the cavernous structure of at least 0.7 nano-rings opening, is selected from one or more the mixture in y-type zeolite, zeolite beta, zeolite L, rare earth Y type zeolite (REY), rare earth hydrogen y-type zeolite (REHY), ultrastable Y－type zeolite (USY), extremely steady y-type zeolite of rare earth (REUSY).
Described inorganic oxide is as caking agent, and choosing can be from silicon-dioxide (SiO
2) and/or aluminium sesquioxide (Al
2o
3).Described clay is as matrix, and carrier, can be selected from kaolin and/or halloysite.
In catalytic cracking method provided by the invention, the second riser tube reaction wherein used contain the type of the selecting zeolite catalyst that mean pore size is less than 0.7 nanometer can be identical with the first riser tube used catalyst, also can be different, preferably the first riser reactor and the second riser reactor use catalyzer of the same race.
Below in conjunction with accompanying drawing, method provided by the present invention is further described:
As shown in Figure 1, the bottom that the regenerated catalyst of heat is introduced riser reactor 2 (the second riser reactor) through regenerator inclined tube 9 respectively, the bottom of introducing riser reactor 1 (the first riser reactor) reaction zone I through regenerator inclined tube 10, and under by pipeline 23 and the 22 pre-lift medium effects of injecting, accelerate upwards to flow respectively.Heavy hydrocarbon after preheating or the various animals and plants oils that are rich in hydrocarbon polymer through pipeline 20 after atomizing steam from pipeline 21 mixes by a certain percentage, the reaction zone I of injecting lift pipe reactor 1 contacts, reacts with regenerated catalyst, oil gas with on catalyst mixture, be advanced into reaction zone II when bottom contact, react with new one high temperature regeneration agent of being introduced by regenerator inclined tube 11 again after continuation up, through the fast separating device (not marking in figure) of riser tube 1 end, oil gas carbon deposited catalyst after reacting is separated, the gasoline fraction that is rich in alkene of simultaneously preheating or not preheating and/or C4 hydro carbons through pipeline 24 after atomizing steam from pipeline 25 mixes by a certain percentage, injecting lift pipe reactor 2, thereafter reaction oil gas upwards contacts with this device cracking masout logistics (through the atomization of certain proportion atomizing steam) of introducing through pipeline 36 in flowing-path along riser tube 2 with catalyst mixture, reaction, reaction oil gas and catalyst mixture be continuation reaction after the outlet sparger (not marking in figure) of riser tube 2 is introduced fluidized-bed reactor 4, finally enter settling vessel 5 and carry out the separated of oil gas and catalyzer.Hydrocarbon ils product, comprises the oil gas of riser tube 1 outlet and by pipeline 30, introduce subsequent product separation systems 6 after the oil gas of fluidized-bed reactor 4 outflows all isolates by settling vessel top cyclone separation system (not marking figure) catalyzer wherein carrying.In separation system 6, catalytic pyrolysis product separation is hydrocarbon gas (being drawn by pipeline 31), pyrolysis gasoline (being drawn by pipeline 32), cracking light oil (being drawn by pipeline 33), cracking masout (being drawn by pipeline 34) and cracking slurry oil (being drawn by pipeline 35).The cracked gaseous hydrocarbons that pipeline 31 is drawn can obtain polymerization-grade propylene product and be rich in the C 4 fraction of alkene after subsequent product is separated, refining, and the C 4 fraction that is wherein rich in alkene can transform production propylene by Returning reactor again.The pyrolysis gasoline that pipeline 32 is drawn partly or entirely Returning reacting system transforms 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 to riser tube 2 and transforms; Pipeline 34 is drawn cracking masout and can in Returning reacting system, be transformed again, and preferably cracking masout returns to riser tube 2 or fluidized-bed 4 transforms again through pipeline 36, and more preferably the position after injecting highly olefinic gasoline point is incorporated into riser tube 2 and reacts and transform.Through the isolated carbon deposited catalyst of fast separating device of riser tube 1 end, introduce fluidized-bed reactor 4 mixed with the catalyzer of riser tube 2 outlet introducings, then flow into stripper 3, stripped vapor injects through pipeline 37, with carbon deposited catalyst counter current contact, by the entrained reaction oil gas of carbon deposited catalyst as much as possible stripping go out, then through fluidized-bed reactor 4, introduce settling vessel 5, through pipeline 30, draw reactor together with other oil gas.Catalyzer after stripping is sent into revivifier 7 coke burning regenerations by spent agent inclined tube 8.Oxygen-containing gas is if air is through pipeline 26 injection revivifiers 7, and regenerated flue gas is drawn through pipeline 27.Reaction zone I, II that catalyzer after regeneration returns to respectively riser reactor 2 and riser reactor 1 through regenerator inclined tube 9,10 and 11 recycle, wherein, the position that regenerator inclined tube 11 is connected with riser reactor 1 makes the residence time of hydrocarbon ils in the I of reaction zone be not less than 0.5s, and the residence time in preferred reaction district I is not less than 1 second.
In above-mentioned embodiment process, the pre-lift medium that the pipeline 22 and 23 of corresponding riser tube 1 and riser tube 2 is introduced respectively can be selected from water vapour, C1～C4 hydro carbons or conventional catalytic pyrolysis dry gas, preferably water steam of the present invention and/or be rich in the C 4 fraction of alkene.
