CN110317630B - Catalyst zoned catalytic cracking method and device - Google Patents
Catalyst zoned catalytic cracking method and device Download PDFInfo
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- CN110317630B CN110317630B CN201910308601.1A CN201910308601A CN110317630B CN 110317630 B CN110317630 B CN 110317630B CN 201910308601 A CN201910308601 A CN 201910308601A CN 110317630 B CN110317630 B CN 110317630B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/182—Regeneration
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/187—Controlling or regulating
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a catalyst zoned catalytic cracking method and a device thereof. The device comprises a main reactor (3), a secondary reactor (11), a regenerator (14), an A catalyst cyclone separator (19) and a B catalyst storage tank (22), a B catalyst primary separator (20) is arranged above the inner part of a B catalyst storage tank (22), a regenerator (14) is respectively connected with a main reactor (3) and the A catalyst primary separator (19) through pipelines, the top of the A catalyst primary separator (19) is connected with the B catalyst primary separator (20) through a pipeline, the bottom of the A catalyst primary separator (19) is connected with the regenerator (14) through a pipeline, the top of the B catalyst primary separator (20) is connected with the regenerator (14) through a pipeline, the bottom of the B catalyst primary separator (20) is provided with an opening communicated with a cavity in the B catalyst storage tank (22), and the bottom of the B catalyst storage tank (22) is connected with a secondary reactor (11) through a pipeline.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a catalyst partition catalytic cracking method and a catalyst partition catalytic cracking device.
Background
The catalytic cracking process is a core process in oil refining technology, is not only a main means for processing heavy oil and a main source for producing light oil components, but also has an irreplaceable position in the aspect of providing light olefin and petrochemical integrated technology.
Catalytic cracking is a typical parallel sequential reaction, and comprises a first reaction and a second reaction, wherein the first reaction mainly comprises a cracking reaction of heavy components to generate light hydrocarbons and olefin products, and the second reaction mainly comprises a cracking reaction of the light hydrocarbons and a further reaction of the olefins, such as continuous cracking of gasoline and diesel fractions, and a hydrogen transfer reaction, an isomerization reaction, an alkylation reaction and the like of the olefins. Researches find that the process conditions and the catalyst properties required by the primary reaction and the secondary reaction in the catalytic cracking have large differences. Thermodynamic results show that the cracking of heavy oil with large molecules only needs lower activation energy, while the cracking of smaller molecules (gasoline) needs higher activation energy, so that the primary cracking of heavy oil needs lower temperature, and the secondary cracking of primary cracking products such as gasoline needs higher temperature, and meanwhile, the secondary reaction needs longer reaction time. In order to meet different requirements of the primary reaction and the secondary reaction on reaction temperature and reaction time, a catalytic cracking zone control process technology has been developed, and different reaction zones are arranged to control the temperature and the reaction time of the different reaction zones so as to meet different thermodynamic characteristics of the primary reaction and the secondary reaction. Such as the DCC-plus process. The DCC-plus process adopts a form of a riser reactor and a fluidized bed reactor, and uses the riser reactor and the fluidized bed reactor to be connected in series to realize different requirements of a primary reaction and a secondary reaction on reaction time. The results show that the riser reactor and the fluidized bed reactor are used in series and the regenerated catalyst is supplemented to the fluidized bed reactor, so that the retention time of oil gas in different reaction zones can be changed, the cracking of heavy oil is increased, the yield of low-carbon olefin is improved, the property of gasoline is improved, the outlet temperature of the riser and the mixing temperature of oil at the inlet of the riser are reduced, and the yield of dry gas and coke can be obviously reduced.
CN201610917106.7 discloses a catalytic cracking method for producing low carbon olefins and light aromatic hydrocarbons, in which a heavy raw material contacts a first portion of catalytic cracking catalyst in a first reactor (riser reactor i) to perform a reaction, and a light raw material rich in saturated hydrocarbons and a light raw material rich in olefins contact a second portion of catalytic cracking catalyst in a second reactor (riser reactor ii) and a third reactor (fluidized bed reactor) to perform a reaction, so as to increase the production of low carbon olefins and light aromatic hydrocarbons. The method is provided with three reactors which are equivalent to three reaction zones, so that the zoned cracking conversion of the raw materials is realized, but the same catalyst is used, and although the regenerated catalysts are used in the first reactor and the second reactor, different catalysts are not matched according to the conversion property difference of the raw materials, the zoned catalyst is not realized, and the raw materials, the catalysts and the process conditions can not be highly matched. CN98101765.7 discloses a method for simultaneously preparing low-carbon olefin and high-aromatic gasoline, which comprises contacting heavy petroleum hydrocarbon and steam with zeolite-containing catalyst at the lower part of a composite reactor composed of a riser and a dense-phase fluidized bed, and contacting light petroleum hydrocarbon entering the upper part of the composite reactor, namely the bottom of the dense-phase fluidized bed, with zeolite-containing catalyst from the riser. The method is provided with two reaction zones, realizes the zone cracking conversion of the raw materials, but uses a catalyst, the catalyst in the second reaction zone (dense-phase fluidized bed) is the catalyst from the first reaction zone (riser reactor), the zone separation of the catalyst is not realized, and the catalyst activity, the catalyst and the raw material conversion performance can not be highly matched.
