TW201217511A - providing higher heavy oil conversion rate and propene yield and lower dry gas and coke yield - Google Patents

Abstract

The present invention discloses a catalytic cracking device and a method thereof, which can be applied to catalytic cracking of heavy oil to provide higher heavy oil conversion rate and propene yield and lower dry gas and coke yield. The catalytic cracking method comprises: in a first riser reactor, reacting and contacting heavy raw material with optional atomized mist and a catalyst containing optionally shaped zeolite with an average aperture less than 0.7 nanometer to obtain a material stream containing a first oil gas product and a first coke catalyst, wherein the first oil gas product and the first coke catalyst are separated by a separator at the terminal of the first riser reactor; introducing a light raw material and optional atomized mist to a second riser reactor to contact and react with a catalyst containing optionally shaped zeolite with an average aperture less than 0.7 nanometer to obtain a second oil gas product and a second coke catalyst, wherein the second oil gas product and the second coke catalyst are introduced to a fluidized bed reactor in serial connection with the second riser reactor to react under the presence of a catalyst containing optionally shaped zeolite with an average aperture less than 0.7 nanometer; meanwhile, introducing cracked heavy oil, preferably the cracked heavy oil prepared by the method of the resent invention, to the second riser reactor and/or the fluidized bed reactor, preferably to the fluidized bed reactor, to carry out a reaction; and obtaining a material stream containing a third oil gas product and a third coke catalyst from the fluidized bed reactor.

Description

201217511 VI. Description of the Invention: TECHNICAL FIELD The present invention relates to a catalytic cracking apparatus and method. [Prior Art] Heavy oil catalytic cracking is an important method for preparing low-carbon olefins such as ethylene, propylene and butene. Industrially used heavy oil catalytic cracking processes for the production of light olefins include the processes disclosed in U.S. Patent No. 4, 858, 053, U.S. Patent No. 5, 670, 037, and U.S. Patent No. 6,210, 562, each of which uses a single riser reactor or a single riser reactor combined with a dense phase fluidized bed (dense-phase fluidized) The reactor structure of bed) is reacted, but the yield of dry gas and coke is high. In recent years, the technology for producing propylene using two riser reactors has received considerable attention. CN1 01 07 43 92 A discloses a method for producing propylene and high quality gasoline and diesel using two-stage catalytic cracking, using a two-stage riser, using a shape-selective molecular sieve-containing catalyst, as a heavy petroleum hydrocarbon or A variety of animal and vegetable oils rich in hydrocarbons are used as raw materials, and the reaction materials of different natures are combined to control the reaction conditions of different materials to achieve the propylene yield, the light oil yield and quality, and the suppression of dryness. The purpose of gas and coke formation. However, the propylene yield is not high and the heavy oil conversion ability is low. CN101293806A discloses a catalytic conversion process for increasing the yield of low-carbon olefins by injecting a hydrocarbon oil feedstock through a feed nozzle into a riser or/and a flow 201217511 chemical bed reactor, and selecting a shape having an average pore diameter of less than 0.7 nanometers (nm). The zeolite catalyst is contacted and reacted, and a hydrogen-rich gas is injected into the reactor to separate the reaction oil and gas from the post-reaction carbon deposition catalyst, wherein the reaction oil and gas are separated to obtain a desired product containing ethylene and propylene, and the carbon deposition catalyst is stripped. After regeneration, return to the reactor for repeated use. The process suppresses the re-conversion reaction of the lower olefin after formation by injecting a hydrogen-rich gas into the reactor to increase the yield of the low-carbon olefin (particularly propylene). However, this method has little effect on reducing dry gas yield and improving heavy oil conversion ability. CN 1 0 1 3 1 47 24A discloses a combined catalytic conversion process of bio-fat and mineral oil, comprising contacting bio-oil and mineral oil in a compound reactor with a catalyst containing modified beta zeolite for catalytic cracking reaction. Low-carbon olefins and gasoline, diesel, heavy oil. The method has high dry gas yield and low heavy oil conversion rate. SUMMARY OF THE INVENTION The technical problem to be solved by the present invention is to provide a catalytic cracking apparatus and method for increasing the yield of low olefins, particularly propylene, and the conversion of heavy oil. In one embodiment, the invention provides a catalytic cracking process comprising: treating a heavy feedstock and optionally atomized water vapor with a catalyst comprising a shape selective zeolite having an average pore size of less than 0.7 nanometers in a first riser reactor The medium contact reaction obtains a stream containing the first hydrocarbon product and the first carbon catalyst -6-201217511, and the first oil and gas product is separated from the first carbon catalyst by a separation device at the end of the first riser, and the light raw material and Optionally atomizing water vapor is introduced to the second riser reactor and reacting with a catalyst comprising a shape selective zeolite having an average pore diameter of less than 0.7 nm to obtain a second hydrocarbon product and a second carbonaceous catalyst 'second hydrocarbon product and The second carbonaceous catalyst is introduced into a fluidized bed reactor in series with the second riser reactor to react in the presence of a catalyst having a shape-selective zeolite having an average pore diameter of less than 〇·7 nm, and at the same time, the heavy oil is cracked, Preferably, the cracked heavy oil produced by the process is introduced to a second riser reactor and/or a fluidized bed reactor, preferably to a fluidized bed reactor for reverse ; Third hydrocarbon-containing product was obtained, and a third coke from the catalyst in the fluidized bed flow reactor. In a further embodiment, the heavy feedstock comprises a heavy hydrocarbon and/or a hydrocarbon-rich animal and vegetable oil; wherein the light feedstock comprises a gasoline fraction and/or a C4 hydrocarbon; wherein the cracking The heavy oil is a cracked heavy oil with an atmospheric distillation range of 3 30 to 550 ° C. In a further embodiment, the catalytic cracking process further comprises: separating the first oil and gas product by a product separation system to obtain a cracking gas, pyrolysis gasoline, cracking light recycle oil, and cracking heavy oil: and/or The third oil and gas product is separated by a product separation system to obtain a cracking gas, a pyrolysis gasoline, a cracked light cycle oil, and a cracked heavy oil. In a further embodiment, the first riser reactor atomizing water vapor accounts for 2 to 50% by weight of the feed amount, preferably 5 to 10% by weight, and the reaction pressure is 0.15 to 0.3 MPa, preferably 0.2~0.25MPa; wherein, the reaction temperature of the first rise 201217511 riser reactor is 480~600 °C, preferably 500~560 °C, the ratio of the agent to oil is 5~20, preferably 7~15, the reaction The time is 0.50 to 10 seconds', preferably 2 to 4 seconds. In a further embodiment, the reaction temperature of the second riser reactor is 520 to 580 ° C, preferably 520 to 560 ° C; the light feedstock to which the second riser reactor is directed includes gasoline fraction, gasoline The ratio of the atomized water vapor of the raw material is 5 to 30% by weight, preferably 10 to 20% by weight; when the light raw material includes the gasoline fraction, the ratio of the ratio of the gasoline to the gasoline in the second riser is It is 10~30', preferably 15~25, the reaction time is 〇.1〇~1.5 seconds, preferably 0.30~0 _ 8 seconds; when the light raw material includes C 4 hydrocarbon, C 4 hydrocarbon atomized water vapor The ratio is from 1 〇 to 40% by weight, preferably from 1 5 to 25% by weight. When the light raw material comprises C4 hydrocarbon, the ratio of the ratio of the C4 hydrocarbon to the second riser is 12 to 40. Preferably, the reaction time is from 0.50 to 2.0 seconds, preferably from 0. 8 to 1 _ 5 seconds. In a further embodiment, the fluidized bed reactor has a reaction temperature of from 500 to 580 ° C, preferably from 510 to 560 ° C, and a WHSV of from 1 to 35 hours -1, preferably from 3 to 30 hours. The reaction pressure of the fluidized bed reactor is 〇. : i 5 to 0.3 MPa, preferably 0.2 to 0.25 MPa. In a further embodiment, the conditions for the reaction of the cracked heavy oil in the fluidized bed include: a ratio of the cracked heavy oil to the catalyst to the oil of the catalyst is from 1 to 50, preferably from 5 to 40; and the cracked heavy oil has a WHSV of 1 in the fluidized bed. ~20 hours -1, preferably 3 to 15 hours of stomach 1; the ratio of atomized water vapor of the cracked heavy oil is 5 to 20% by weight, preferably 10 to 15% by weight. In a further embodiment, to the second riser reactor and /

-8 - 201217511 or the weight ratio of the cracked heavy oil in the fluidized bed reactor to the reverse feedstock to the first riser is 0.05 to 0.30:1. In a further embodiment, when the light raw material fraction is used, the weight ratio of the gasoline fraction introduced to the second riser reactor to the heavy raw material of the riser reactor is 0.05 to 0.20:1. When the raw material includes a gasoline fraction and a C 4 hydrocarbon, the weight ratio of the gasoline fraction in the light raw material in the light raw material is 0 to 2 1 . In a further embodiment, the gasoline fraction is lightly olefin-rich gasoline fraction having an olefin content of from 20 to 95 parts by weight and not more than 85 ° C; the C4 hydrocarbon light feedstock is an olefin-rich CM olefin. The content is more than 50% by weight. In a further embodiment, the gasoline fraction includes pyrolysis gasoline separated by the product separation system. In a further embodiment, the catalytic cracking unit combines the first hydrocarbon product with the third hydrocarbon product and directs it to the production separation. In a further embodiment, the catalytic cracking side first introduces the first carbon deposition catalyst to the fluidized bed reactor, mixes with the catalyst of the flow device, and then leads to the stripper, or directs the first agent. To the stripper. In a further embodiment, the catalytic cracking side directs the first carbon deposition catalyst and/or the third carbon deposition catalyst with water and the stripping water vapor entrained with the oil and gas product to the fluidized bed, in an embodiment. The invention provides a catalytic cracking device comprising a gasoline to a first extraction; when the C4 hydrocarbon and a raw material are: %, a final C4 hydrocarbon, the raw material packaging method further comprises a product separation method, further comprising The chemical bed catalytic carbon deposition catalysis also includes a steam stripping reactor. Included, its package -9 - 201217511 includes: a first riser reactor (1) for cracking heavy feedstock, the first riser reactor having one or more heavy feedstocks located at the bottom of the riser a second riser reactor (2) for cracking a light feedstock, the second riser reactor having one or more light feedstock inlets at the bottom of the riser and a top of the riser a discharge port, a fluidized bed reactor (4) having one or more feed ports, and the fluidized bed reactor is connected via a connecting member, preferably a low pressure outlet distributor, a fine arched distributor) connected to a discharge port of the second riser reactor, a separation device disposed at the end of the first riser, preferably a quick separation device, the separation device including oil and gas a discharge port and a catalyst discharge port, wherein the second riser reactor and/or the fluidized bed reactor further have one or more cracks located above the one or more light feed inlets Heavy oil feed port, preferably, said a cracking heavy oil feed port between one-half of the length of the second riser reactor and the second riser discharge port, and more preferably, the cracked heavy oil feed port is in the fluidization a bottom of the bed reactor, and optionally a 'product separation system (6) that separates the cracked heavy oil from the oil and gas products from the first riser reactor and/or the fluidized bed reactor, and via A cracking heavy oil loop directs the cracked heavy oil to the one or more cracked heavy oil feed ports.