The following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment is identical with catalyzer with the stock oil using in comparative example.The raw material A that adopts is a kind of cracking masout, and raw material B is a kind of atmospheric residue, and raw material C is a kind of pyrolysis gasoline that is rich in alkene, and specific nature is in Table 1.The catalyzer adopting is the MMC-2 that Sinopec Shandong catalyst plant is produced, and is less than 0.7nm selects type zeolite containing mean pore size, and its specific nature is in Table 2.
Embodiment 1
The present embodiment explanation: (the present invention claims again fresh feed as reaction feed to take raw material B, lower same), use MMC-2 catalyzer in the situation of medium-sized double lifting leg+fluidized-bed combined reactor testing apparatus (introduce second strand of regenerator on the first riser reactor and form two reaction zones) catalyzed conversion test of successive reaction-regenerative operation.
This middle-scale device first riser tube internal diameter is 16 millimeters, is highly 3800 millimeters, locates opening set up second strand of regenerated catalyst route of introducing 1200 millimeters of distance the first riser tube bottoms; The internal diameter of the second riser tube is 16 millimeters, is highly 3200 millimeters.Leg outlet connects fluidized-bed reactor, and the internal diameter of fluidized-bed reactor is 64 millimeters, 600 millimeters of height, and its configuration is as shown in Figure 1.Test adopts freshening mode to operate.High temperature regeneration agent through three strands of regenerator sloped tubes by revivifier enter respectively two riser tube conversion zones bottom and first riser tube apart from bottom 1200 millimeters of opening parts, and upwards mobile under the effect of pre-lift medium (water vapor).Stock oil B, after preheating mixes with atomized water steam, enters in the first riser tube (it is highly 3800 millimeters) regenerator hot with two strands by feed nozzle and successively contacts and carry out catalytic conversion reaction.The mixture that contains reaction oil gas and catalyzer is introduced reaction oil gas and catalyzer sharp separation equipment carries out gas solid separation along riser tube is up by leg outlet.After reaction oil gas derivation reactor, introduce product separation system and be separated into gas and product liquid, wherein light gasoline fraction and cracking masout cut part freshening continue catalyzed conversion as the charging of second riser tube and fluidized-bed reactor.The catalyzer that contains coke (spent agent) is introduced the stripper that inflow communicates with fluidized-bed after the fluidized-bed be connected with second leg outlet and catalyzer wherein and air-fuel mixture, contact reacts, and water stripping steam stripping goes out on spent agent, after adsorbs hydrocarbons product, by fluidized-bed, to enter settling vessel and carry out gas solid separation.Spent agent after stripping enters revivifier by inclined tube to be generated, contacts carry out high temperature coke burning regeneration with air.Catalyzer after regeneration returns in two riser reactors and recycles through regenerator sloped tube.
After mixing with atomized water steam, the petroleum naphtha that participates in freshening from separation system enters the second riser reactor and high temperature catalyst contact reacts by the second riser tube bottom nozzle, after mixing with atomized water steam, cracking masout enters fluidized-bed reactor and high temperature catalyst contact reacts by fluidized-bed reactor bottom nozzle, reaction oil gas enters settling vessel by fluidized-bed, isolate after the catalyzer wherein carrying, reaction oil gas is introduced product separation system and is carried out separation; The reacted catalyzer that contains coke (spent agent) is introduced stripper with the catalyzer from the first riser reactor, and the spent agent after stripping enters revivifier by inclined tube to be generated, contacts carry out recycling after high temperature coke burning regeneration with air.
The main operational condition of experiment and the results are shown in table 3.
Embodiment 2
The present embodiment explanation: take raw material B as reaction feed, use MMC-2 catalyzer in the situation of the upper catalyzed conversion test of medium-sized double lifting leg+fluidized-bed combined reactor testing apparatus (not introducing second strand of regenerator on first riser tube) of successive reaction-regenerative operation.
Device in the middle-scale device using in this comparative example and embodiment 1 is substantially similar, and difference is that the first riser tube is not set up and introduces second strand of regenerated catalyst route.The main operational condition of experiment and the results are shown in table 3.
Embodiment 3
The present embodiment explanation: take raw material B as reaction feed, use MMC-2 catalyzer in the situation of medium-sized double lifting leg+fluidized-bed combined reactor testing apparatus (introduce second strand of regenerator on first riser tube and form two reaction zones) catalyzed conversion test of successive reaction-regenerative operation.
Testing apparatus is consistent with embodiment 1.Compare with embodiment 1, except adjusting operation operating mode, the freshening that has also increased C 4 fraction transforms, and from the C 4 fraction of separation system participation freshening, introduces the second riser tube pre-lift pipe and catalyzer contact reacts.The main operational condition of experiment and the results are shown in table 4.
Embodiment 4
The present embodiment explanation: take raw material B as reaction feed, use MMC-2 catalyzer in the situation of the upper catalyzed conversion test of medium-sized double lifting leg+fluidized-bed combined reactor testing apparatus (not introducing second strand of regenerator on first riser tube) of successive reaction-regenerative operation.
