CN114262624B - Method and device for catalytic cracking of double-component granular catalyst coupling fluidized bed - Google Patents
Method and device for catalytic cracking of double-component granular catalyst coupling fluidized bed Download PDFInfo
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Abstract
The invention relates to the field of petrochemical industry, in particular to a method and equipment for catalytic cracking of a double-component particle coupling fluidized bed. In view of the great difference of the physical properties of the two catalysts, the invention provides a fluidized bed-riser reactor, wherein the lower part of the fluidized bed-riser reactor is mainly a catalytic cracking fluidized bed reactor of a large-particle-size catalyst, the upper part of the fluidized bed-riser reactor is mainly a catalytic cracking riser reactor of a small-particle-size catalyst, most of the small-particle-size catalyst and a small amount of large-particle-size catalyst after reaction enter a regenerator together from a spent catalyst inclined tube for coke burning regeneration, and the heat complementation of the two catalysts is realized. After the two regenerated catalysts return to the fluidized bed reactor from the regenerator inclined tube, most of the small-particle-size catalysts flow upwards and enter the riser reactor to participate in cracking reaction, and most of the large-particle-size catalysts enter the bed layer of the fluidized bed reactor to perform catalytic cracking reaction.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a method for coupling catalytic cracking of heavy hydrocarbon and fluidized catalytic reaction of light hydrocarbon in a fluidized bed-riser reactor by utilizing different physical properties of two catalysts with large differences.
Background
The heavy oil catalytic cracking is a process for producing gasoline, diesel and liquefied gas by high-temperature cracking of atmospheric residue in the presence of a catalyst. Because the catalytic cracking raw material is gradually heavy in the catalytic cracking reaction process of the heavy oil, the coke formation amount in the catalytic cracking process of the heavy oil is continuously increased, and an external heat collector is often required to be arranged beside a regenerator of the catalytic cracking raw material to meet the heat balance of a catalytic cracking reaction regeneration system, so that the equipment cost for the catalytic cracking production of the heavy oil is increased.
Light hydrocarbon catalytic cracking refers to a process of cracking petroleum hydrocarbons at high temperature in the presence of a catalyst to produce low-carbon olefins such as ethylene, propylene and butylene, and simultaneously produce light aromatics. The hydrogen content in the light hydrocarbon catalytic cracking raw material is higher, so that the yield of coke is less than 1 wt%, which is far less than 4.5 wt% of the average coke formation amount of heavy oil catalytic cracking, and the coke formation amount of catalytic cracking is difficult to maintain the heat balance of a self reaction-regeneration system, and additional heat is required to be supplemented, so that the energy consumption cost of light hydrocarbon catalytic cracking production is increased.
Based on the heat balance problem existing in the heavy oil catalytic cracking reaction and the light hydrocarbon catalytic cracking reaction, if the two reactions can be coupled, the heat compensation can be realized, the production cost can be greatly reduced, and the production benefit can be improved.
However, because the requirements of the heavy oil catalytic cracking reaction and the light hydrocarbon catalytic cracking reaction on the activity, the selectivity and the reaction conditions of the catalyst are different greatly, although the prior art provides a coupling process of catalytic cracking and catalytic cracking, the conversion rate of the heavy oil catalytic cracking and the yield of the light hydrocarbon catalytic cracking cannot be considered by adopting a single catalyst system. For example, patent application nos. CN01808100.2 and CN01808224.6 propose that raw oil, cycle oil and steam for catalytic cracking are injected into the upper part of a catalytic cracking riser together, and under the condition of a reaction temperature of 600-720 ℃, the total yield of propylene and butylene is increased by only 10wt%, and the improvement level of the yield of the cracking reaction is limited.