In addition, catalytic cracking is a monomolecular endothermic reaction that occurs at strong acid sites, while hydrogen transfer reactions are bimolecular exothermic reactions that occur at weak acid sites and require higher acid density. Isomerization is a monomolecular exotherm that occurs at the stronger acid sites. Moreover, the isomerization performance of the catalyst varies with the pore size, and for example, the isomerization performance of the zeolite gradually decreases as the pore size of the zeolite decreases. After the Y molecular sieve is modified by rare earth or phosphorus, the isomerization performance of the Y molecular sieve is enhanced. Cracking of heavy oil macromolecules requires a larger catalyst pore size, while cracking of light oil macromolecules requires a smaller catalyst pore size. It is difficult to achieve the above properties simultaneously for the same catalyst, and this is often a concern. In order to make up for the defect that the same catalyst cannot give consideration to multiple performances, the current method is to use two catalysts, such as a mixture of USY and ZSM series catalysts, and to enhance the secondary reaction of small molecules by adding the ZSM series catalysts so as to increase the yield of low-carbon olefins. CN200410006189.1 discloses a chemical oil refining method for producing light olefins and aromatics, in which the catalytic cracking catalyst is a mixture of a medium-pore ZSM series catalyst and a large-pore Y series catalyst, and has the problem that the primary cracking and condensation reaction of heavy oil can also occur on the surface of the ZSM series catalyst, so that the surface of the ZSM series catalyst and the entrance of the pore channel are covered with coke, which prevents small molecules from entering the pore channel of the ZSM series catalyst to continue the reaction, and seriously reduces the catalytic activity of the ZSM series, resulting in less secondary reaction of light oil on the ZSM series catalyst.
Disclosure of Invention
In order to solve the problems, the invention provides a catalytic cracking method and a catalytic cracking device with catalyst zones, which use two catalysts with different properties to meet the requirement that the same catalyst cannot give consideration to multiple performances. Meanwhile, the two regenerated catalysts are separated and enriched through a catalyst primary separator, then the two catalysts are conveyed to different reaction zones, different raw materials are matched in each reaction zone, and different process conditions are matched according to thermodynamic properties, so that the catalysts, the raw materials and the process conditions are highly matched, the catalytic performance of each catalyst is enhanced, and the catalytic performance of the catalysts is fully exerted. The influence of one catalyst on the other catalyst when the catalysts are mixed for use is avoided.
An object of the present invention is to provide a catalyst zone catalytic cracking apparatus;
it is another object of the present invention to provide a process for catalytic zone catalytic cracking.
In order to achieve the above objects, in one aspect, the present invention provides a catalyst-zoned catalytic cracking apparatus, wherein the apparatus comprises a main reactor 3 for heavy feedstock oil catalytic cracking reaction, a secondary reactor 11 for light feedstock oil catalytic cracking reaction, a regenerator 14, an a catalyst cyclone separator 19 and a B catalyst storage tank 22, a B catalyst cyclone separator 20 is disposed above the inside of the B catalyst storage tank 22, the regenerator 14 is connected with the main reactor 3 and the a catalyst cyclone separator 19 through pipes, respectively, the top of the a catalyst cyclone separator 19 is connected with the B catalyst cyclone separator 20 through a pipe, and the bottom thereof is connected with the regenerator 14 through a pipe, the top of the B catalyst cyclone separator 20 is connected with the regenerator 14 through a pipe, the bottom of the B catalyst cyclone separator 20 is provided with an opening communicated with the cavity inside the B catalyst storage tank 22, the bottom of the B catalyst storage tank 22 is connected with the secondary reactor 11 through a pipeline.
According to some embodiments of the invention, the primary reactor and the secondary reactor are in the form of one or more of a riser reactor, a transport bed reactor, a riser plus fast bed reactor, a turbulent bed plus fast bed reactor, respectively.
The primary catalyst separator is a cyclone separator for primary catalyst separation, and the cyclone separator is a known product and is a common separation device in the chemical field.
According to some embodiments of the present invention, the primary A catalyst separator is a cyclone separator capable of separating 50-100 wt% of the A catalyst, and the air inlet of the primary A catalyst separator is opened at an upper or middle position. One skilled in the art can select a suitable size of primary separator based on the separation criteria described herein.
Wherein the parameters of the catalyst A are as follows: the bulk density of the catalyst is 0.8-1.5g/cm3Preferably 0.9 to 1.2g/cm3(ii) a The average particle size is 80-140 μm, preferably 90-120 μm; particle size distribution: the particles with the particle diameter larger than 80 mu m account for 60 to 100wt percent of the total weight of the catalyst A, and preferably account for 80 to 100wt percent
According to some embodiments of the invention, the primary B catalyst separator is a cyclone separator capable of separating 50-100 wt% of the B catalyst, and the air inlet of the primary B catalyst separator is opened at the upper or middle position.
Wherein the parameters of the catalyst B are as follows: the bulk density of the catalyst is 0.4-0.7g/cm3Preferably 0.5 to 0.65g/cm3(ii) a The average particle size is 20-80 μm, preferably 40-60 μm; particle size distribution: the particles with the particle diameter of 30-50 mu m account for 60-100 wt% of the total weight of the catalyst B, and preferably 80-100 wt%.
According to some embodiments of the present invention, the regenerator 14 is connected to the bottom of a regenerated catalyst standpipe 18 through a first regeneration inclined tube 16, and the top of the regenerated catalyst standpipe 18 is connected to an a catalyst cyclone 19; the bottom of the A catalyst primary separator 19 is connected with the regenerator 14 through an A catalyst conveying pipe 21; the bottom of the B catalyst storage tank 22 is connected with the secondary reactor 11 through a second regeneration inclined pipe 24; the regenerator 14 is connected to the main reactor 3 by a third regeneration ramp 25.