Testing apparatus is consistent with embodiment 2.Compare with embodiment 2, except adjusting operation operating mode, the freshening that has also increased C 4 fraction transforms, and the C 4 fraction from separation system participation freshening enters the second riser tube pre-lift pipe and catalyzer contact reacts.The main operational condition of experiment and the results are shown in table 4.
From table 3, table 4, catalytic cracking method provided by the invention, can effectively improve heavy oil conversion, increase productivity of propylene, and suppresses dry gas and coke generation.
Embodiment 5
Experiment is carried out at middle-scale device, and raw material is for being rich in olefin cracking petroleum naphtha C and cracking masout A (in C: A=1: 1.5 ratios) mixture, catalyzer is MMC-2.In the middle-scale device of this successive reaction-regenerative operation, the internal diameter of riser tube is 16 millimeters, is highly 3200 millimeters, and leg outlet connects fluidized-bed reactor, and the internal diameter of fluidized-bed reactor is 64 millimeters, 600 millimeters of height.All chargings all participate in reaction from the nozzle access to plant of riser tube bottom.
The operating method that test adopts one way to pass through.High-temperature regenerated catalyst enters riser tube conversion zone bottom through regenerator sloped tube by revivifier, and upwards flows under the effect of water vapor pre-lift medium.Stock oil, after preheating mixes with atomized water steam, is entered in riser tube with hot regenerator and is contacted and carry out catalytic conversion reaction by feed nozzle.Reaction oil gas and catalyst mixture enter by leg outlet the fluidized-bed reaction being connected and continue to enter settling vessel after up, reaction along riser tube is up, and reaction oil gas and the catalyzer sharp separation equipment by settling vessel top carries out gas solid separation subsequently.Reaction oil gas is separated into gas and product liquid after deriving reactor by pipeline, the catalyzer that contains coke (spent agent) flows into stripper because of action of gravity, and water stripping steam stripping goes out on spent agent, after adsorbs hydrocarbons product, by fluidized-bed, to enter settling vessel and carry out gas solid separation.Spent agent after stripping enters revivifier by inclined tube to be generated, contacts carry out high temperature coke burning regeneration with air.Catalyzer after regeneration returns in riser reactor and recycles through regenerator sloped tube.
The main operational condition of experiment and the results are shown in table 5.
Comparative example 1
In test, use stock oil, catalyzer and stock oil feeding manner identical with embodiment 5.Different is that reactor is only riser tube, there is no fluidized-bed reactor.The internal diameter of this riser reactor is 16 millimeters, is highly 3800 millimeters.
The same operating method that adopts one way to pass through of test.High temperature regeneration agent enters riser tube conversion zone bottom through regenerator sloped tube by revivifier, and upwards flows under the effect of pre-lift medium.Stock oil, after preheating mixes with atomized water steam, is entered in riser tube with hot regenerator and is contacted and carry out catalytic conversion reaction by feed nozzle.Contain reaction oil gas and catalyst mixture and by leg outlet, enter settling vessel along riser tube is up, by settling vessel top, reaction oil gas is being housed subsequently and catalyzer sharp separation equipment carries out gas solid separation.Reaction oil gas is separated into gas and product liquid after deriving reactor by pipeline, the catalyzer that contains coke (spent agent) flows into stripper because of action of gravity, and water stripping steam stripping goes out on spent agent, to enter settling vessel after adsorbs hydrocarbons product and carry out gas solid separation.Spent agent after stripping enters revivifier by inclined tube to be generated, contacts carry out high temperature coke burning regeneration with air.Catalyzer after regeneration returns in riser reactor and recycles through regenerator sloped tube.
The operational condition of experiment and the results are shown in table 5.
Embodiment 6
Described in embodiment 5, on middle-scale device, testing.Be rich in olefin cracking petroleum naphtha C and cracking masout A injection ratio is 1: 1, its Raw C is from the raw material nozzles injecting lift pipe of riser tube bottom, and raw material A participates in reaction from the raw material nozzles injecting lift pipe of riser tube length 1/2.The main operational condition of experiment and the results are shown in table 6.
Embodiment 7
Test is carried out on middle-scale device described in embodiment 5.Be rich in olefin cracking petroleum naphtha C and cracking masout A injection ratio is 1: 1.2, its Raw C is from the raw material nozzles injecting lift pipe of riser tube bottom, and raw material A participates in reaction from fluidized-bed bottom raw material nozzles injecting lift pipe.The main operational condition of experiment and the results are shown in table 6.
Comparative example 2
This comparative example explanation: be rich in two kinds of raw materials of olefin cracking petroleum naphtha C and cracking masout A and separate charging at the reaction result of independent riser reactor catalyzed conversion, to further illustrate implementation result of the present invention.
Test is carried out on middle-scale device described in comparative example 1.Be rich in olefin cracking petroleum naphtha C and cracking masout A injection ratio is 1: 1, its Raw C is from the raw material nozzles injecting lift pipe of riser tube bottom, and raw material A participates in reaction from the raw material nozzles injecting lift pipe of riser tube length 1/2.The main operational condition of experiment and the results are shown in table 6.