In order to improve the yield of the micromolecule olefin, the patent publication No. CN100448954C discloses a reactor containing double lifting pipes, and the process is that preheated raw material oil is injected into a main lifting pipe to contact with a catalytic cracking catalyst to generate catalytic cracking reaction; the liquefied gas product after separating out the propylene is injected into an auxiliary riser to contact with a second catalyst, and then reactions such as olefin polymerization, polymerization product cracking, alkane dehydrogenation and the like can be carried out. Although the technology improves the yield of ethylene and propylene by assisting the further cracking reaction in the lift pipe, the technology ignores the problem that the two catalysts interfere with each other, cannot effectively regenerate and separate the two catalysts, and has great difficulty in industrial implementation.
Patent publication No. CN102690683A discloses a catalytic cracking method and a catalytic cracking device for increasing the yield of propylene. The device related to the method adopts a double-reactor configuration, a clapboard is arranged in the stripper to divide the stripper into two independent stripping areas, and a clapboard is arranged in the regenerator to divide the stripper into two independent regeneration areas. One of the stripping zones is connected with one reactor to form a separate reaction and stripping route, and the other stripping zone is connected with the other reactor to form another separate reaction and stripping route. However, in specific applications, the method and the device face two difficult engineering problems: the method comprises the following steps that firstly, the carbon content difference of two spent catalysts is large, the temperature difference of two sides of a partition plate is large due to partition plate regeneration, the heat of the spent catalyst after heavy hydrocarbon reaction is excessive after the spent catalyst is burnt, the regeneration heat of the spent catalyst after light hydrocarbon reaction is insufficient, and the two reaction systems are difficult to effectively transfer heat; secondly, a dilute phase zone in the regenerator belongs to a common mixed zone of two catalysts, the two catalysts are seriously polluted after long-term operation, and the industrial production effect is difficult to exert.
Patent publication No. CN1315990C discloses a process for coupled regeneration of catalyst system, which is set up a secondary regenerator for novel fluidized catalytic reaction and a riser reactor for novel fluidized catalytic reaction beside a conventional catalytic cracker regenerator. The process utilizes the difference of physical properties of the catalytic cracking catalyst and the special catalyst, realizes the mixing and separation of the two catalysts in a novel regenerator, and realizes the heat complementation and mutual noninterference of the two reactions, but the device has a double-riser reactor and a regenerator, has a complex equipment structure, is difficult to apply and popularize, and the countercurrent classification of the two catalysts in the device determines that the operating conditions of the device are harsh.
In summary, although the prior art attempts to provide a plurality of coupled processes for heavy oil catalytic cracking and light hydrocarbon catalytic cracking, and can achieve the purpose of thermal compensation of the two processes, there are also many problems that are difficult to be solved in practical engineering, such as: the yield of two reactions is difficult to balance due to a single catalyst system, and the promotion is limited; the two catalysts are mutually interfered and difficult to regenerate and separate; heat compensation is difficult to realize, or the catalytic effect is not ideal when the catalyst is operated for a long time; the equipment structure is too complex and difficult to apply and popularize.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method and a device for catalytic cracking of a bi-component particle catalyst coupled fluidized bed. By utilizing the method and the device, not only can the heavy oil catalytic cracking process and the light hydrocarbon fluidized catalytic process be coupled to realize thermal compensation, but also the two reactions can adopt respectively most suitable catalysts and operating conditions, and the olefin is maximally byproduct under the premise of not influencing the light hydrocarbon fluidized catalytic process, thereby solving various problems existing in the coupling process of the two processes.
In a first aspect, the present invention provides a method for coupled fluid catalytic cracking of a bicomponent particulate catalyst, comprising: under different operation gas velocities, the concentration distribution of two catalysts with different particle sizes in different regions in the axial direction of a fluidized bed-riser reactor is different, so that a large-particle-size catalyst is enriched in a fluidized bed section reaction region of the reactor for light hydrocarbon fluidized catalytic reaction, and a small-particle-size catalyst is enriched in a riser section reaction region of the reactor for heavy hydrocarbon catalytic cracking;
in a regenerator, the mixed spent catalyst is contacted with air and then is uniformly mixed in a fluidization mode and is burnt for regeneration; the regenerated mixed catalyst is led out from the dense phase section of the regenerator and returned to the fluidized bed-riser reactor.