-10- 201217511 In a further embodiment, the catalytic cracking unit further comprises: a stripper (3), a settler (5), a product separation system (6), a regenerator (7), and a cyclone separation system: The stripper has an inlet for stripping water vapor, an outlet of the stripped catalyst, and an outlet for stripping water vapor with steam; wherein the settler is in communication with a discharge port of the fluidized bed reactor, and Having one or more inlets for receiving the reaction oil and one or more outlets connected to the product separation system; wherein the regenerator includes a regeneration section, one or more spent catalyst inclined tubes, and one or more a regenerated catalyst inclined tube 'where preferably a used catalyst inclined tube is connected to the stripper, and a regenerated catalyst inclined tube is connected to the first and / or second riser reactor; wherein the product separation system will be C4 hydrocarbon , pyrolysis gasoline, and cracked heavy oil are separated from the oil and gas products from the first riser reactor and/or the fluidized bed reactor, and the cracked heavy oil is led to the one via the cracking heavy oil circuit Or a plurality of cracked heavy oil feed ports, and/or directing pyrolysis gasoline to the one or more light feedstock feed ports via a pyrolysis gasoline loop, and/or introducing CM hydrocarbons to the one or more through a C4 hydrocarbon loop A light feedstock feed port; wherein the cyclone separation system is disposed at the top of the settler and is coupled to the outlet of the settler for further separation of the hydrocarbon product and catalyst solid particles. The invention is based on a combined reactor composed of a double riser and a fluidized bed, and is optimized by a technical method, equipped with a suitable catalyst, and selectively converts different feeds, and significantly increases the production of propylene on the basis of effectively improving the conversion of heavy oil. 201217511 rate, suppresses dry gas and coke formation, and can improve the properties of pyrolysis gasoline and light oil. Compared with the prior art, the separation of the first oil and gas product from the first carbon deposition catalyst through the separation device (fast branching device) at the end of the first riser reactor can reduce dry gas yield and inhibit low carbon olefins, especially propylene. Re-conversion after production: The present invention produces the olefin-rich gasoline fraction and/or C4 hydrocarbon as a feedstock to the second riser reactor connected to the fluidized bed reactor while the apparatus/method is produced The cracked heavy oil is led to the second riser reactor or the fluidized bed reactor to participate in the conversion. On the one hand, the secondary conversion of heavy oil is enhanced to increase the degree of heavy oil conversion of the whole apparatus, the cracked heavy oil fraction is used to increase the production of propylene, and the olefin-rich gasoline fraction is simultaneously The chilling of the reaction with and/or the C4 hydrocarbon is terminated, inhibiting the low-carbon olefins, especially the re-conversion reaction after propylene formation, thereby effectively maintaining high propylene yield. In addition, the method of the invention introduces the stripped water vapor entrained with oil and gas to the fluidized bed reactor, and passes through the fluidized bed reactor and exits the reactor, thereby effectively reducing the partial pressure of the oil and gas product and shortening the oil product in the settler. The residence time increases the production of propylene while reducing the dry gas and coke yield. [Embodiment] In the present invention, unless otherwise indicated, the reaction temperature of the riser reactor refers to the outlet temperature of the riser reactor; the reaction temperature of the fluidized bed reactor refers to the bed temperature of the fluidized bed reactor. In the present invention, the ratio of the agent to the oil refers to the weight ratio of the catalyst to the oil/hydrocarbon unless otherwise indicated. In the present invention, unless otherwise stated, the reaction pressure of the riser reactor -12 - 201217511 force refers to the absolute pressure of the outlet of the reactor. In the present invention, the gasoline fraction is used interchangeably with the gasoline feedstock unless otherwise indicated. In the present invention, the proportion of the atomized water vapor of the gasoline raw material means the ratio of the atomized steam of the gasoline to the amount of the gasoline fed, unless otherwise stated. In the present invention, unless otherwise indicated, the C4 hydrocarbon atomized water vapor ratio refers to the ratio of the atomized water vapor of the C4 hydrocarbon to the C4 feed amount. In the present invention, the atomized water vapor ratio of the cracked heavy oil means the ratio of the atomized water vapor to the amount of the cracked heavy oil, unless otherwise stated. In the present invention, unless otherwise indicated, the reaction pressure of the fluidized bed reactor refers to the absolute pressure of the outlet of the reactor, and in the case where the fluidized bed reactor is connected to the settler, it means the absolute pressure of the outlet of the settler. In the present invention, the WHSV of the fluidized bed means, in terms of the total feed of the fluidized bed reactor, unless otherwise stated. In the present invention, the quick-distribution device is a cyclone capable of achieving rapid separation of catalyst solids and oil and gas products unless otherwise indicated. Preferably, the cyclone separator is a primary cyclone separator. According to the present invention, the heavy raw material and the atomized water vapor are subjected to catalytic cracking reaction in the first riser reactor to obtain a stream containing the first oil and gas product and the first carbon deposition catalyst, the first oil and gas product and the first product. The carbon catalyst is separated by a separation device at the end of the first riser. In one embodiment, the separation device is a fast separation device for rapidly separating oil and gas products from a carbon deposition catalyst. In one embodiment, an existing fast dispensing device can be employed. A preferred quick-distribution device is a coarse cyclone separator. -13- 201217511 First riser reactor reaction operating conditions: reaction temperature is 480 to 600 ° C, preferably 5 00 to 5 60 ° C, and the ratio of the agent to oil is 5 to 20, preferably 7 to 1 5, the reaction time is 0.5 0 to 10 seconds, preferably 2 to 4 seconds, the atomized water vapor accounts for 2 to 50% by weight of the feed fl, preferably 5 to 10% by weight, and the reaction pressure is 0.15. 〜0.3 MPa, preferably 0.2 to 0.25 MPa. According to the present invention, a light feedstock and optionally atomized water vapor are introduced to a second riser reactor for contact reaction with a catalyst comprising a shape-selective zeolite having an average pore diameter of less than 0.7 nm to obtain a second hydrocarbon product and a second The carbonaceous catalyst, the second oil and gas product and the second carbonaceous catalyst are introduced to a fluidized bed reactor in series with the second riser reactor, in the presence of a catalyst comprising a shape selective zeolite having an average pore diameter of less than 0.7 nm. The reaction, at the same time, will crack the heavy oil, preferably, the cracked heavy oil produced by the method is introduced to the second riser reactor and/or the fluidized bed reactor, preferably to the fluidized bed reactor for reaction; A stream comprising a third hydrocarbon product and a third carbon catalyst is obtained in a fluidized bed reactor. The third hydrocarbon product and the third carbon deposition catalyst are separated by a settler to separate the third oil product and the third carbon catalyst, and the third oil product is led to the product separation system to obtain cracking gas, pyrolysis gasoline, and cracking light. Cycle oil and crack heavy oil. The light feedstock to the second riser reactor is a gasoline fraction and/or a C4 hydrocarbon, preferably an olefin-rich C4 hydrocarbon and/or an olefin-rich gasoline fraction. The second riser has a reaction temperature of about 520 to 580 ° C, preferably 520 to 560 t. Reaction operating conditions of the gasoline fraction introduced to the second riser reactor: the ratio of the ratio of the gasoline to the raw material in the second riser is 10 to 30, preferably 15 to 2 5; the gasoline raw material is in the second riser The reaction time is 〇. 1 〇~1 · 5 seconds,