From table 5 and table 6, embodiment 7 Raw C participate in the feeding manner of reaction from raw material nozzles injecting lift pipe and the raw material A of riser tube bottom from fluidized-bed bottom raw material nozzles injecting lift pipe, compare with comparative example 2 under the substantially suitable condition of the heavy oil conversion degree of depth, can obviously reduce dry gas and coke yield (reducing respectively 1.73 and 0.68 percentage points), propylene and butylene productive rate still increase respectively 1.15 and 0.28 percentage points simultaneously, dry gas selectivity index (dry gas yied and transformation efficiency ratio) is 6.25, compared with comparative example 2 dry gas selectivity index falls, reach 23.17%.
Table 1
| Title | Raw material A | Raw material B | Raw material C |
| Density/(g/cm 3) | 1.0186 | 0.8950 | 0.6696 |
| Refractive index (n d 70) | 1.5835 | 1.4888 | / |
| Kinematic viscosity/(mm 2/s) | |||
| 80℃ | 22.46 | 34.92 | / |
| 100℃ | 10.89 | 20.09 | / |
| Condensation point/℃ | 16 | 48 | / |
| W (carbon residue)/% | 1.61 | 6.05 | / |
| Elementary composition | |||
| (C/H)/m％ | 89.40/9.40 | 86.34/13.10 | 85.18/14.44 |
| (S/N)/m％ | 1.00/0.25 | 0.32/0.24 | 0.015/0.001 |
| Group composition | |||
| (stable hydrocarbon/aromatic hydrocarbons)/m% | 32.3/65.6 | 57.1/20.2 | / |
| (colloid/bituminous matter)/m% | 2.1/0.0 | 22.5/0.2 | / |
| (alkene)/m% | 70 | ||
| Metal content/(μ g/g) | |||
| Ni/V | 0.20/0.29 | 18.30/0.27 | / |
| Boiling range/℃ | |||
| Initial boiling point | 274 | 278 | 32 |
| 5％ | 380 | 362 | 39 |
| 10％ | 403 | 393 | 40 |
| 30％ | 427 | 447 | 44 |
| 50％ | 443 | 503 | 48 |
| 70％ | 464 | 539(57.8) | 53 |
| 90％ | 506 | 65 | |
| 95％ | 534 | 69 |
Table 2
| Catalyzer title | MMC-2 |
| Chemical property, % by weight Al 2O 3 Na 2O RE 2O 3 | 49.2 0.072 0.61 |
| Physical properties total pore volume, ml/g micro pore volume, ml/g specific surface, m 2/ g molecular sieve specific surface, m 2/ g matrix specific surface, m 2/ g tap density, g/ml | 0.208 0.024 155 50 105 0.72 |
| Size-grade distribution, V% 0～20 μ m 0～40 μ m 0～80 μ m 0～110 μ m 0～149 μ m | 1.6 14.2 53.8 72.6 89.5 |
| Lytic activity, % by weight | 66 |
Table 3
| Case | Embodiment 1 | Embodiment 2 |
| Material name | Raw material B | Raw material B |
| Reaction pressure, MPa (a) | 0.21 | 0.21 |
| Regeneration temperature, ℃ | 700 | 700 |
| The first riser reactor | ||
| Reaction zone I | ||
| Temperature of reaction, ℃ | 560 | 530 (the first leg outlets) |
| The oil gas reaction times, s | 1 | 3 |
| Agent-oil ratio, (weight ratio) | 7.8 | 9.7 |
| Atomized water vapor ratio (to fresh feed), % by weight | 7 | 8 |
| Reaction zone II | / | |
| Outlet temperature of riser, ℃ | 530 | / |
| The oil gas reaction times, s | 2 | / |
| Agent-oil ratio, (weight ratio) | 9.7 | / |
| Introduce the ratio of reaction zone I and the cracking catalyst of reaction zone II | 1∶0.25 | / |
| The second riser tube and fluidized-bed combined reactor | ||
| Outlet temperature of riser, ℃ | 540 | 540 |
| Bed temperature, ℃ | 530 | 530 |
| Bed weight hourly space velocity, h -1 | 10 | 10 |
| Petroleum naphtha freshening ratio (to fresh feed), % by weight | 12 | 12 |
| Freshening petroleum naphtha final boiling point, ℃ | 85 | 85 |
| Petroleum naphtha injection phase | Riser tube bottom | Riser tube bottom |
| The agent-oil ratio of petroleum naphtha, (weight ratio) | 15 | 15 |
| The petroleum naphtha riser tube reaction times, s | 0.6 | 0.6 |
| Petroleum naphtha total reaction time, s | 1.8 | 1.8 |
| Petroleum naphtha atomized water vapor ratio, % by weight | 15 | 15 |
| Cracking masout freshening ratio (to fresh feed), % by weight | 12 | 20 |
| Cracking masout injection phase | Fluidized-bed bottom | Fluidized-bed bottom |
| The cracking masout reaction times, s | 1.2 | 1.2 |
| Cracking masout atomized water vapor ratio, % by weight | 10 | 10 |
| Catalyzer | MMC-2 | MMC-2 |
| Material balance, % by weight | ||
| H 2-C2 | 5.60 | 5.32 |
| C3-C4 | 36.00 | 34.72 |
| C5+ pyrolysis gasoline | 31.00 | 31.28 |
| Pyrolysis gas oil PGO | 14.00 | 13.31 |
| Cracking masout | 3.50 | 5.73 |
| Coke | 9.90 | 9.64 |
| Amount to | 100.00 | 100.00 |
| Gasoline+diesel oil | 45.00 | 44.59 |
| Liquefied gas+gasoline+diesel oil | 81.00 | 79.31 |
| Lighter hydrocarbons productive rate (to fresh feed), % by weight | ||