According to some embodiments of the present invention, the primary reactor 3 and the secondary reactor 11 are riser reactors; the top of the main reactor 3 is connected with the bottom of the stripper 4 and penetrates through the stripper 4 to enter the settler 5, the top of the stripper 4 is connected with the bottom of the settler 5, and the top of the secondary reactor 11 is connected with the settler 5; the bottom of the main reactor 3 is connected with the regenerator 14 through a third regeneration inclined tube 25; the bottom of the secondary reactor 11 is connected with the bottom of a B catalyst storage tank 22 through a second regeneration inclined pipe 24; the lower end of the stripper 4 is connected with the lower end of a regenerator 14 through a to-be-regenerated inclined pipe 13.
According to some embodiments of the invention, a primary separator 12 is arranged in the settler 5, and the top of the secondary reactor 11 is connected with the primary separator 12.
According to some embodiments of the present invention, a second primary separator 6 connected to the main reactor 3 is further disposed in the settler 5, and a secondary cyclone 7 is disposed at the top of the settler 5, wherein the top of the secondary cyclone 7 passes through the top of the settler 5 to communicate with the outside.
According to some embodiments of the present invention, a cyclone 27 is provided at an upper portion of the regenerator 14, and the top of the cyclone 27 is connected to the outside through the top of the regenerator 14 by a pipe.
The catalytic cracking reaction device is additionally provided with a set of catalyst primary cyclone separation system on the original DCC-plus device, the catalyst primary cyclone separation system is used for separating and enriching A, B catalyst, and divides A, B catalyst into a main reactor and a secondary reactor, and matches with raw materials with larger cracking property difference, the primary cyclone separation system is composed of two cyclone separation or coarse cyclone or cyclone heads which are connected in series, and simultaneously comprises a catalyst B storage tank and a catalyst conveying pipe.
In another aspect, the present invention also provides a catalyst-zoned catalytic cracking method, wherein the method comprises using two different catalysts in the catalytic cracking reaction of petroleum hydrocarbon, including using a catalyst in the catalytic cracking reaction of heavy raw oil and using B catalyst in the catalytic cracking reaction of light raw oil.
According to some embodiments of the invention, wherein the bulk density of the A catalyst is from 0.8 to 1.5g/cm3Average particle diameter of 80 to 140 μm, particle size distribution: the particles with the particle diameter larger than 80 mu m account for 60-100 wt% of the total weight of the catalyst A.
According to some embodiments of the invention, wherein the bulk density of the A catalyst is from 0.9 to 1.2g/cm3。
According to some embodiments of the invention, wherein the A catalyst has an average particle size of 90 to 120. mu.m.
According to some embodiments of the invention, wherein a catalyst particle size distribution: the particles with the particle diameter larger than 80 mu m account for 80-100 wt% of the total weight of the catalyst A. According to some embodiments of the invention, wherein the B catalyst has a bulk density of 0.4 to 0.7g/cm3Average particle diameter of 20 to 80 μm, particle size distribution: the particles with the particle diameter of 30-50 mu m account for 60-100 wt% of the total weight of the catalyst B.
According to some embodiments of the invention, wherein the B catalyst has a bulk density of 0.5 to 0.65g/cm3。
According to some embodiments of the invention, wherein the B catalyst has an average particle size of 40 to 60 μm.
The catalyst A has high heavy raw material cracking performance and high matrix cracking activity; the catalyst B has high olefin selectivity, low hydrogen transfer activity and strong secondary conversion capability of light oil.
The catalyst A used in the present invention may be any catalyst suitable for the catalytic cracking process of heavy raw oil.
According to some embodiments of the invention, the catalyst a comprises the following components in weight percent: 15-40% of natural mineral substances, 10-35% of ZSM-5 molecular sieve or modified ZSM-5 molecular sieve and 50-75% of Y-type molecular sieve.
The natural mineral is selected from at least one of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite. The Y-type molecular sieve is selected from at least one of DASY molecular sieve, DASY molecular sieve containing rare earth, USY molecular sieve containing rare earth, REY molecular sieve, REHY molecular sieve and HY molecular sieve.
The catalyst B used in the present invention may be any catalyst suitable for the catalytic cracking of light raw oil.
According to some embodiments of the invention, the catalyst B comprises the following components in weight percent: 15-40% of natural mineral substances, 50-75% of ZSM-5 molecular sieve or modified ZSM-5 molecular sieve and 10-35% of Y-type molecular sieve.
The natural mineral is selected from at least one of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite. The Y-type molecular sieve is selected from at least one of DASY molecular sieve, DASY molecular sieve containing rare earth, USY molecular sieve containing rare earth, REY molecular sieve, REHY molecular sieve and HY molecular sieve.
According to some embodiments of the invention, wherein B catalyst particle size distribution: the particles with the particle diameter of 30-50 mu m account for 80-100 wt% of the total weight of the catalyst B.
According to some embodiments of the present invention, the method further comprises regenerating the deactivated catalyst after the reaction, and subjecting the regenerated catalyst to two times of separation and enrichment to obtain a regenerated a catalyst rich in a catalyst and a regenerated B catalyst rich in B catalyst, respectively, and then transporting the regenerated a catalyst for the heavy raw oil catalytic cracking reaction and the regenerated B catalyst for the light raw oil catalytic cracking reaction.