-14- 201217511 is preferably 0.3 0 to 0 · 8 seconds; the ratio of atomized water vapor of the gasoline raw material is 5 to % ‘preferably 10 to 2 0% by weight. Reaction operating conditions of C 4 hydrocarbons: the ratio of the hydrocarbon to the hydrocarbon in the second riser is 12 to 40, preferably the reaction time of the 17 C4 hydrocarbon in the second riser is 〇50 to 2.0 seconds, which is ί 1.5 The ratio of C4 hydrocarbon atomized water vapor is from 1 to 40% by weight, preferably by weight. According to the present invention, the reaction operating conditions of the fluidized bed reactor are at a pressure of 0.15 to MPa3. 3 MPa, preferably 0.2 to 0.25 MPa; and the flow temperature is about 500 to 580 ° C, preferably 510 to 560 ° C. The flow WHSV is 1 to 3 5 hours -1, preferably 3 to 3 0 -1. According to the present invention, the reaction operating conditions for cracking the heavy oil fraction in the second riser reactor and/or the flow reactor are: the ratio of catalyst to crack contact agent oil is 1 to 50, preferably 5 to 40; The flow WHSV is 1 to 20 hours, preferably 3 to 15 hours -1, and the ratio of the cracked heavy oil to water vapor is 5 to 20% by weight, preferably 10 to 15% by weight. According to the present invention, the light source introduced to the second riser reactor is an olefin-rich gasoline fraction and/or an olefin-rich C4 hydrocarbon, and the olefin-containing gasoline fraction feedstock is selected from the gasoline plant produced by the apparatus of the present invention. The gasoline fraction, preferably, the pyrolysis gasoline obtained by the separation of the product. The gasoline fraction produced by other units may be selected from one or a mixture of gasoline fractions produced by FCC naphtha, stabilized gasoline stabilized gasoline, coker gasoline, viscous pyrolysis gasoline for refining or chemical processes. The olefin content of the olefin-rich gasoline feedstock is 20 30 wt% C4 〜30: I 0.8 〜 1 5 〜25 Included: the reversed bed of the reaction bed is reversed from the atomized material in the heavy oil bed Preferably, the FCC and other systems are separated by catalytic cracking (FCC and other above ~95 weight -15-201217511%% is preferably 3 5~90% by weight, optimally above 50% by weight. The gasoline raw material may be The full distillation range of the gasoline fraction, the final boiling point does not exceed 204. (:, can also be a narrow fraction of it, such as the distillation range of 40 ~ 8 5 (: between the gasoline fraction. Lead to the second riser reaction The weight ratio of the gasoline fraction of the apparatus to the heavy raw material introduced to the first riser reactor is 0.05 to 0.20:1, preferably 0·08 to 0.15:1. The C4 hydrocarbons are at normal temperature (0-3). Low-molecular hydrocarbons in the form of a gas at atmospheric pressure (1 atm) and having a C4 fraction as a main component, including alkanes, alkenes and alkynes having a carbon number of 4. It may be produced by the device. The gaseous hydrocarbon product rich in C4 fraction may also be a gaseous hydrocarbon rich in C4 fraction produced by other process processes, of which Is the self-produced C4 fraction of the apparatus. The C4 hydrocarbon is preferably an olefin-rich C4 fraction, wherein the C4 olefin content is more than 50% by weight, preferably more than 60% by weight, most preferably more than 70% by weight. In one embodiment, the weight ratio of the C4 hydrocarbon to the gasoline fraction in the light raw material is 0 to 2:1, preferably 0 to 1.2:1, more preferably 0 to 0.8:1. According to the present invention, the light raw material and any The selected atomized water vapor is introduced to the second riser reactor, and after the reaction in the second riser reactor, the second oil and gas product and the second carbon deposition catalyst are obtained, and the second oil product and the second carbon catalyst are led to The fluidized bed reactor continues the reaction and the cracked heavy oil obtained from the product separation system of the present invention is introduced into a second riser reactor for reaction, and/or directed to a fluidized bed reactor for reaction. In one embodiment Introducing the cracked heavy oil to the second riser reactor, the introduction position of the cracked heavy oil is higher than the introduction position of the light raw material, preferably, the introduction position of the cracked heavy oil is at the riser reactor length (riser) Gasoline entrance to -16 - 201217511 Between one-half of the portion between the riser outlets and the riser outlet. In one embodiment, the cracked heavy oil is directed to a fluidized bed reactor, preferably, the cracked heavy oil is directed to The bottom of the fluidized bed reactor. The cracked heavy oil is the cracked heavy oil obtained from the product separation system of the present invention, that is, most of the liquid remaining after separating the gas, gasoline and diesel from the oil and gas products entering the product separation system. The product has a normal pressure distillation range of 330 to 550 ° C, preferably a normal pressure distillation range of 350 to 530 ° C. The second riser is injected or injected into the fluidized bed reactor or injected into the second riser and the flow. The weight ratio of the cracked heavy oil of the chemical bed reactor to the heavy raw material injected into the first riser reactor is 0.05 to 0.30:1, preferably 0.10 to 0.25:1. The actual amount of cracked heavy oil refining depends on the degree of reaction of the first riser. The greater the degree of reaction, the lower the amount of cracked heavy oil. Preferably, when the cracked heavy oil is injected, the amount of carbon deposited on the catalyst in the reactor is not more than 0.5% by weight, preferably 0.1 to 0.3% by weight. The introduction of cracked heavy oil between one-half of the length of the riser reactor and the riser outlet or in the fluidized bed reactor reduces coke and dry gas yields while increasing the selectivity to propylene. According to the present invention, the separation device at the end of the first riser reactor separates the first hydrocarbon product from the first carbon deposition catalyst, and the first hydrocarbon product is directed to the product separation system for separation. The third hydrocarbon product leaving the fluidized bed reactor is advanced into the settler' to settle out the catalyst carried therein and then to the subsequent product separation system. In the product separation system, the oil and gas products are separated to obtain cracked gas, pyrolysis gasoline, cracked light cycle oil, and cracked heavy oil. Preferably, the first oil and gas product and the third oil and gas product share a product separation system, wherein the first oil and gas product and the third oil and gas product are mixed and introduced to the product separation system -17-201217511. The product separation system described is prior art and the present invention is not required. According to the present invention, the first coke catalyst obtained by separating the ends of the first riser reactor can be directly introduced to the stripper for introduction to the fluidized bed reactor, and after being combined with the fluidized bed reactor, Enter the stripping system for stripping. Preferably, the first agent is first introduced to the fluidized bed reactor, and after passing through the fluidized bed reactor, the stripper is stripped. The catalyst (carbon catalyst) leaving the fluidized bed reactor is led to a stripper for stripping. The first carbon-catalyzed carbon deposition catalyst is preferably stripped in the same stripper, stripped to a regenerator for regeneration, and the regenerated catalyst is introduced to the first lift and/or the second riser reactor for reuse. According to the present invention, the stripping water vapor and the stripped oil are flown to the bottom of the reactor and the partial pressure of the oil and gas products in the reactor is discharged through the fluidized bed, thereby shortening the residence of the oil and gas product in the settler to produce propylene while reducing dry gas, Coke yield. The heavy raw materials described in the present invention are heavy hydrocarbons or rich in animal and vegetable oil raw materials. The heavy hydrocarbons are selected from one or a mixture of one or more of petroleum hydrocarbons and synthetic oils. It is known to those skilled in the petroleum hydrocarbon field, for example, a vacuum oil, a vacuum-reduced wax oil blended partially vacuum residue or other secondary processing to obtain the hydrocarbon oil obtained by the other secondary processing, such as coking wax oil, One or more of the lysaldehyde-refined raffinate oil. The mineral oil is selected from one or more of coal liquefied oil and shale oil, and has a special device for separating and stripping, and the catalyst is mixed with carbon to catalyze the re-entry into the steam, that is, the third product and the third catalyst tube reaction. The product is introduced to reduce the time, and each of the hydrocarbons and mineral oils are hydrocarbon oils. A mixture of green oil, eucalyptus oil and oil sands. -18- 201217511 Synthetic oil is obtained by F-Τ synthesis of coal, natural gas or asphalt. The hydrocarbon-rich animal and vegetable oils are animal and vegetable oils and fats. According to the present invention, there is provided a catalytic cracking apparatus for a first riser reactor for cracking heavy feedstock. The first riser reactor has a raw material feed port at the bottom of the riser for cracking light raw materials. Two riser reactors! The second riser reactor has a feed inlet at the bottom of the riser and a discharge port at the top of the riser, a fluidized bed reactor (4), a plurality of feed ports of the fluidized bed reactor, and The fluidized bed reactor is connected to the outlet of the reactor through a low pressure outlet distributor, more preferably, an arched distributor, and is disposed at the end of the first riser, preferably, the separation The apparatus includes an oil and gas discharge port and a catalyst discharge wherein the second riser reactor and/or the stream further has a cracked heavy oil feed port located above the one or more light feedstock feed ports, preferably The cracked heavy oil enters between one-half of the length of the second