| Ethene | 2.96 | 2.81 |
| Propylene | 17.55 | 16.41 |
| Iso-butylene | 6.04 | 5.48 |
Table 4
| Embodiment numbering | Embodiment 3 | Embodiment 4 |
| Material name | Raw material B | Raw material B |
| Reaction pressure, MPa (a) | 0.21 | 0.21 |
| Regeneration temperature, ℃ | 700 | 700 |
| The first riser reactor | ||
| Reaction zone I | ||
| Outlet temperature of riser, ℃ | 580 | 550 |
| The oil gas reaction times, s | 1.1 | 2.5 |
| Agent-oil ratio, (weight ratio) | 8.68 | 12.4 |
| Atomized water vapor ratio (to fresh feed), % by weight | 8 | 15 |
| Reaction zone II | ||
| Outlet temperature of riser, ℃ | 550 | / |
| The oil gas reaction times, s | 1.4 | / |
| Agent-oil ratio, (weight ratio) | 12.4 | / |
| Introduce the ratio of reaction zone I and the cracking catalyst of reaction zone II | 1∶0.3 | / |
| The second riser tube and fluidized-bed combined reactor | ||
| Outlet temperature of riser, ℃ | 560 | 560 (the first leg outlets) |
| Bed temperature, ℃ | 548 | 548 |
| Bed weight hourly space velocity, h -1 | 5 | 5 |
| C4 hydrocarbon freshening ratio (to fresh feed), % by weight | 8 | 8 |
| C4 hydrocarbon injection phase | Riser tube pre lift zone | Riser tube pre lift zone |
| The agent-oil ratio of C4 hydrocarbon, (weight ratio) | 29 | 29 |
| The C4 hydrocarbon riser tube reaction times, s | 0.78 | 0.78 |
| C4 hydrocarbon total reaction time, s | 1.78 | 1.78 |
| C4 hydrocarbon atomized water vapor ratio, % by weight | 10 | 10 |
| Petroleum naphtha freshening ratio (to fresh feed), % by weight | 10 | 10 |
| Freshening petroleum naphtha final boiling point, ℃ | 85 | 85 |
| Petroleum naphtha injection phase | Riser tube bottom | Riser tube bottom |
| The agent-oil ratio of petroleum naphtha, (weight ratio) | 23 | 23 |
| The petroleum naphtha riser tube reaction times, s | 0.55 | 0.55 |
| Petroleum naphtha total reaction time, s | 1.55 | 1.55 |
| Injected water vapor ratio, % by weight | 15 | 15 |
| Cracking masout freshening ratio (to fresh feed), % by weight | 7 | 10 |
| Cracking masout injection phase | Fluidized-bed bottom | Fluidized-bed bottom |
| The cracking masout reaction times, s | 1.0 | 1.0 |
| Cracking masout atomized water vapor ratio, % by weight | 10 | 10 |
| Catalyzer | MMC-2 | MMC-2 |
| Material balance, % by weight | ||
| H 2-C2 | 8.45 | 8.15 |
| C3-C4 | 46.50 | 44.93 |
| C5+ pyrolysis gasoline | 21.72 | 21.86 |
| Pyrolysis gas oil PGO | 11.00 | 10.84 |
| Cracking masout | 2.00 | 4.39 |
| Coke | 10.33 | 9.83 |
| Amount to | 100.00 | 100.00 |
| Gasoline+diesel oil | 32.72 | 32.70 |
| Liquefied gas+gasoline+diesel oil | 79.22 | 77.63 |
| Lighter hydrocarbons productive rate (to fresh feed), % by weight | ||
| Ethene | 3.95 | 3.81 |
| Propylene | 24.20 | 23.38 |
| Iso-butylene | 4.40 | 4.25 |
Table 5
| Case | Embodiment 5 | Comparative example 1 |
| Material name | Raw material A and raw material C | Raw material A and raw material C |
| Reaction pressure, MPa (a) | 0.21 | 0.21 |
| Regeneration temperature, ℃ | 700 | 700 |
| Structure of reactor | Riser tube and fluidized-bed combined reactor | Independent riser reactor |
| Riser tube length, mm | 3200 | 3800 |
| Fluidized-bed reactor height, mm | 600 | / |
| Temperature of reaction, ℃ | 520 | 520 |
| Petroleum naphtha and cracking masout injection mode | Mix and inject | Mix and inject |
| Petroleum naphtha injection phase | Riser tube bottom | Riser tube bottom |
| Cracking masout injection phase | Riser tube bottom | Riser tube bottom |
| Petroleum naphtha and cracking masout inject ratio | 1∶1.5 | 1∶1.5 |
| Total atomized water vapor ratio, % by weight | 13 | 13 |
| Total agent-oil ratio, (weight ratio) | 8 | 8 |
| Petroleum naphtha reaction operating mode | ||
| Petroleum naphtha agent-oil ratio, (weight ratio) | 20.0 | 20.0 |
| The petroleum naphtha riser tube reaction times, s | 0.91 | 1.19 |
| Petroleum naphtha total reaction time, s | 1.16 | 1.19 |
| Petroleum naphtha atomized water vapor ratio, % by weight | 10.00 | 10.00 |
| Cracking masout reaction operating mode | ||
| Cracking masout agent-oil ratio, (weight ratio) | 13.3 | 13.3 |
| The cracking masout riser tube reaction times, s | 0.91 | 1.19 |
| Cracking masout total reaction time, s | 1.16 | 1.19 |
| Cracking masout atomized water vapor ratio, % by weight | 15 | 15 |
| Bed temperature, ℃ | 520 | / |