According to some embodiments of the present invention, the weight ratio of the catalyst a and the catalyst B in the regenerated catalyst a delivered for the heavy feed oil catalytic cracking reaction is 7: 3 to 9: 1; the weight ratio of the catalyst B to the catalyst A in the regenerated catalyst B conveyed for the catalytic cracking reaction of the light raw oil is 7: 3 to 9: 1.
according to some embodiments of the present invention, wherein the weight ratio of the catalyst a to the catalyst B in the regenerated catalyst a delivered for the heavy feed oil catalytic cracking reaction is 8: 2.
according to some embodiments of the present invention, wherein the weight ratio of the catalyst B to the catalyst a in the regenerated catalyst B to be fed for the light feed oil catalytic cracking reaction is 8: 2.
according to some embodiments of the present invention, wherein, in the reaction system for catalytic cracking of petroleum hydrocarbon, the weight ratio of the A catalyst to the B catalyst is 6: 4 to 9: 1.
according to some embodiments of the present invention, wherein, in the reaction system for catalytic cracking of petroleum hydrocarbon, the weight ratio of the A catalyst to the B catalyst is 7: 3 to 8: 2.
according to some embodiments of the invention, the light feed oil comprises a mixture of one or more of a hydrocarbon fraction enriched in one or more of C4, C5, C6, a gasoline fraction, and a diesel fraction; the heavy raw oil comprises one or more of petroleum hydrocarbon, oil sand asphalt, mineral oil, synthetic oil, animal oil and fat and vegetable oil and fat.
The gasoline and diesel oil fractions can be part of gasoline and diesel oil fractions obtained from reaction, or one or more of catalytic cracking, thermal cracking, coking gasoline, diesel oil fractions, straight-run gasoline and diesel oil fractions.
The invention realizes hydrocarbon zone conversion by the catalyst zone, enriches mixed catalysts with different properties and then conveys the mixed catalysts to different reaction zones, simultaneously matches different raw materials, improves the matching degree of the catalyst and the raw materials, makes up the defect that the same catalyst can not give consideration to the raw materials with various properties, greatly improves the efficiency of the catalyst, can directionally control the hydrocarbon conversion (such as cracking, aromatization, isomerization, superposition and other reactions) and improves the selectivity of target products. In addition, the occurrence of side reactions can be greatly reduced by adjusting the process parameters. For example, in the main reactor, the reaction temperature is lowered to moderately crack the heavy raw material, and in the secondary reactor, the reaction temperature is raised to fully react the light raw material, so as to reduce the yield of dry gas and coke.
According to some embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of the heavy feed oil comprise: preheating heavy raw oil at 160-350 ℃, reacting at 460-550 ℃, carrying out a catalyst-oil ratio of 4-12, carrying out a catalyst micro-reaction at 50-70, reacting for 1.0-7.0 s, and carrying out a reaction at 0.1-0.4 MPa; the reaction conditions of the catalytic cracking reaction of the light raw oil comprise: the preheating temperature of the light raw oil is 40-200 ℃, the reaction temperature is 460-600 ℃, the catalyst-oil ratio is 4-15, the micro-reaction activity of the catalyst is 50-80, the reaction time is 0.3-7 s, and the reaction pressure is 0.1-0.4 MPa.
According to some embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of the heavy feed oil comprise: the preheating temperature of the heavy raw oil is 180-280 ℃.
According to some embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of the heavy feed oil comprise: the reaction temperature is 490-530 ℃.
According to some embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of the heavy feed oil comprise: the agent-oil ratio is 6-9.
According to some embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of the heavy feed oil comprise: the micro-activity of the catalyst is 58-65.
According to some embodiments of the present invention, the reaction conditions for the catalytic cracking reaction of the heavy feed oil comprise: the reaction time is 1.5-4.5 s.
According to some embodiments of the present invention, the reaction conditions for the light raw oil catalytic cracking reaction include: the preheating temperature of the light raw oil is 60-150 ℃.
According to some embodiments of the present invention, the reaction conditions for the light raw oil catalytic cracking reaction include: the reaction temperature is 500-580 ℃.
According to some embodiments of the present invention, the reaction conditions for the light raw oil catalytic cracking reaction include: the agent-oil ratio is 6-9.
According to some embodiments of the present invention, the reaction conditions for the light raw oil catalytic cracking reaction include: the micro-reaction activity of the catalyst is 60-75.
According to some embodiments of the present invention, the reaction conditions for the light raw oil catalytic cracking reaction include: the reaction time is 1-6 s.
According to some embodiments of the invention, the method comprises performing a catalytic cracking reaction using the apparatus of any of the preceding claims.
According to some embodiments of the invention, wherein the A catalyst primary separator defines an inlet gas velocity of 6 to 12 m/s; the gas velocity at the inlet of the primary catalyst separator B is limited to be 12-22 m/s, and the gas velocity at the inlet of the primary catalyst separator B is 6-10 m/s higher than that at the inlet of the primary catalyst separator A.