riser reactor and the first feed port, and more preferably, the cracked heavy oil feed port is at the bottom of the reactor, and optionally Ground, a product separation system (6) that cracks heavy oil from the first riser reactor and/or fluidized distillate. One or more of the following: (1), the one or more heavy masses [2), the one or more lightweight ones have one or more components, preferably the second riser ground, the quick splitting mouth, the chemical bed One or more of the reactors are separated from the -19-201217511 oil and gas product of the bed reactor by the fluidized bed reverse separation system of the second riser and directing the cracked heavy oil to the one or more via a cracking heavy oil circuit One cracked heavy oil feed port. In a further embodiment, the present invention provides a catalytic cracking unit further comprising: a stripper (3), a settler (5), a product separation system (6), a regenerator (7), and a cyclone separation system. In still further embodiments, the stripper has an inlet for steam for stripping, an outlet for stripped catalyst, and an outlet for stripping steam with oil and gas. In still further embodiments, wherein the settler is in communication with a discharge port of the fluidized bed reactor and has one or more inlets for receiving reaction oil and gas, and one or more associated with a product separation system Export. In still further embodiments, wherein the regenerator comprises a regeneration section, one or more spent catalyst tubes, and one or more regenerated catalyst tubes, wherein preferably the used catalyst tubes and steam are used The riser is connected and the regenerated catalyst ramp is connected to the first and/or second riser reactor. In still further embodiments, wherein the product separation system separates C4 hydrocarbons, pyrolysis gasoline, and cracked heavy oil from oil and gas products from a first riser reactor and/or a fluidized bed reactor, and via cracking heavy oil The loop directs the cracked heavy oil to the one or more cracked heavy oil feed ports, and/or directs the cracked gasoline to the one or more light feedstock feeds via a pyrolysis gasoline loop, and/or C4 via a C4 hydrocarbon loop Hydrocarbon is introduced to the one or more light feedstock feed ports. In still further embodiments, wherein the cyclonic separation system is located at the top of the settler and is connected to the outlet of the settler for further separation of the hydrocarbon product and catalyst solid particles. According to the present invention, the catalytic cracking unit preferably employs a combination of a double riser and a fluidized bed, wherein one of the risers is coaxially connected in series with the fluidized bed, and is juxtaposed with the other riser, and the riser and fluidize The bed reaction coaxial series structure is further disposed coaxially with the stripper. In the coaxial series combination of the riser and the fluidized bed reaction, the riser outlet is preferably a low pressure outlet distributor having a pressure drop of less than 1 OKPa. Existing low pressure outlet distributors, such as arched distributors, can be used. According to the present invention, the riser reactor is selected from one or a combination of two of a constant diameter riser, an equal line speed riser and a variable diameter riser, wherein the first riser reactor and the second riser The reactors can be of the same type or of different types. The fluidized bed reactor is selected from the group consisting of a fixed fluidized bed, a fluidized bed, a bubbling bed, a turbulent bed, a fast bed, a transport bed, and a dense phase fluidized bed reactor. According to the present invention, the shape-selective zeolite having an average pore diameter of less than 0.7 nm is selected from the group consisting of ZSM series zeolites, ZRP zeolites, ferrierites, chabazite, cyclolite, erionite, A zeolite, column zeolite, turbidite, and One or more of the above-mentioned zeolites obtained by physical and/or chemical treatment. The ZSM series zeolite is selected from one of ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similarly structured zeolites or - more than one mixture. A more detailed description of ZSM-5 can be found in USP 3,702,886, and a more detailed description of ZRP can be found in USP 5,232,675. The catalyst of the shape-selective zeolite having an average pore diameter of less than 〇. 7 nm may be a combination of one or more of the catalysts provided by the prior art, and may be commercially available or prepared according to an existing method. The catalyst comprises zeolite, inorganic oxide and optionally clay, which comprises: 5 to 50% by weight of zeolite, 5 to 95% by weight of inorganic oxide, 0 to 70% by weight of clay. The zeolite comprises an average pore diameter smaller than 〇 7 nm shape-selective zeolite and optionally large-pore zeolite, the average pore diameter of less than 〇. 7 nm of the shape-selective zeolite accounts for 25 to 100% by weight of the active component, preferably 5 0 to 1 〇〇% by weight 'macroporous zeolite accounts for 〇~75 wt% of the active component, preferably 0 to 50 wt%. The large pore zeolite is a zeolite having a pore structure of at least 0.7 nm ring opening, and is selected from the group consisting of Y type zeolite, β type zeolite, L type zeolite, rare earth Y type zeolite (REY), rare earth hydroquinone type zeolite (REHY). One or a mixture of two or more of ultra-stable cerium type zeolite (USY) and rare earth ultra-stable cerium type zeolite (REUSY). The inorganic oxide is used as a binder and is selected from the group consisting of cerium oxide (SiO 2 ) and/or aluminum oxide (Al 2 〇 3 ). The clay acts as a substrate, ie a carrier, selected from the group consisting of kaolin and/or halloysite. In the catalytic cracking method provided by the present invention, the catalyst containing the shape-selective zeolite having an average pore diameter of less than 0.7 nm used in the second riser reactor may be the same as or different from the catalyst used in the first riser. Preferably, the first riser reactor and the second riser reactor use the same catalyst. The method provided by the present invention will be further described below with reference to the accompanying drawings: -22- 201217511 In the method shown in FIG. 1, the hot regenerated catalyst enters the riser reactor 1 through the regenerated catalyst inclined tubes 9 and 10, respectively. The bottom of 2 is accelerated upward by the pre-lifting medium injected by lines 22 and 23, respectively. The preheated heavy raw material is mixed with the atomized water vapor from the line 21 by a certain ratio through the line 20, and then injected into the riser reactor 1 to be reacted to obtain a first oil and gas product and a first carbon deposition catalyst, the first The oil and gas product and the first carbon deposit catalyst are separated by a quick-distribution device (not shown) at the end of the riser 1: the olefin-rich gasoline fraction and/or C4 hydrocarbons which are preheated or not preheated are connected via line 24 and The atomized water vapor from line 25 is mixed in a certain ratio, injected into the riser reactor 2, and flows upward along the riser 2 together with the catalyst, and contains a certain proportion of atomized water vapor introduced during the flow and through the line 36. The cracked heavy oil (preferably, self-produced) stream is contacted to obtain a second oil and gas product and a second carbonaceous catalyst, and the second hydrocarbon product and the second carbonaceous catalyst are passed through an outlet distributor of the riser 2 (not shown) The fluidized bed reactor 4 is further reacted to obtain a third oil and gas product and a third carbonaceous catalyst, and finally enters the settler 5 to separate the oil and gas products from the catalyst. The oil and gas products including the first oil and gas product and the third oil and gas product are led to a cyclone separation system (not shown) at the top of the settler to separate the solids such as the catalyst carried therein, and then introduced to the product separation system through the pipeline 30. . In the product separation system 6, the catalytic cracking product is separated into pyrolysis gas (extracted from line 3), pyrolysis gasoline (derived from line 32), cracked light cycle oil (derived from line 33), and cracked heavy oil (derived from line 34). And pyrolysis slurry (extracted by line 35). The cracked gas from line 31 is subjected to subsequent product separation and refining to obtain a polymer grade propylene product and an olefin-rich C 4 fraction, wherein -23-201217511 olefin-rich C4 fraction can be returned to the second riser reactor 2. The pyrolysis gasoline drawn from line 32 may be partially or completely returned to the second riser reactor 2; the gasoline may be first cut into light and heavy gasoline fractions, and the light gasoline fraction may be partially or completely returned to the second riser reactor 2, preferably The light gasoline is returned to the second riser reactor 2; the cracked heavy oil drawn from the line 34 can be returned to any reactor in the reaction system, preferably partially or completely cracked heavy oil is returned to the riser 2 or the fluidized bed via the line 36. More preferably, it is led to the riser 2 at a position after introduction of the olefin-rich gasoline fraction. The first carbon deposition catalyst separated by the quick-distribution device at the end of the riser 1 is