| Bed air speed, h -1 | 10 | / |
| Catalyst type | MMC-2 | MMC-2 |
| Material balance, % by weight | ||
| H 2-C2 | 3.20 | 2.50 |
| C3-C4 | 27.59 | 22.56 |
| C5+ pyrolysis gasoline | 35.88 | 37.36 |
| Pyrolysis gas oil PGO | 14.09 | 12.08 |
| Cracking masout | 12.74 | 19.71 |
| Coke | 6.50 | 5.79 |
| Amount to | 100.00 | 100.00 |
| Lighter hydrocarbons productive rate, % by weight | ||
| Ethene | 1.78 | 1.34 |
| Propylene | 14.05 | 10.36 |
| Total butylene | 12.77 | 9.99 |
Table 6
| Case | Embodiment 6 | Comparative example 2 | Embodiment 7 |
| Material name | Raw material A and raw material C | Raw material A and raw material C | Raw material A and raw material C |
| Reaction pressure, MPa (a) | 0.21 | 0.21 | 0.21 |
| Regeneration temperature, ℃ | 700 | 700 | 700 |
| Structure of reactor | Riser tube and fluidized-bed combined reactor | Independent riser reactor | Riser tube and fluidized-bed combined reactor |
| Riser tube length, mm | 3200 | 3800 | 3200 |
| Fluidized-bed reactor height, mm | 600 | / | 600 |
| Temperature of reaction, ℃ | 560 | 560 | 545 |
| Petroleum naphtha and cracking masout injection mode | Separately inject | Separately inject | Separately inject |
| Petroleum naphtha injection phase | Riser tube bottom | Riser tube bottom | Riser tube bottom |
| Cracking masout injection phase | Riser tube length 1/2 place | Riser tube length 1/2 place | Fluidized-bed bottom |
| Petroleum naphtha and cracking masout inject ratio | 1∶1 | 1∶1 | 1∶1.2 |
| Total atomized water vapor ratio, % by weight | 15 | 15 | 14.5 |
| Total agent-oil ratio, (weight ratio) | 12 | 12 | 11.3 |
| Petroleum naphtha reaction operating mode | |||
| Petroleum naphtha agent-oil ratio, (weight ratio) | 24.0 | 24.0 | 24.9 |
| The petroleum naphtha riser tube reaction times, s | 0.40 | 0.54 | 0.71 |
| Petroleum naphtha total reaction time, s | 0.87 | 0.92 | 0.94 |
| Petroleum naphtha atomized water vapor ratio, % by weight | 20.00 | 20.00 | 20.00 |
| Cracking masout reaction operating mode | |||
| Amount of coke on contact cracking heavy oil procatalyst, % by weight | 0.15 | 0.15 | 0.12 |
| Cracking masout agent-oil ratio, (weight ratio) | 24.0 | 24.0 | 20.7 |
| The cracking masout riser tube reaction times, s | 0.40 | 0.54 | / |
| Cracking masout total reaction time, s | 0.60 | 0.54 | 0.23 |
| Cracking masout atomized water vapor ratio, % by weight | 10 | 10 | 10 |
| Bed temperature, ℃ | 560 | / | 545 |
| Bed air speed, h -1 | 7 | / | 8 |
| Catalyst type | MMC-2 | MMC-2 | MMC-2 |
| Material balance, % by weight | |||
| H 2.C2 | 6.50 | 6.23 | 4.50 |
| C3-C4 | 36.17 | 33.00 | 32.00 |
| C5+ pyrolysis gasoline | 29.52 | 31.50 | 30.30 |
| Pyrolysis gas oil PGO | 10.45 | 7.43 | 11.50 |
| Cracking masout | 10.98 | 15.95 | 16.50 |
| Coke | 6.38 | 5.88 | 5.20 |
| Amount to | 100.00 | 100.00 | 100.00 |
| Transformation efficiency, w% | 78.57 | 76.62 | 72.00 |
| Dry gas yied *100/ transformation efficiency | 8.27 | 8.13 | 6.25 |
| Lighter hydrocarbons productive rate, % by weight | |||
| Ethene | 3.73 | 3.45 | 2.58 |
| Propylene | 18.10 | 14.86 | 16.01 |
| Total butylene | 13.54 | 11.70 | 11.98 |
Claims (17)
1. a catalytic cracking method, comprising:
Heavy feed stock and regeneration are less than to cracking catalyst contact reacts in the reaction zone I of the first riser reactor that at least comprises two reaction zones that 0.7nm selects type zeolite containing mean pore size, then reactant flow is introduced in the reaction zone II of the first riser reactor and with the regeneration of introducing reaction zone II and be less than containing mean pore size the cracking catalyst contact reacts that 0.7nm selects type zeolite, the tripping device exporting by this riser reactor is separated with carbon deposited catalyst after reaction by oil gas, oil gas obtains cracked gas through follow-up product separation system separation, pyrolysis gasoline, cracking light oil and cracking masout, the temperature of reaction of reaction zone I is 500～700 ℃, and agent-oil ratio is 5～20, and the reaction times is 0.4～10 second, the temperature of reaction of reaction zone II is 480～600 ℃, and agent-oil ratio is 7～20, and the reaction times is 0.5～8 second, introducing reaction zone I is 1: 0.05～0.5 with the ratio of the cracking catalyst of reaction zone II, described heavy feed stock is heavy hydrocarbon and/or the various animals and plants oils that are rich in hydrocarbon polymer,