According to some embodiments of the present invention, the method comprises leading the regenerated catalyst mixture (mixture of a catalyst and B catalyst) from the regenerator through a first regeneration inclined tube, passing through a regenerated catalyst riser, then passing through an a catalyst cyclone separator, separating and enriching the heavy catalyst a with larger particles, and sending the heavy catalyst a back to the regenerator through an a catalyst conveying pipe, wherein the regenerated a catalyst rich in the a catalyst is conveyed to the bottom end of the main reactor through a third regeneration inclined tube to react with the heavy raw material; the unseparated catalyst mixture rich in the B catalyst is separated and enriched by the B catalyst primary separator to obtain a regenerated B catalyst rich in the B catalyst, and the regenerated B catalyst is collected in a B catalyst storage tank and then conveyed to the bottom of a secondary reactor through a second regeneration inclined pipe to react with the light raw material.
According to some embodiments of the invention, the overflowed gas is separated by the cyclone separator and discharged together with the flue gas.
In conclusion, the invention provides a method and a device for catalytic cracking of a catalyst by zones. The method of the invention has the following advantages:
the process has the technical advantages that two catalysts are used in a directional matching mode according to the properties and production purposes of the raw materials, A, B catalysts are respectively enriched after regeneration and are conveyed to different reactors to be in contact reaction with the raw materials with different properties, and the high directional matching of the catalysts and the raw materials is realized through the catalyst partition and the partitioned raw materials. According to the characteristics of catalytic reactions in different zones, the optimized process conditions are matched, high matching among the catalyst, the raw materials and the process conditions is realized, so that the directional conversion efficiency of the raw materials and the directional catalytic efficiency of the catalyst are improved, the catalytic cracking capability is enhanced, the catalytic performance of each catalyst is enhanced, and the catalytic performance of the catalyst is fully exerted. The influence of one catalyst on the other catalyst is avoided when the catalysts are mixed for use, the generation of byproducts is reduced, and the yield of target products is improved.
Drawings
FIG. 1 is a schematic view of an apparatus of example 1 of the present invention.
Detailed Description
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is not intended to limit the scope of the present disclosure.
The device connection relationship of the embodiments is shown in fig. 1.
The method is that a first regeneration inclined pipe 16 is connected with a regenerated catalyst vertical pipe 18 outside a regenerator 14 of a conventional double-riser catalytic cracking device, the regenerated catalyst vertical pipe 18 is connected with a catalyst primary separator A19, the lower end of the catalyst primary separator A19 is connected with the regenerator 14 through a catalyst conveying pipe A21, the upper end of the catalyst primary separator A19 is connected with a catalyst primary separator B20, the catalyst primary separator B20 is arranged in a catalyst storage tank B22, the upper part of the catalyst primary separator B20 is connected with the upper part of the regenerator 14, and the lower part of the catalyst storage tank B22 is connected with a secondary reactor 11 through a second regeneration inclined pipe 24.
The technological process includes feeding preheated heavy material oil 1 from the lower part of the main reactor 3, reacting with regenerated catalyst A from the regenerator 14 rich in catalyst A while raising in the raising action of the pre-raising steam 2, separating oil from gas in the primary separator 6, raising oil and gas in the secondary cyclone separator 7 to obtain oil gas 8, and cooling and separating oil gas 8 in the cooling and separating system. The cyclone separated catalyst is stripped by stripping steam 9 in the stripping section 4 and then conveyed to a regenerator 14 for regeneration through a spent inclined tube 13.
The preheated light raw oil 10 is introduced into the lower part of a secondary reactor 11 and reacts with a regenerated catalyst B rich in catalyst B from a catalyst B storage tank 22 in the secondary reactor 11, oil gas and deactivated catalyst are primarily separated in a primary separator 12 after the reaction, the oil gas is obtained after the separation in a secondary cyclone separator 7 and discharged, the deactivated catalyst enters a stripping section 4 through a settler 5, and is conveyed to a regenerator 14 for regeneration through a to-be-regenerated inclined tube 13 after being stripped by stripping steam 9.
The deactivated catalyst entering the regenerator 14 is regenerated under the action of the regenerated air 15, the regenerated catalyst is led out of the regenerator 14 through a first regeneration inclined tube 16, is lifted into an A catalyst primary separator 19 under the action of a regenerated catalyst vertical tube 18 and a lifting air 17, the A catalyst is enriched in the A catalyst primary separator 19, the enriched regenerated A catalyst enters the regenerator 14 through an A catalyst conveying tube 21, and is led into the bottom of the main reactor 3 through a third regeneration inclined tube 25 to be in contact reaction with the heavy raw oil. The catalyst which is not separated by the A catalyst primary separator 19 enters the B catalyst primary separator 20, so that the B catalyst is enriched to obtain a regenerated B catalyst which is rich in the B catalyst and is stored in a B catalyst storage tank 22, the regenerated B catalyst is introduced into the bottom of the secondary reactor 11 through a second regeneration inclined pipe 24 to be in contact reaction with the light raw oil under the action of the loosening air 23, and the overflowing gas 26 at the top of the B catalyst primary separator enters a regenerator.
The properties of the heavy feed oil are shown in table 1, and the light feed oil is a gasoline fraction produced by primary cracking of the heavy feed oil and C4 hydrocarbons.