led to the fluidized bed reactor 4, mixed with the catalyst at the outlet of the riser 2, and after the reaction, is led to the stripper 3. The stripping water vapor is injected through the line 37, and is in countercurrent contact with the carbon deposition catalyst, and the oil and gas product entrained by the carbon deposition catalyst is stripped as much as possible, and then introduced to the settler 5 through the fluidized bed reactor 3, together with other oil and gas products. It is led via line 30 to a subsequent product separation system. The stripped catalyst is sent to the regenerator 7 through the used catalyst tube 8 to be charred. The oxygen-containing gas such as air is injected into the regenerator 7 via line 26, and the regenerated flue gas is withdrawn via line 27. The regenerated catalyst was returned to the riser reactors 1 and 2 via the regenerated catalyst inclined tubes 9 and 10, respectively. In the above-described embodiment, the pre-lifting medium is introduced to the riser 1 and the riser 2 through lines 22 and 23, respectively. The pre-elevation medium is well known to those skilled in the art and may be selected from one or more of water vapor, C 1 to C 4 hydrocarbons or conventional catalytic cracking dry gas, preferably water vapor and/or olefin-rich C4 fraction. . The invention will be further illustrated by the following examples. -24- 201217511 The raw materials used in the examples and comparative examples include the raw material A, the raw material B, the raw material C, the raw material E and the raw material F, and the specific properties are shown in Table 1. The raw material A is a cracked heavy oil, the raw material B is an atmospheric heavy oil, and the raw material C is an olefin-rich cracked light gasoline. The raw material E and the raw material F are different side liquid products of the F-T device, wherein the raw material E and the raw material F correspond to light and heavy flows, respectively. The catalyst used was a Μ M C - 2 catalyst produced by Qilu Branch of Sinopec Catalyst. The specific properties are shown in Table 2. The catalyst contains a shape-selective zeolite having an average pore diameter of less than 〇. EXAMPLE 1 This example was carried out on a medium-sized plant having a mixture of olefin-rich pyrolysis light gasoline C and cracked heavy oil hydrazine (in a ratio of C: A = 1:1.5). The catalyst was MMC-2. In the continuous reaction-regeneration operation of the medium-sized unit, the riser has an inner diameter of 16 mm and a height of 32 00 mm, and the riser outlet is connected to the fluidized bed reactor. The fluidized bed reactor has an inner diameter of 64 mm and a height. 600 mm. All feeds enter the unit from the nozzle inlet at the bottom of the riser. This embodiment was carried out in a single pass operation without refining of the cracked heavy oil. The high temperature regenerated catalyst flows from the regenerator to the bottom of the riser reaction section via the regenerated catalyst inclined tube and flows upward under the action of the water vapor pre-lifting medium. After the preheating is mixed with the atomized water vapor, the feedstock oil enters the riser through the feed nozzle to contact the hot regenerated catalyst for catalytic conversion reaction. The reaction mixture goes up the riser through the riser outlet to the fluidized bed reaction connected to the riser, and the reaction mixture continues to rise. After the reaction, it enters the sedimentation-25-201217511, and then the gas-solid separation is carried out by the quick-distribution device set at the top of the settler. . The oil and gas products are separated into gas and liquid products by a pipeline, and the coke-containing catalyst (used catalyst) flows into the stripper by gravity, and the stripping steam vapor is used to adsorb the hydrocarbon product adsorbed on the used catalyst. Gas-solid separation is carried out through a fluidized bed into a settler. The used catalyst after stripping enters the regenerator through the used catalyst inclined tube and is contacted with air for high temperature scorch regeneration. The regenerated catalyst is recycled to the riser reactor via a regenerated catalyst ramp. The main operating conditions and results of this example are listed in Table 3. Comparative Example 1 In the present embodiment, the feedstock oil, the catalyst, and the feedstock oil were fed in the same manner as in Example 1. The difference is that the reactor is only a riser and there is no fluidized bed reactor. The riser reactor has an inner diameter of 16 mm and a height of 3800 mm. This example was also carried out in a single pass operation without refining of the cracked heavy oil. The high temperature regenerated catalyst passes through the regenerative catalyst inclined tube and enters the bottom of the riser reaction section through the regenerator, and flows upward under the action of the pre-lifting medium. After the preheating is mixed with the atomized water vapor, the feedstock oil is fed into the riser through the feed nozzle to contact the hot regenerated catalyst for catalytic conversion reaction. The reaction mixture travels up the riser through the riser outlet into the settler, whereupon the gas-solid separation is carried out through a quick-distribution device placed at the top of the settler. The oil and gas products are separated into gas and liquid products by a pipeline, and the coke-containing catalyst (used catalyst) flows into the stripper by gravity. -26- 201217511 The stripping steam is adsorbed on the used catalyst. The hydrocarbon product is then passed to a settler for gas-solid separation. The stripped spent catalyst is passed through a used catalyst tube into the regenerator and contacted with air for high temperature charring regeneration. The regenerated catalyst is reused in the riser reactor via the regenerated catalyst inclined tube. The operating conditions and results of this example are listed in Table 3. Example 2 This example was carried out on the medium-sized apparatus described in Example 1. The olefin-containing cracked light gasoline C and the cracked heavy oil A are injected in a ratio of 1:1, wherein the raw material C is injected into the riser from the raw material nozzle at the bottom of the riser, and the raw material A is injected into the riser from the raw material nozzle at the length 1/2 of the riser. Reacted. The main operating conditions and results of this example are listed in Table 4. Embodiment 3 This embodiment was carried out on the medium-sized apparatus described in Embodiment 1. The olefin-containing cracked light gasoline C and the cracked heavy oil A are injected in a ratio of 1:1.2, wherein the raw material C is injected into the riser from the raw material nozzle at the bottom of the riser, and the raw material A is injected into the riser from the raw material nozzle at the bottom of the fluidized bed to participate in the reaction. The main operating conditions and results of this example are listed in Table 4. Comparative Example 2 This example was carried out on the medium-sized apparatus described in Comparative Example 1. The olefin-rich cracked light gasoline C and cracked heavy oil A injection ratio is 1: 丨, where -27- 201217511 raw material C is injected into the riser from the raw material nozzle at the bottom of the riser, and the raw material A is from the original length of the riser 1/2 The nozzle is injected into the riser to participate in the reaction. The main operating conditions and results of this example are shown in Table 4. It can be seen from Table 4 that the raw material C in the third embodiment is injected into the riser from the raw material nozzle at the bottom of the riser and the feed material A is injected into the riser from the bottom of the fluidized bed to participate in the reaction, and the heavy oil is compared with Comparative Example 2. Under the condition that the degree of conversion is basically equivalent, the dry gas and coke yield can be significantly reduced (reduced by 1.73 and 0.68 percentage points, respectively), while the yields of propylene and butene are still increased by 1.15 and 0.28 percentage points respectively, and the dry gas selectivity index ( The ratio of dry gas yield to conversion ratio was 6.2, which was a decrease of 23.17% compared with the dry gas selectivity index of Comparative Example 2. Example 4 This embodiment was carried out on a medium-sized apparatus in which the first riser reactor had an inner diameter of 16 mm and a height of 3800 mm, and the second riser had an inner diameter of 16 mm and a height of 3200 mm. The tube outlet is connected to the fluidized bed reactor. The inner diameter of the fluidized bed reactor is 64 mm and the height is 600 mm. The configuration is as shown in Fig. 1. This embodiment uses the refining mode to operate. The tubes are led by the regenerator to the bottom of the first and second riser reaction sections, respectively, and flow upward under the action of the pre-lifting medium. After the feedstock oil B is preheated and mixed with the atomized water vapor, the first riser reactor 1 is injected into the first riser reactor 1 through the feed nozzle to contact the hot regenerated catalyst for catalytic conversion reaction, and the reaction mixture rises along the riser reactor 1 and passes through the riser. The quick separation device set at the outlet of the reactor 1 performs gas-solid separation, and the oil and gas products are led to the settler.