Lightweight material and regeneration are contained to mean pore size and be less than catalyzer that 0.7 nanometer selects type zeolite in the second riser reactor contact reacts, then introduce the fluidized-bed reactor of connecting with the second riser tube and continue reaction, meanwhile, cracking masout is introduced to the second riser reactor and/or fluidized-bed reactor bottom; In fluidized-bed reactor, reacted oil gas is introduced settling vessel and is isolated solid wherein, and hydrocarbon product is introduced subsequent products separation system and obtained cracked gas, pyrolysis gasoline, cracking light oil and cracking masout; Wherein, described lightweight material is gasoline fraction and/or C4 hydrocarbon; The temperature of reaction of the second riser reactor is 520～580 ℃; When lightweight material comprises gasoline fraction, described gasoline fraction is 10～30 at the agent-oil ratio of the second lifting inner reaction tube, and the reaction times is 0.1～1.5 second; When lightweight material comprises C4 hydrocarbon, described C4 hydrocarbon is 12～40 at the agent-oil ratio of the second lifting inner reaction tube, and the reaction times is 0.5～2 second; The temperature of reaction of fluidized-bed reactor is 500～580 ℃, and the weight hourly space velocity of fluidized-bed is 1～35 hour
-1.
2. according to catalytic cracking method claimed in claim 1, it is characterized in that, the temperature of reaction of described the first riser reactor reaction zone I is 520～650 ℃, and agent-oil ratio is 7～12, and the reaction times is 0.5～1.5 second.
3. according to catalytic cracking method claimed in claim 1, it is characterized in that, the temperature of reaction of the first riser reactor reaction zone II is 500-580 ℃, and agent-oil ratio is 8～15, and the reaction times is 1～2 second.
4. according to catalytic cracking method claimed in claim 1, it is characterized in that, the temperature of reaction of fluidized-bed reactor is 510～560 ℃, and fluidized-bed weight hourly space velocity is 3～30 hours
-1; The temperature of reaction of the second riser reactor is 520～560 ℃.
5. according to catalytic cracking method claimed in claim 1, it is characterized in that, the first riser reactor heavy feed stock charging atomized water steam accounts for 2～50 % by weight of inlet amount, and reaction pressure is 0.15～0.35MPa; In the second riser reactor, gasoline stocks atomized water steam accounts for 5～30 % by weight of gasoline feeding amount, and C4 hydrocarbon atomized water steam accounts for 10～40 % by weight of C4 hydrocarbon inlet amount; The reaction pressure of fluidized-bed reactor is 0.15～0.3MPa.
6. according to catalytic cracking method claimed in claim 5, it is characterized in that, the heavy feed stock charging atomized water steam of the first riser reactor accounts for 5～15 % by weight of inlet amount; In the second riser reactor, gasoline stocks atomized water steam accounts for 10～20 % by weight of gasoline feeding amount, and C4 raw material hydrocarbon atomized water steam accounts for 15～25 % by weight of C4 hydrocarbon inlet amount.
7. according to catalytic cracking method claimed in claim 1, it is characterized in that, introducing the condition that the cracking masout of the second riser reactor or fluidized-bed reactor reacts in fluidized-bed comprises: the agent-oil ratio of catalyzer and cracking masout is 1～30, and cracking masout weight hourly space velocity in fluidized-bed is 1～20 hour
-1.
8. according to catalytic cracking method claimed in claim 7, it is characterized in that, introducing the condition that the cracking masout of the second riser reactor or fluidized-bed reactor reacts in fluidized-bed comprises: the agent-oil ratio of catalyzer and cracking masout is 5～20, and cracking masout weight hourly space velocity in fluidized-bed is 3～15 hours
-1.
9. according to catalytic cracking method claimed in claim 1, it is characterized in that, the cracking masout of introducing the second riser reactor and fluidized-bed reactor is 0.05～0.30: 1 with the weight ratio of introducing the heavy feed stock of the first riser reactor; The normal pressure boiling range of described cracking masout is between 330～550 ℃.