The research of the invention finds that the physical property (particle size and density) difference of the two catalysts can realize the coupling of the catalytic cracking of heavy hydrocarbon and the fluidized catalytic reaction of light hydrocarbon in the same reaction device, thereby improving the fluidization performance of the catalysts; in addition, in the regeneration process, the excessive coke-burning heat in the catalytic cracking of the heavy hydrocarbon can directly contact with the catalyst for heat exchange to supply the large-particle-size light hydrocarbon catalyst, so that the heat compensation effect is realized, and the consumption of fuel is saved; meanwhile, the regenerated high-temperature mixed catalyst enters a fluidized bed-riser reactor and provides heat required by the two reactions of catalytic cracking of heavy oil and catalytic fluidizing of light hydrocarbon.
Moreover, the method of the invention can adopt two catalysts which are most suitable for reaction, thereby solving the problem of mutual interference of the two catalysts used in the same catalytic cracking unit from the engineering aspect; meanwhile, the method has no more limitation on the reactor for realizing the two reactions, and the size of the reactor can be adjusted according to the dynamic thermodynamic characteristics of the corresponding reactions, so that the optimal reaction conditions are created for each reaction.
Further, the concentration distribution difference in the axial direction is specifically:
in the fluidized bed section reaction zone, the large-particle-size catalyst accounts for 70-95 wt%, preferably 85-95 wt%;
in a reaction zone of the lift pipe section, the large-particle-size catalyst accounts for 1-15 wt%, preferably 3-10 wt%;
the ratio of the large-particle-size catalyst in the stripping section and the regenerator is consistent with that in the reaction zone of the lifting pipe section.
Research shows that in the fluidized bed section, the fluidization performance of the large-particle-size catalyst can be enhanced to a certain extent by the proper amount of the small-particle-size catalyst in the large-particle-size catalyst. In the riser section, the light hydrocarbon raw material and the cracking products enter the riser section, so that the atomization performance of the heavy oil catalytic cracking raw material can be enhanced, and the reaction oil gas partial pressure is reduced, thereby reducing the use amount of pre-lifting steam in the heavy oil catalytic cracking.
Furthermore, the invention realizes the concentration distribution difference of the catalysts with different particle sizes in different areas in the axial direction by controlling the operating gas velocity, thereby realizing heat complementation. Specifically, in the fluidized bed section reaction zone, the operation gas velocity is controlled to be 0.8-4.0 m/s, and the preferable gas velocity is 1.5-3.5 m/s; in the reaction zone of the lift pipe section, the operating gas velocity is controlled to be 8-22 m/s, preferably 10-20 m/s.
Further, for the coupling reaction of heavy hydrocarbon catalytic cracking and light hydrocarbon catalytic cracking, the small-particle-size catalyst is a heavy hydrocarbon catalytic cracking catalyst taking Y-type zeolite as a main active component; the average particle size distribution is 40 to 200 μm, the average particle size is 60 to 75 μm, and the bulk density is 800 to 1300kg/m 3 . The large-particle-size catalyst is a light hydrocarbon fluidized catalytic reaction taking a ZSM-5 type zeolite molecular sieve, a CRP catalyst or a CEP catalyst as a main active component, the average particle size of the large-particle-size catalyst is 500-2000 mu m, and the bulk density of the large-particle-size catalyst is 600-1300 kg/m 3 。
Researches show that the density and the particle size of the catalyst with the particle size are changed, so that the two catalysts are in specific and differential distribution in a fluidized bed section and a riser section under the same operation condition, and the reaction benefit is improved.
The reaction is a coupling reaction of heavy hydrocarbon catalytic cracking and light hydrocarbon fluidized catalytic reaction; the light hydrocarbon fluidized catalytic reaction can be a light hydrocarbon catalytic cracking reaction, a gasoline deep olefin-reducing modification reaction, a catalytic gasoline aromatization reaction, a catalytic gasoline catalytic cracking reaction, a catalytic gasoline catalytic desulfurization reaction and a light hydrocarbon (C is less than or equal to 4) catalytic cracking reaction.