-28- 201217511, and then introduced to the product separation system to separate into gas and liquid products, wherein the light gasoline fraction is refining as the feed of the second riser reactor 2 'cracking heavy oil fraction refining as the fluidized bed reactor 3 The material continues to undergo catalytic conversion. The coke-containing catalyst (used catalyst) from the riser reactor 1 is first dropped into the fluidized bed reactor 3 by gravity and mixed with the catalyst and oil and gas products from the outlet of the riser reactor 2, and then enters the fluidized bed. In the same stripper, the stripping steam is used to adsorb the hydrocarbon product on the used catalyst, and then enters the settler through the fluidized bed for gas-solid separation. The used catalyst after stripping enters the regenerator through the used catalyst inclined tube and is contacted with air for high temperature scorch regeneration. The regenerated catalyst was returned to the two riser reactors via a regenerated catalyst ramp to reuse. Light gasoline and atomized water vapor from the product separation system are injected through the bottom nozzle of the riser reactor 2, and the cracked heavy oil is mixed with the atomized water vapor and introduced through the bottom nozzle of the fluidized bed reactor 3 to contact with the high temperature catalyst. The reaction, the oil and gas product enters the settler through the fluidized bed, and is separated from the oil and gas product of the riser reactor 1 by a cyclone separation system at the top of the settler; the oil and gas product is taken out of the reactor through the pipeline and enters the product separation system, the catalyst Introduced to a fluidized bed reactor. The coke-containing catalyst in the fluidized bed reactor (used catalyst, including catalyst from the first riser reactor and the second riser reactor) is led to a stripper, and the used catalyst after stripping is passed The used catalyst inclined tube enters the regenerator, and is contacted with air for high-temperature scorch regeneration, and then used. The main operating conditions and results of this example are shown in Table 5. The properties of some of the liquid products are shown in Table 6. -29-201217511 Example 5 This example was carried out in the same apparatus as in Example 4. In addition to the adjustment of the operating conditions, in addition to the adjustment of the operating conditions, the reductive conversion of the CM fraction was increased, i.e., the C4 fraction from the separation system participating in the refining process entered the preheating tube of the riser reactor 2 in contact with the catalyst. The main operating conditions and results of this example are listed in Table 7, and the properties of some of the liquid products are shown in Table 8. From the results of Tables 5, 6, 7, and 8, the method proposed by the present invention can be found to have the characteristics of low dry gas yield and high propylene yield, and at the same time, pyrolysis gasoline having a high aromatic content can be produced, which can be extracted as an aromatic hydrocarbon. raw material. The properties of the cracking light cycle oil (which has a hexadecane enthalpy of 22) also have a corresponding improvement to some extent and can be used as a fuel oil component. Example 6 This example was carried out in the same apparatus as in Example 4. In comparison with Example 4, in addition to adjusting the operating conditions, the feed was changed to the raw material E and the raw material F, wherein the ratio of the raw material E to the raw material F was 1:1. This embodiment operates only in the cracked heavy oil refining mode. The high-temperature regenerated catalyst is introduced from the regenerated catalyst to the bottom of the first and second riser reaction sections through the regenerated catalyst inclined tube, and flows upward under the action of the pre-lifting medium. After the preheating and the atomized water vapor are mixed, the feedstock oil F is injected into the first riser reactor 1 through the feed nozzle to contact the hot regenerated catalyst to carry out a catalytic conversion reaction, and the reaction mixture rises along the riser reactor 1 and passes through the riser. The quick separation device provided at the outlet of the reactor 1 performs gas-solid separation, and the oil and gas product is led to a settler, and then introduced to a product separation system to separate into gas and liquid products, wherein the cracked heavy oil fraction is rectified as a fluidized bed -30-201217511 reactor The feed of 3 continues to catalyze the conversion. The coke-containing catalyst (used catalyst) from the riser reactor 1 is firstly dropped by gravity into the fluidized bed reactor 3 and mixed with the catalyst and oil and gas products from the outlet of the riser reactor 2, and then enters the fluidized bed. In the same stripper, the stripping steam is used to adsorb the hydrocarbon product on the used catalyst, and then enters the settler through the fluidized bed for gas-solid separation. The stripped used catalyst enters the regenerator through the used catalyst tube and is exposed to air for high temperature scorch regeneration. The regenerated catalyst was returned to the two riser reactors via a regenerated catalyst inclined tube for reuse. The raw material E and the atomized water vapor are sprayed through the bottom nozzle of the riser reactor 2, and the cracked heavy oil is mixed with the atomized water vapor and introduced through the bottom nozzle of the fluidized bed reactor 3, and reacted with the high temperature catalyst, and the oil and gas product passes through the fluidized bed. Entering the settler, the gas-solid separation is carried out together with the oil and gas products to the riser reactor 1 at the cyclone separation system at the top of the settler; the oil and gas products are led out of the reactor through the pipeline and then enter the product separation system, and the catalyst is led to the fluidized bed reactor. The coke-containing catalyst in the fluidized bed reactor (used catalyst, including catalyst from the first riser reactor and the second riser reactor) is led to a stripper, and the used catalyst after stripping is passed The used catalyst inclined tube enters the regenerator and is heated in contact with air for high-temperature scorch regeneration. The main operating conditions and results of this example are listed in Table 9. -31 - 201217511 Table 1 Name Raw Material A Raw Material B Raw Material C Raw Material E Raw Material F Density / (g/cm3) 1.0186 0.8950 0.6696 0.7562 0.8850 Refractive Index (η/) 1.5835 1.4888 / Kinematic Viscosity / (mm2/s) 80°C 22.46 34.92 / loot: 10.89 20.09 / Freezing point A: 16 48 / W (carbon residue) /% 1.61 6.05 / Elemental composition w(C/H)/% 89.40/9.40 86.34/13.10 85.18/14.44 83.31/13.43 86.37/12.22 w (S/N)/% 1.00/0.25 0.32/.24 0.015/0.001 / 0.0011/ <0.0005 Group composition w (saturated hydrocarbon hydrocarbon) /% 32.3/65.6 57.1/20.2 / / w (colloid / asphaltene) / % 2.1/0.0 22.5/0.2 / / Metal content / (pg / g) Ni / V 0.20 / 0.29 18.30 / 0.27 / / < 0.1 / 0.3 Wide range C initial boiling point 274 278 32 42 202 5% 380 362 39 66 280 10% 403 393 40 78 305 30% 427 447 44 107 354 50% 443 503 48 140 402 70% 464 539 (57.8) 53 174 463 90% 506 65 238 540 95% 534 69 267 -32- 201217511 Table 2 Catalyst Name MMC-2 Chemical Properties, Weight % Al2〇3 49.2 Na2〇0.072 RE2〇3 0.61 Physical Properties Total Pore Volume, ml/g 0.208 Micropore Volume, ml/g 0.024 Specific Surface , m2/g 155 molecular sieve specific surface, m2/g 50 matrix specific surface, m2/g 105 bulk density, g/ml 0.72 particle size distribution, φ% 0 〜20μηι 1.6 0 〜40μιη 14.2 0 〜80μηι 53.8 0~1 ΙΟμΓη 72.6 0 ～149μιη 89.5 Lysis activity, wt% 66 -33- 201217511 Case---^ 1 Shen A no mouth - raw material name reaction pressure, MPa (a) one όΙΓ ^ one raw material ---- Π 11 ' --- - Regeneration temperature, °C ~ 7nn Reactor structure riser and flow enthalpy reactor / uu Individual riser reactor riser length, mm 3200 3800~ Fluidized bed reactor height, mm 600 / reaction temperature, °C 520 520 — Light gasoline and cracked heavy oil injection method Mixed injection Mixed injection Light gasoline injection position Lifting pipe bottom Lifting pipe bottom Cracking heavy oil injection position Lifting pipe bottom Lifting pipe bottom Light gasoline and cracking heavy oil injection ratio 1:1.5 1:1.5 Total atomized water Vapor ratio, weight% 13 13 total oil ratio, (weight ratio) 8 8 light gasoline reaction conditions light gasoline oil to oil ratio, (weight ratio) 20.0 20.0 light gasoline riser reaction time, s 0.91 1.19 Light gasoline