Table 1 heavy feedstock properties
| Item | Data of | Item | Data of |
| Density (20 ℃ C.) kg/m3 | 914 | Nitrogen content, wt% | 0.02 |
| Carbon residue in wt% | 0.24 | Analysis of hydrocarbon group composition | |
| Elemental analysis | Saturated hydrocarbon, wt.% | 69.8 | |
| Hydrogen content, wt.% | 12.57 | Aromatic hydrocarbons, wt.% | 23.7 |
| Carbon content, wt% | 86.67 | Gum, wt% | 6.1 |
| Sulfur content, wt.% | 0.33 | Asphaltenes, wt.% | <0.4 |
Example 1
The main reactor is a riser reactor, and the secondary reactor is a riser plus a bed reactor. A. The properties of the catalyst B are shown in table 2, delivered to the main reactor catalyst composition: 70 wt% A +30 wt% B, delivered to the secondary reactor catalyst composition: 70 wt% B +30 wt% A, the main process conditions are as follows
The reaction results are shown in Table 3 and Table 4.
TABLE 2 catalyst Properties
TABLE 3 Main Process conditions
| Preheating temperature of heavy raw material, DEG C | 240 | Preheating temperature of light raw material, DEG C | 100 |
| Main reactor reaction temperature, deg.C | 500 | Reaction temperature in the secondary reactor, DEG C | 540 |
| Main reactor's ratio of catalyst to oil | 7 | Ratio of catalyst to oil in secondary reactor | 6 |
| Main reactor reaction time, s | 7 | Secondary reactor reaction time, s | 4 |
| Main reactor reaction pressure, MPa | 0.3 | Secondary reactor reaction pressure, MPa | 0.3 |
| Micro-reaction activity of catalyst | A：50B：60 | Regeneration temperature of | 680 |
TABLE 4 product distribution
| Example 1 | Comparative example (DCC-plus process) | |
| Yield of product, wt.% | ||
| Dry gas | 6.24 | 7.54 |
| Liquefied gas | 40.26 | 40.16 |
| C5+ gasoline | 33.21 | 30.17 |
| Diesel oil | 11.14 | 11.25 |
| Oil slurry | 2.83 | 3.07 |
| Coke | 5.76 | 7.23 |
| Conversion in wt.% | 85.47 | 85.68 |
| Total olefin yield, wt% | 36.12 | 33.76 |
| Ethylene | 4.55 | 3.86 |
| Propylene (PA) | 17.83 | 17.16 |
| Butene (butylene) | 13.74 | 12.74 |
Example 2
The main reactor is a riser reactor, and the secondary reactor is a riser plus a bed reactor. A. The properties of the B catalyst are shown in table 5, delivered to the main reactor catalyst composition: 80 wt% A +20 wt% B, delivered to the secondary reactor catalyst composition: 80 wt% B +20 wt% A, the main process conditions are shown in Table 6, and the reaction results are shown in Table 7.
TABLE 5 catalyst Properties
TABLE 6 Main Process conditions
| Preheating temperature of heavy raw oil, DEG C | 240 | Preheating temperature of light raw oil, DEG C | 100 |
| Main reactor reaction temperature, deg.C | 515 | Reaction temperature in the secondary reactor, DEG C | 560 |
| Main reactor's ratio of catalyst to |
8 | Ratio of catalyst to oil in secondary reactor | 7 |
| Main reactor reaction time, |
8 | Secondary reactor reaction time, |
5 |
| Main reactor reaction pressure, MPa | 0.3 | Secondary reactor reaction pressure, MPa | 0.3 |
| Micro-reaction activity of catalyst | A：60B：70 | Regeneration temperature of | 680 |
TABLE 7 product distribution
| Example 2 | Comparative example (DCC-plus process) | |
| Yield of product, wt.% | ||
| Dry gas | 5.44 | 7.54 |
| Liquefied gas | 41.67 | 40.16 |
| C5+ gasoline | 34.18 | 30.17 |
| Diesel oil | 9.37 | 11.25 |
| Oil slurry | 2.06 | 3.07 |
| Coke | 6.41 | 7.23 |
| Conversion in wt.% | 87.70 | 85.68 |
| Total olefin yield, wt% | 39.59 | 33.76 |
| Ethylene | 5.88 | 3.86 |
| Propylene (PA) | 19.23 | 17.16 |
| Butene (butylene) | 14.48 | 12.74 |
Example 3
The main reactor is a riser reactor, and the secondary reactor is a riser plus a bed reactor. A. The properties of the B catalyst are shown in table 8, delivered to the main reactor catalyst composition: 90 wt% A +10 wt% B, delivered to the secondary reactor catalyst composition: 90 wt% B +10 wt% A, the main process conditions are shown in Table 9, and the reaction results are shown in Table 10.
TABLE 8 catalyst Properties
TABLE 9 Main Process conditions
| Preheating temperature of heavy raw material, DEG C | 240 | Preheating temperature of light raw material, DEG C | 100 |
| Reaction temperature of main reactorDegree, degree C | 530 | Reaction temperature in the secondary reactor, DEG C | 580 |
| Main reactor's ratio of catalyst to |
9 | Ratio of catalyst to oil in |
8 |
| Main reactor reaction time, |
9 | Secondary reactor reaction time, s | 6 |
| Main reactor reaction pressure, MPa | 0.3 | Secondary reactor reaction pressure, MPa | 0.3 |
| Micro-reaction activity of catalyst | A：70B：75 | Regeneration temperature of | 680 |
TABLE 10 product distribution
| Example 3 | Comparative example (DCC-plus process) | |
| Yield of product, wt.% | ||
| Dry gas | 5.24 | 7.54 |
| Liquefied gas | 41.26 | 40.16 |
| C5+ gasoline | 34.46 | 30.17 |
| Diesel oil | 10.14 | 11.25 |
| Oil slurry | 2.68 | 3.07 |
| Coke | 5.37 | 7.23 |
| Conversion in wt.% | 86.33 | 85.68 |
| Total olefin yield, wt% | 38.46 | 33.76 |
| Ethylene | 5.49 | 3.86 |
| Propylene (PA) | 18.23 | 17.16 |
| Butene (butylene) | 14.74 | 12.74 |
The data in the table show that by adopting the catalytic cracking process and the device of the present patent catalyst zone, the yield of the target product is obviously improved, such as the yield of low carbon olefin is improved by 2.36 wt% -5.83 wt%, and the yield of the by-product is obviously reduced, such as the yield of dry gas and coke is respectively reduced by 1.30 wt% -2.30 wt% and 0.82 wt% -1.86 wt%.