The feedstock for the catalytic cracking of heavy hydrocarbons according to the present invention is selected from the group consisting of petroleum hydrocarbons, mineral oils and synthetic oils and mixtures thereof, such as vacuum distillate, delayed coking distillate, atmospheric and vacuum heavy oils and mixtures thereof.
The raw material for catalytic cracking of the light hydrocarbon is selected from one or more than one mixture of petroleum hydrocarbon, mineral oil and synthetic oil, such as naphtha, atmospheric diesel oil, vacuum wax oil, atmospheric residue, vacuum residue and light hydrocarbon obtained by secondary processing of the atmospheric residue and the vacuum residue, and can also be light hydrocarbon produced after catalytic cracking of heavy hydrocarbon in the device.
In a second aspect, the present invention provides an apparatus for implementing the foregoing method, including: the device comprises a reactor, a regenerator and a regeneration inclined pipe for connecting the reactor and the regenerator;
the reactor comprises a fluidized bed section and a lifting pipe section connected with the fluidized bed section;
the outlet of the regeneration chute is located at the dense phase to dilute phase interface of the fluidized bed section, specifically above 1/3 of the fluidized bed section.
The device with the structural design can better realize the coupling of the two reactions, and is more beneficial to the regeneration and separation effects of the two catalysts, thereby better improving the benefits of the two reactions. Meanwhile, the fluidized bed section reactor and the lift pipe section reactor can adjust the size of the reactor according to the dynamic thermodynamic characteristics of corresponding reactions so as to create optimal reaction conditions for each independent reaction. The device has compact structure, easy implementation, simple and flexible operation and is more suitable for industrial large-scale use.
Furthermore, the research of the invention finds that if the relative particle size difference of the two selected catalysts is large, the concentration of the large-particle-size catalyst in the fluidized bed section is too high, and the large-particle-size catalyst is difficult to be effectively entrained to the lift pipe section under normal operation gas. For this purpose, an inner member is also arranged in the fluidized bed section, and the inner member comprises a guide cylinder, a gas distributor or an annular distributor so as to improve the fluidization quality of the large-particle-size catalyst.
The guide shell is coaxial with the fluidized bed section, the ratio of the diameter of the guide shell to the diameter of the fluidized bed section is 0.6-0.85, and the fluidized bed section is divided into a guide shell inner reaction zone and an annular space reaction zone; the circulation of the mixed catalyst in the fluidized bed section is strengthened by the arrangement of the guide cylinder.
The height of the guide cylinder is determined according to the height of a dense-phase bed layer in the fluidized bed section, the ratio of the height to the total height of the fluidized bed section is preferably 0.2-0.8, and the height of a dilute-phase space in the fluidized bed section is at least kept at 2 m.
Furthermore, the concentration distribution difference of two large-difference catalysts in the fluidized bed-riser reactor can be strengthened by reasonably arranging the height of the guide shell and matching the position of the regeneration inclined tube. Preferably, the operating air speed in the guide shell is kept between 1.5 and 5.0 m/s.
The annular distributor is arranged below the area between the fluidized bed and the guide cylinder; and in an annular space area formed by the annular distributor, the apparent gas velocity is maintained between 0.2 and 0.8 m/s. For a fluidizable mixed particle system, the annular gas velocity can be reduced or the annular distributor can be eliminated.
The gas distributor is arranged right below the guide shell.
The inner member further comprises a tapered inner member; the surface of the conical inner member is provided with sieve pores, and the diameter of the conical section is gradually increased from bottom to top; it is arranged in an annular space between the guide shell and the outer wall of the fluidized bed and below an outlet of the regeneration inclined tube. The mixing degree of the two catalysts in the guide shell is effectively reduced by setting the conical inner member, and the concentration distribution difference of the large-difference bi-component catalyst in the fluidized bed-riser reactor is strengthened.