total reaction time, S 1.16 1.19 Light gasoline injection steam ratio, weight% 10.00 10.00 Cracking heavy oil reaction conditions cracking heavy oil to oil ratio, (weight ratio) 13.3 13.3 cracking heavy oil riser reaction time, S 0.91 1.19 cracking heavy oil Total reaction time, S 1.16 1.19 Pyrolysis heavy oil atomized water vapor ratio, weight % 15 15 Bed temperature, °C 520 / Bed space velocity, h·1 10 / Catalyst type MMC-2 MMC-2 Material balance, wt% H2-C2 3.20 2.50 C3-C4 27.59 22.56 C5+ pyrolysis gasoline 35.88 37.36 Cracking light cycle oil 14.09 12.08 Cracking heavy oil 12.74 19.71 Coke 6.50 5.79 Total 100.00 100.00 Light hydrocarbon yield, wt% Ethylene 1.78 1.34 Propylene 14.05 10.36 Total butene 12.77 9.99 - 34- 201217511 Table 4 Case Implementation^> Raw Material Name Raw Material A~~ ---- Raw Material A and Reaction Pressure, MPa(a) Regeneration Temperature, 700~0.21 700 Reactor Structure 700 fee riser and fluidized bed combination reaction単 提升 提升 提升 提升 反应 反应 菅 菅 菅 菅 菅 菅 菅 and fluidized bed combination reactor riser length, mm 3200 3800 3200 flow _ Boring bed reactor height, mm 600 / 600 Μ Μ temperature, °C 560 560 545 Light gasoline and cracked electric oil injection method separately injected separately injection separately injected light gasoline injection position riser bottom bottom riser bottom riser bottom cracking heavy oil injection position The length of the riser is 1/2, the length of the riser is 1/2, and the ratio of light gasoline and cracked heavy oil at the bottom of the fluidized bed is 1:1 1:1 1:1.2 Total atomization water vapor ratio 重量, weight% 15 15 14.5 Total oil Ratio, ί 雷量比) 12 12 11.3 Light gasoline reaction i condition light gasoline oil to oil ratio, (respective ratio) 24.0 24.0 24.9 Light gasoline riser reaction time, s 0.40 0.54 0.71 light gasoline total reaction time, S 0.87 0.92 0.94 Light gasoline atomization steam ratio, weight% 20.00 20.00 20.00 Cracking heavy oil reaction conditions Contact cracking heavy oil pre-catalyst coke amount, storage volume % 0.15 0.15 0.12 cracking heavy oil ratio oil, ί weight ratio) 24.0 24.0 20.7 cracking heavy oil riser reaction Time, S 0.40 0.54 / total reaction time of cracking heavy oil, S 0.60 0.54 0.23 ratio of cracked heavy oil atomized water vapor, weight% 10 10 10 Bed temperature, °C 560 / 545 Bed space velocity, h·1 7 / 8 Catalyst type MMC-2 MMC-2 MMC-2 Material balance, wt% Hz-C2 6.50 6.23 4.50 C3-C4 36.17 33.00 32.00 C5+ cracking Gasoline 29.52 31.50 30.30 Cracking light cycle oil 10.45 7.43 11.50 Cracking heavy oil 10.98 15.95 16.50 Coke 6.38 5.88 5.20 Total 100.00 100.00 100.00 Conversion rate, W% 78.57 76.62 72.00 One dry gas yield “〇〇Taction rate 8.27 8.13 6.25 Carcinogenic hydrocarbon production, Thunder amount % Ethylene 3.73 3.45 2.58 Propylene 18.10 14.86 16.01 Total butene 13.54 11.70 11.98 -35- 201217511 Table 5 Case example 4 Raw material name Raw material B Reaction pressure, MPa (a) 0.21 Regeneration temperature, °c 700 First riser reaction Riser outlet temperature, °C 530 oil and gas reaction time, s 3 agent to oil ratio, (weight ratio) 9.7 atomized water vapor ratio (for fresh feed), weight % 8 second riser and fluidized bed combined reactor Riser outlet temperature, °C 540 bed temperature, t 530 bed WHSV, h'1 10 light gasoline refining ratio (for fresh feed), weight % 12 refining light gasoline end Distillation point, °c 85 Light gasoline injection position The ratio of light gasoline to fuel oil at the bottom of the riser, (weight ratio) 15 Light gasoline riser reaction time, s 0.6 Light gasoline total reaction time, s 1.8 Light gasoline atomized water vapor ratio, Weight % 15 Cracked heavy oil refining ratio (for fresh feed), weight % 20 cracking heavy oil injection position Fluidized bed bottom cracking heavy oil reaction time, S 1.2 Cracking heavy oil atomized water vapor ratio, weight % 10 Catalyst type MMC-2 material Equilibrium, wt% H2-C2 5.32 C3-C4 34.72 C5+ pyrolysis gasoline 31.28 Cracking light cycle oil 13.31 Cracking heavy oil 5.73 Coke 9.64 Total 100.00 Light hydrocarbon yield (for fresh feed), wt% Ethylene 2.81 Propylene 16.41 Isobutene 5.48 Table 5 The fresh feed is a heavy feedstock that is directed to the first riser reaction.

-36- 201217511 Table 6 Logistics Name Pyrolysis Gasoline Cracking Light Cycle Oil Density (2〇°C)/(g/cm3) 0.75 0.91 Movement Viscosity (20°C), mm2/S / 5.2 Octane値 / RON 97 / MON 82 / hexadecane 値 / 30 hydrocarbon group composition / weight % / alkane 27 / olefin 35 / aromatics 38 / distillation range, ° C / initial boiling point 44 / 10% 85 / 30% 121 / 50% 134 / 70% 146 / 90% 172 / Final boiling point 200 / -37- 201217511 Table 7 Case Example 5 Raw material name Raw material B Reaction pressure, MPa (a) 0.21 Regeneration temperature, °C 700 First riser reactor riser outlet temperature, ° C 550 oil and gas reaction time, s 2.5 agent to oil ratio, (weight ratio) 12.4 atomized water vapor ratio (for fresh feed), weight % 15 second riser and fluidized bed combined reactor riser outlet temperature, °C 560 bed temperature, °C 548 bed WHSV, h-1 5 C4 hydrocarbon refining ratio (for fresh feed), weight % 8 C4 hydrocarbon injection position riser pre-lift section C4 hydrocarbons oil to oil ratio, (weight ratio 29 C4 hydrocarbon riser reaction time, s 0.78 C4 hydrocarbon total reaction time, s 1.78 C4 hydrocarbon atomization water vapor ratio For example, weight % 10 light gasoline back to dry ratio (for fresh feed), weight % 10 refining light gasoline final boiling point, °c 85 light gasoline injection position to raise the ratio of light gasoline to the bottom of the lift pipe, (weight ratio) 23 Light gasoline riser reaction time, s 0.55 light gasoline total reaction time, s 1.55 light gasoline atomized water vapor ratio, weight % 15 cracked heavy oil refining ratio (for fresh feed), weight % 10 cracking heavy oil injection position fluidized bed Bottom cracking heavy oil reaction time, s 1.0 cracking heavy oil atomized water vapor ratio, weight% 10 catalyst type MMC-2 material balance, weight % H2-C2 8.15 C3-C4 44.93 C5+ pyrolysis gasoline 21.86 cracking light cycle oil 10.84 cracking heavy oil 4.39 coke 9.83 Total 100.00 Light hydrocarbon yield (for fresh feed), wt% ethylene 3.81 Propylene 23.38 isobutylene 4.25 The fresh feed described in Table 7 is the heavy feed to the first riser reaction. -38- 201217511 Table 8 Logistics Name Pyrolysis Gasoline Cracking Light Cycle Oil Density (20 °C) / (g / cm3) 0.82 0.92 Movement Viscosity (2 ° ° C), mm2 / s 6 Octane 値 / RON 100 / MON 85 / Hexadecane 22 Hydrocarbon composition/% by weight / Alkane 12.1 / Alkene 13.2 / Aromatic 74.7 / Distillation range, °C / Initial boiling point 40 / 10% 88 / 30% 125 / 50% 140 / 70% 150 / 90 % 180 / final boiling point 202 / -39 - 201217511 Table 9 Case Example 6 Raw material name Raw material E and raw material F Reaction pressure, MPa (a) 0.21 Regeneration temperature, t 700 First riser reactor feed stream raw material F upgrade Tube outlet temperature, t 580 oil and gas reaction time, s 3 agent oil ratio, w/w 9.7 injection water vapor ratio (for raw material F), weight % 8 second riser and fluidized bed combined reactor fresh feed logistics material E Refining logistics cracking heavy oil riser outlet temperature, °c 600 bed temperature, °c 580 bed WHSV, h_1 10 raw material E injection position riser bottom material E oil to oil ratio, weight / weight 15 raw material E riser reaction time , s 0.6 total reaction time of raw material E, s 1.8 steamed water Proportion, wt% 15 cracking heavy oil refining ratio (for raw material F), weight % 5 cracking heavy oil injection position, fluidized bed bottom cracking heavy oil reaction time, s 1.2 injection steam ratio (for cracking heavy oil), weight % 10 catalyst type MMC -2 Material balance (to the sum of raw material E and raw material F), wt% C02 & C0 1.41 Hz-C2 13.56 C3-C4 45.82 C5+ pyrolysis gasoline 23.10 cracking light cycle oil 7.23 cracking heavy oil 0.70 generating water 1.48 coke 6.70 total 100.00 light hydrocarbon production Rate (to the sum of raw material E and raw material F), w % ethylene 7.52 propylene 23.44 isobutylene 6.01 -40- 201217511 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic flow chart of a catalytic cracking method according to the present invention [Signature of main components] 1 2 is a riser reactor, 3 is a stripper, 4 is a fluidized bed reactor, 5 is a settler, 6 is a product separation system, 7 is a regenerator, 8 is a used catalyst inclined tube, 9, 10 In order to regenerate the catalyst inclined tube, the riser 2 and the fluidized bed 4 are coaxially connected in series through the settler 5 and the riser 1 to be juxtaposed, and simultaneously connected to the stripper 3 at high and low coaxial .