Claims (18)
1. A catalyst zoning catalytic cracking device, wherein the device comprises a main reactor (3) for heavy raw oil catalytic cracking reaction, a secondary reactor (11) for light raw oil catalytic cracking reaction, a regenerator (14), an A catalyst cyclone separator (19) and a B catalyst storage tank (22), the B catalyst cyclone separator (20) is arranged above the inner part of the B catalyst storage tank (22), the regenerator (14) is respectively connected with the main reactor (3) and the A catalyst cyclone separator (19) through pipelines, the top of the A catalyst cyclone separator (19) is connected with the B catalyst cyclone separator (20) through a pipeline, the bottom of the A catalyst cyclone separator (19) is connected with the regenerator (14) through a pipeline, the top of the B catalyst cyclone separator (20) is connected with the regenerator (14) through a pipeline, the bottom of the B catalyst cyclone separator (20) is provided with an opening communicated with a cavity in the B catalyst storage tank (22), the bottom of the catalyst storage tank (22) is connected with the secondary reactor (11) through a pipeline; the regenerator (14) is connected with the bottom of a regenerated catalyst vertical pipe (18) through a first regenerated inclined pipe (16), and the top of the regenerated catalyst vertical pipe (18) is connected with a catalyst A cyclone separator (19); the bottom of the A catalyst primary separator (19) is connected with the regenerator (14) through an A catalyst conveying pipe (21); the bottom of the catalyst storage tank (22) B is connected with the secondary reactor (11) through a second regeneration inclined tube (24); the regenerator (14) is connected to the main reactor (3) via a third regeneration inclined tube (25).
2. The apparatus according to claim 1, wherein the primary reactor (3) and the secondary reactor (11) are in the form of one or more of a riser reactor, a transport bed reactor, a riser + fast bed reactor, a turbulent bed + fast bed reactor, respectively, each independently.
3. The apparatus according to claim 1, wherein the A catalyst primary separator (19) is a cyclone separator capable of separating 50-100 wt% of A catalyst, and the air inlet of the A catalyst primary separator is opened at an upper or middle position; the catalyst B primary separator (20) is a cyclone separator capable of separating 50-100 wt% of the catalyst B, and an air inlet of the cyclone separator is arranged above or in the middle.
4. The apparatus according to claim 1, wherein the primary reactor (3) and the secondary reactor (11) are each a riser reactor; the top of the main reactor (3) is connected with the bottom of the stripper (4) and penetrates through the stripper (4) to enter the settler (5), the top of the stripper (4) is connected with the bottom of the settler (5), and the top of the secondary reactor (11) is connected with the settler (5); the bottom of the main reactor (3) is connected with a regenerator (14) through a third regeneration inclined tube (25); the bottom of the secondary reactor (11) is connected with the bottom of the B catalyst storage tank (22) through a second regeneration inclined pipe (24); the lower end of the stripper (4) is connected with the lower end of the regenerator (14) through a to-be-regenerated inclined pipe (13).
5. The apparatus according to claim 4, wherein a first primary separator (12) is arranged in the settler (5), and the top of the secondary reactor (11) is connected with the first primary separator (12).
6. The device according to claim 5, wherein a second primary separator (6) connected with the main reactor (3) is arranged in the settler (5), and a secondary cyclone separator (7) is arranged at the top of the settler (5), and the top of the secondary cyclone separator (7) passes through the top of the settler (5) to be communicated with the outside.
7. The apparatus as claimed in claim 5, wherein a cyclone (27) is provided in the upper part of the regenerator (14), and the top of the cyclone (27) is connected to the outside through the top of the regenerator (14) by a pipe.
8. A catalyst partition catalytic cracking method, wherein the method comprises the step of carrying out catalytic cracking reaction by using the catalyst partition catalytic cracking device of any one of claims 1 to 7, wherein two different catalysts are used in the catalytic cracking reaction of petroleum hydrocarbon, the catalyst A is used in the catalytic cracking reaction of heavy raw oil, and the catalyst B is used in the catalytic cracking reaction of light raw oil; the bulk density of the A catalyst is 0.8-1.5g/cm3(ii) a The average grain diameter is 80-140 mu m; particle size distribution: the particles with the particle size larger than 80 mu m account for 60-100 wt% of the total weight of the catalyst A; the bulk density of the catalyst B is 0.4-0.7g/cm3(ii) a The average grain diameter is 20-80 μm; particle size distribution: the particles with the particle diameter of 30-50 mu m account for 60-100 wt% of the total weight of the catalyst B.