10. according to catalytic cracking method claimed in claim 1, it is characterized in that, described cracking masout is introduced fluidized-bed reactor.
11. according to catalytic cracking method claimed in claim 1, it is characterized in that, the weight ratio of the heavy feed stock of the lightweight material of the second riser reactor and the first riser reactor is 0.05～0.20: 1.
12. according to catalytic cracking method claimed in claim 1, it is characterized in that, in lightweight material, the weight ratio of C4 hydrocarbon and gasoline fraction is 0～2: 1.
13. according to catalytic cracking method claimed in claim 1, it is characterized in that, described lightweight material comprises the gasoline fraction that is rich in alkene and/or the C4 hydrocarbon that described product separation system obtains.
14. according to the catalytic cracking method described in claim 1～13 any one, it is characterized in that, described lightweight material is the C4 hydrocarbon that is rich in the gasoline fraction of alkene or is rich in alkene, the described olefin(e) centent that is rich in the gasoline fraction of alkene is 20～95 % by weight, is rich in the boiling range of gasoline stocks of alkene between 40～85 ℃; In the described C4 hydrocarbon feed that is rich in alkene, the content of C4 alkene is greater than 50 % by weight.
15. according to catalytic cracking method claimed in claim 1, it is characterized in that, the water vapour after stripping is introduced fluidized-bed reactor bottom, and the first riser reactor carbon deposited catalyst after separation is introduced fluidized-bed reactor.
16. according to catalytic cracking method claimed in claim 1, it is characterized in that, for the cat-cracker of the method, comprise the catalyst transfer line (11) of the first riser reactor (1), the second riser reactor (2), stripper (3), fluidized-bed reactor (4), settling vessel (5), product separation system (6), revivifier (7) and the first riser reactor reaction zone II; Wherein the second riser reactor (2) is arranged in juxtaposition mutually with the first riser reactor (1) after connecting with fluidized-bed reactor (4) is coaxial, riser reactor (2) and fluidized-bed reactor (4) and the coaxial arranged in series of stripper (3).
17. according to the catalytic cracking method described in claim 1 or 16, it is characterized in that the first described riser reactor be selected from equal diameter riser tube, etc. linear speed riser tube or straighten footpath riser reactor; The second described riser reactor be selected from equal diameter riser tube, etc. linear speed riser tube or straighten footpath riser reactor; That described fluidized-bed reactor is selected from is fixed fluidized bed, dispersion fluidized bed, bubbling bed, turbulent bed, fast bed, conveying bed and dense bed reactor.
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| CN102899078B (en) * | 2011-07-29 | 2015-03-18 | 中国石油化工股份有限公司 | Catalytic cracking method for producing propylene |
| CN103131464B (en) * | 2011-11-23 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of hydrocarbons catalytic conversion method producing low-carbon alkene and light aromatic hydrocarbons |
| CN103131463B (en) * | 2011-11-23 | 2015-07-01 | 中国石油化工股份有限公司 | Hydrocarbon catalytic conversion method for increasing propylene yield |
| CN103360197B (en) * | 2012-03-30 | 2015-07-01 | 中国石油化工股份有限公司 | High-selectivity method for producing propylene by using C4-C8 olefins |
| CN103509596B (en) | 2013-09-29 | 2015-08-26 | 中国石油大学(北京) | A kind of method of processing inferior heavy oil |
| CN106609153A (en) * | 2015-10-21 | 2017-05-03 | 中国石油天然气股份有限公司 | Riser catalytic cracking process |
| CN108946741B (en) * | 2017-05-17 | 2020-05-12 | 新特能源股份有限公司 | Process method for recovering silicon-containing high-boiling-point substance in polycrystalline silicon cold hydrogenation process and cold hydrogenation process |
| CN109385296B (en) * | 2017-08-08 | 2021-01-01 | 中国石油天然气股份有限公司 | Catalytic conversion method of hydrocarbon oil |
| CN110305694B (en) * | 2018-03-20 | 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 |
| CN110540861B (en) * | 2018-05-28 | 2021-11-16 | 中国石油化工股份有限公司 | Catalytic cracking process and system |
| CN110724550B (en) | 2018-07-16 | 2021-04-06 | 中国石油化工股份有限公司 | Method and system for catalytic cracking by adopting fast fluidized bed |
| CN110724553B (en) * | 2018-07-16 | 2021-04-06 | 中国石油化工股份有限公司 | Method and system for catalytic cracking by adopting dilute phase conveying bed and rapid fluidized bed |
| CN111423905B (en) * | 2019-01-09 | 2023-10-10 | 中国石油化工股份有限公司 | Catalytic cracking process and system |
| CN111423904B (en) * | 2019-01-09 | 2023-10-13 | 中国石油化工股份有限公司 | Catalytic cracking process and system |
| CN110129076B (en) * | 2019-04-23 | 2021-07-06 | 湖南现代环境科技股份有限公司 | Biomass low-temperature carbon gas co-production device, biomass low-temperature carbon gas co-production device and biomass low-temperature carbon gas co-production method |
| CN112536001B (en) * | 2019-09-20 | 2022-09-09 | 中国石油化工股份有限公司 | Catalytic conversion reactor and system |
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