Claims (1)

201217511 VII. Patent application scope: 1. A catalytic cracking method comprising: contacting a heavy raw material and optionally atomized water vapor with a catalyst containing a shape-selective zeolite having an average pore size of 0.7 nm in a first riser Obtaining a first hydrocarbon product and a first carbon deposition catalyst, wherein the first oil and gas product is separated from the first carbon catalyst by a first extraction device, and the light raw material and optionally atomized water vapor are led to the second The lifter is contacted with a shape-selective zeolite agent having an average pore diameter of less than 〇·7 nm to obtain a second oil and gas product and a second carbon deposition catalyst, and the gas product and the second carbon catalyst are led to react with the second riser In a fluidized bed reactor, the reaction is carried out in the presence of a catalyst containing an optional zeolite having an average pore diameter of less than 0.7 nm, and at the same time, the cracking heavy oil prepared by the method is preferably transferred to the second riser counter/ Or a fluidized bed reactor, preferably to a fluidized bed reactor, for obtaining a stream comprising a third hydrocarbon product and a third soot from a fluidized bed reactor. 2. The catalytic cracking process of claim 1, wherein the heavy feedstock comprises a heavy hydrocarbon and/or a hydrocarbon-rich plant or plant, wherein the light feedstock comprises a gasoline fraction and/or a C4 hydrocarbon; The cracked heavy oil is a cracked heavy oil with a normal pressure range of 3 3 0 to 5 50 °C. 3. The catalytic cracking method according to claim 1, wherein the first oil and gas product is separated by a product separation system to obtain pyrolysis cracked gasoline, light recoil oil, and a fluid droplet having a smaller crack diameter than the reactor. The second tube of the tube end reaction is catalyzed by a tandem shape oil selection, a comparator and a reaction; the oil in the catalyst; the gas further comprising a desulfurized oil - 42 - 201217511 : and / or wherein the third The oil and gas products are separated by a product separation system to obtain cracking gas, pyrolysis gasoline, cracking light cycle oil and cracking heavy oil. 4. The catalytic cracking method according to claim 1, wherein the first riser reactor atomized water vapor accounts for 2 to 50% by weight of the feed amount, preferably 5 to 10% by weight, and the reaction pressure is 0.15. 〜0.3MPa, preferably 0.2~0.2 5 MPa; wherein the reaction temperature of the first riser reactor is 480~600 °C, preferably 500~560 °C, and the ratio of agent to oil is 5~20, preferably Ground 7~15, the reaction time is 5. 5 0~1 leap seconds, preferably 2~4 seconds. 5. The catalytic cracking method according to claim 1, wherein the second riser reactor has a reaction temperature of 520 to 580 ° C, preferably 520 to 560 ° C; and the second riser reactor introduces light When the raw material comprises a gasoline fraction, the ratio of atomized water vapor of the gasoline raw material is 5 to 30% by weight, preferably 1 to 20% by weight: when the light raw material includes a gasoline fraction, the gasoline fraction is in the second lift The ratio of the ratio of the agent to the oil in the tube is 10 to 30, preferably 15 to 25, and the reaction time is 〇.1 〇~1. 5 seconds, preferably 0.30 to 0.8 seconds; when the light raw material includes C 4 hydrocarbon, The C 4 hydrocarbon atomized water vapor ratio is 10 to 40% by weight, preferably 15 to 25% by weight, and when the light raw material includes C4 hydrocarbon, the C4 hydrocarbon is operated in the second riser The ratio is 12 to 40, preferably 17 to 30, and the reaction time is 〇·5 0 to 2.0 seconds, preferably 〇·8 to 1.5 seconds. 6. The catalytic cracking method according to claim 1, wherein the fluidized bed reactor has a reaction temperature of 500 to 580 ° C. Preferably, 510 to 560 ° C, and a WHSV of 1 to 3 5 hours _ 1, Preferably, it is 3 to 30 hours·1; and the reaction pressure of the fluidized bed reactor is 0.15 to 〇3 MPa, preferably 0.2 to 0.25 MPa. 7. The catalytic cracking method according to claim 1, wherein the reaction condition of the cracked-43-201217511 heavy oil in the fluidized bed comprises: the ratio of the cracked heavy oil to the catalyst is from 1 to 50, preferably 5~40; the split heavy oil has a WHSV of 1 to 20 hours-1, preferably 3 to 15 hours-1 in the fluidized bed; the ratio of atomized water vapor of the cracked heavy oil is 5 to 20% by weight, preferably 10~ 15% by weight. 8. The catalytic cracking process of claim 1, wherein the weight of the cracked heavy oil introduced to the second riser reactor and/or the fluidized bed reactor and the heavy feedstock introduced to the first riser reactor is 8. The ratio is 〇.〇5~0.30:1 〇9. The catalytic cracking method according to claim 1, wherein when the light raw material comprises a gasoline fraction, the gasoline fraction introduced to the second riser reactor The weight ratio of the heavy raw material introduced to the first riser reactor is 0.05 to 0.20:1; when the light raw material includes the gasoline fraction and the C4 hydrocarbon, the C4 hydrocarbon in the light raw material and the light raw material The weight ratio of the gasoline fraction is 0 to 2: 1. 10. The catalytic cracking method according to claim 2, wherein the gasoline raw material is an olefin-rich gasoline fraction having an olefin content of 20 to 9.5 wt% and a final boiling point of not more than 8 5 ° C; the C 4 hydrocarbon light feedstock is an olefin-rich C4 hydrocarbon having a C4 olefin content of greater than 50% by weight. 11. The catalytic cracking process of claim 3, wherein the gasoline fraction light feedstock comprises pyrolysis gasoline separated by the product separation system. 12. The catalytic cracking process of claim 3, further comprising the step of: mixing the first hydrocarbon product and the third hydrocarbon product into a product separation system for separation. -44- 201217511 13. As in the catalytic cracking of claim 1, the first carbon deposition catalyst is first introduced to the catalyst of the fluidized bed reactor, and then introduced to the stripper, or the catalyst is directly Lead to the stripper. 14. The catalytic cracking of claim 1, wherein the first carbonaceous catalyst and/or the third carbonaceous gas is stripped and the stripping water vapor entrained with the hydrocarbon product is directed to the reactor. 15. A catalytic cracking unit comprising: a first riser reactor for cracking a heavy feedstock; a first riser reactor having a feedstock inlet at the bottom of the riser for cracking light feedstock Two riser reactor ^ The second riser reactor has a raw material feed port at the bottom of the riser and a discharge port at the top of the riser, a fluidized bed reactor (4), which has many fluidized bed reactors a feed port and the fluidized bed reactor is connected to the outlet of the first reactor via a connection low pressure outlet distributor, more preferably, an arched distributor, and a separation device disposed at the end of the first riser The quick separation device, the separation charge port and the catalyst discharge port, wherein the second riser reactor and/or the stream further have the one or more light feedstock feeds Above the mouth method, which further comprises, in combination with the fluidized bed, a first carbon deposition method, which further comprises a water vaporized bed reaction (1), said mass or mass: 2), said or more Lightweight with one or two pieces (preferably two The riser is counter-ground, the quick-distribution device comprises one or more -45 - 201217511 cracked heavy oil feed ports of the oil-gas bed reactor. Preferably, the cracked heavy oil enters one-half of the length of the second riser reactor More preferably, the cracked heavy oil feed port is at the bottom of the reactor, and optionally the 'product separation system (6), the product cracking heavy oil from the first lift The tube reactor and/or the fluidized oil and gas product are separated and passed through a cracking heavy oil circuit (1 〇 heavy oil is introduced to the one or more cracked heavy oil feed ports. 16. The catalytic cracking device as claimed in claim 15 The chemical cracking unit further comprises: a stripper (3), a settler (5 off system (6), a regenerator (7) and a cyclone separation system: the stripper has an inlet for stripping water vapor, and an outlet for the vapor And an outlet for the stripping water vapor entrained with the oil and gas; wherein the settler is outlet of the fluidized bed reactor and having one or more inlets for receiving the reaction oil and gas and a product separation system: wherein the regeneration Regeneration Stage, one or more stont catalyst inclined tubes and one or more regenerations, wherein preferably used catalyst inclined tubes and stripper phase catalyst inclined tubes react with the first and / or second riser tubes The product separation system wherein the product separation system separates the C4 hydrocarbons, pyrolysis gasoline oil from the first riser reactor and/or the fluidized bed reactant, and the cracked heavy oil or the plurality of cracked heavy oil feed ports via the cracking heavy oil circuit And / or through the pyrolysis gasoline feed port in the two riser out of the fluidized bed anti-separation system, the op reactor of the bed reactor will be cracked, the catalyst, the product is extracted from the catalytic material port, Or a plurality of oil and gas production lines connected to the used catalyst, and the regeneration and the cracker are introduced to the one circuit to direct the cracking -46-201217511 gasoline to the one or more light material feed ports, And/or by introducing a C4 hydrocarbon to the one or more light feedstock feed ports in a hydrocarbon loop; wherein the cyclonic separation system is disposed at the top of the settler and connected to the outlet of the settler for further separation of the oil and gas And the catalyst solids. The catalytic cracking apparatus of claim 15, wherein the first riser reactor is selected from the group consisting of an equal diameter riser, an equal line riser or a variable diameter riser reactor; The second riser reactor is selected from the group consisting of a constant diameter riser, a constant line riser or a variable diameter riser reactor; the fluidized bed reactor is selected from the group consisting of a fixed fluidized bed, a bulk fluidized bed, and a bubbling bed. , turbulent bed, fast bed 'conveying bed and dense-phase fluidized bed reactor. -47-