9. The process of claim 8, wherein the bulk density of the A catalyst is from 0.9 to 1.2g/cm3(ii) a The average grain diameter is 90-120 mu m; catalyst particle size distribution: the particles with the particle size larger than 80 mu m account for 80-100 wt% of the total weight of the catalyst A; the bulk density of the catalyst B is 0.5-0.65g/cm3(ii) a The average grain diameter is 40-60 μm; particle size distribution: the particles with the particle diameter of 30-50 mu m account for 80-100 wt% of the total weight of the catalyst B.
10. The method according to claim 8, wherein the method further comprises regenerating the deactivated catalyst after the reaction, and subjecting the regenerated catalyst to two times of separation and enrichment to obtain a regenerated A catalyst rich in the A catalyst and a regenerated B catalyst rich in the B catalyst, respectively, and then conveying the regenerated A catalyst for the heavy raw oil catalytic cracking reaction and the regenerated B catalyst for the light raw oil catalytic cracking reaction.
11. The process according to claim 10, wherein the weight ratio of the A catalyst to the B catalyst in the regenerated A catalyst delivered for the heavy feed oil catalytic cracking reaction is 7: 3 to 9: 1; the weight ratio of the catalyst B to the catalyst A in the regenerated catalyst B conveyed for the catalytic cracking reaction of the light raw oil is 7: 3 to 9: 1.
12. the process according to claim 11, wherein the weight ratio of the A catalyst to the B catalyst in the regenerated A catalyst delivered for the heavy feed oil catalytic cracking reaction is 8: 2; the weight ratio of the catalyst B to the catalyst A in the regenerated catalyst B conveyed for the catalytic cracking reaction of the light raw oil is 8: 2.
13. the method of any one of claims 8 to 12, wherein the weight ratio of the A catalyst to the B catalyst in the petroleum hydrocarbon catalytic cracking reaction system is 6: 4 to 9: 1.
14. the method of claim 13, wherein the weight ratio of the a catalyst to the B catalyst in the petroleum hydrocarbon catalytic cracking reaction system is 7: 3 to 8: 2.
15. the method of any one of claims 8 to 12, wherein the light raw oil comprises a mixture of one or more of hydrocarbon fractions rich in one or more of C4, C5, C6, gasoline fractions, and diesel fractions; the heavy raw oil comprises one or more of petroleum hydrocarbon, oil sand asphalt, mineral oil, synthetic oil, animal oil and fat and vegetable oil and fat.
16. The method according to any one of claims 8 to 12, wherein the reaction conditions of the catalytic cracking reaction of the heavy raw oil comprise: preheating the heavy raw oil at 160-350 ℃; the reaction temperature is 460-550 ℃; the agent-oil ratio is 4-12; the micro-reaction activity of the catalyst is 50-70; the reaction time is 1.0-7.0 s; the reaction pressure is 0.1-0.4 MPa; the reaction conditions of the catalytic cracking reaction of the light raw oil comprise: the preheating temperature of the light raw oil is 40-200 ℃; the reaction temperature is 460-600 ℃; the agent-oil ratio is 4-15; the micro-reaction activity of the catalyst is 50-80; the reaction time is 0.3-7 s; the reaction pressure is 0.1-0.4 MPa.
17. The process according to claim 16, wherein the reaction conditions for the catalytic cracking reaction of the heavy feed oil comprise: preheating the heavy raw oil at 180-280 ℃; the reaction temperature is 490-530 ℃; the agent-oil ratio is 6-9; the micro-inverse activity of the catalyst is 58-65; the reaction time is 1.5-4.5 s; the reaction conditions of the catalytic cracking reaction of the light raw oil comprise: the preheating temperature of the light raw oil is 60-150 ℃; the reaction temperature is 500-580 ℃; the agent-oil ratio is 6-9; the micro-reaction activity of the catalyst is 60-75; the reaction time is 1-6 s.
18. The process of any one of claims 8 to 12, wherein the a catalyst primary separator defines an inlet gas velocity of 6 to 12 m/s; the gas velocity at the inlet of the primary catalyst separator B is limited to be 12-22 m/s, and the gas velocity at the inlet of the primary catalyst separator B is 6-10 m/s higher than that at the inlet of the primary catalyst separator A.
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| US4755282A (en) * | 1987-07-22 | 1988-07-05 | Shell Oil Company | Process for the reduction of NH3 in regeneration zone off gas by select recycle of certain-sized NH3 decomposition catalysts |
| US6248297B1 (en) * | 1988-08-26 | 2001-06-19 | Uop Llc | FCC reactor arrangement for sequential disengagement and progressive temperature reduction |
| CN102690679A (en) * | 2011-03-25 | 2012-09-26 | 中国石油化工股份有限公司 | Catalytic cracking method for producing propylene |
| CN104419457A (en) * | 2013-09-09 | 2015-03-18 | 中石化洛阳工程有限公司 | Catalytic cracking method and device employing double lift pipes |
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| US4755282A (en) * | 1987-07-22 | 1988-07-05 | Shell Oil Company | Process for the reduction of NH3 in regeneration zone off gas by select recycle of certain-sized NH3 decomposition catalysts |
| US6248297B1 (en) * | 1988-08-26 | 2001-06-19 | Uop Llc | FCC reactor arrangement for sequential disengagement and progressive temperature reduction |
| CN102690679A (en) * | 2011-03-25 | 2012-09-26 | 中国石油化工股份有限公司 | Catalytic cracking method for producing propylene |
| CN104419457A (en) * | 2013-09-09 | 2015-03-18 | 中石化洛阳工程有限公司 | Catalytic cracking method and device employing double lift pipes |
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