The height of the conical inner member is 0.1-0.5 m, and the lower end opening of the conical inner member is located 0.3-1.5 m, preferably 0.6-1.2 m below the outlet of the guide cylinder; the cone angle of the conical inner part is 30-120 degrees, preferably 60 degrees.
And in an annular space formed between the guide cylinder and the outer wall, the gas velocity of the reaction oil gas passing through the through hole of the conical inner component is 0.3-2.5 m/s.
The structure of the device can be high and low parallel or coaxial.
The invention has the following beneficial effects:
1. the method and the device provided by the invention can realize the coupling process of the catalytic cracking of heavy hydrocarbon and the fluidized catalytic reaction of multiple light hydrocarbons, and the heat complementation between the two reactions; and the problem that two catalysts are used in the same catalytic cracking device to interfere with each other is well solved in engineering, and the yield is ensured.
2. In the fluidized bed section, the small-particle-size catalyst which is properly present in the large-particle-size catalyst can enhance the fluidization performance of the large-particle-size catalyst to a certain extent.
3. In the riser section, the light hydrocarbon raw material and the cracking products enter the riser section, so that the atomization performance of the heavy oil catalytic cracking raw material can be enhanced, and the usage amount of pre-lift steam is reduced.
4. In the device, the size of the fluidized bed section reactor and the lift pipe section reactor can be adjusted according to the dynamic thermodynamic characteristics of corresponding reactions, and optimal reaction conditions are created for each independent reaction.
5. The device has the advantages of compact structure, easy implementation, simple and flexible operation, and is more suitable for industrial large-scale use.
Drawings
FIG. 1 is a schematic flow diagram of a process for dual component particulate catalyst coupled fluid catalytic cracking in accordance with the present invention.
FIG. 2 is a high-low parallel device diagram of a bi-component particle catalyst coupled fluid catalytic cracking device.
FIG. 3 is a diagram of a coaxial apparatus of the bi-component granular catalyst coupled fluid catalytic cracking apparatus of the present invention. The device has the characteristics of an external fluidized bed-riser reactor and coaxial stripper regenerator.
Fig. 4 is an optimized structure of the bi-component granular catalyst coupled fluidized bed catalytic cracking unit, which improves fluidization quality and enhances catalyst separation effect.
Fig. 5 is an optimized structure of the bi-component granular catalyst coupled fluidized catalytic cracking unit according to the present invention, which enhances the catalyst separation effect.
In each figure:
a gas distributor 1; a fluidized bed section reaction zone 2; a riser section reaction zone 3; a stripper 4; an outlet oil separator 5; a settler 6; a cyclone 7; a spent inclined tube 8 for mixing the catalyst; a regeneration inclined tube 9 of the mixed catalyst; fluidized bed top lamina 11; a regenerator 12; a settling tank 13; a regenerator cyclone 14; an overflow weir 15;
a light hydrocarbon catalytic cracking feedstock 21; a heavy hydrocarbon catalytic cracking feedstock 22; steam 23; regenerator air 24; a stripper outlet 25; a regenerator outlet 26;
a draft tube 30; a dilute phase fluidized bed section 31; a reaction zone 32 within the draft tube; an annular space reaction zone 33; an annular distributor 34;
the inner member lamina 41.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
Referring to fig. 1, in order to realize steady-state operation, the method of the present invention is divided into 4 processes, and has the following characteristics:
1. fluidized bed section reaction zone: the catalyst with large particle size in the reaction zone is a main catalyst, but the excessive concentration of the catalyst with large particle size in the bed layer is not beneficial to the fluidization of the bed layer, and the excessive concentration of the catalyst with small particle size is not beneficial to the catalytic cracking reaction. The catalyst with large particle size in the bed layer needs to be maintained at a certain air speed to control the proportion of the catalyst with large particle size in the bed layer to be 80-95 wt%, and meanwhile, part of the catalyst with large particle size is brought into a riser area and is circularly regenerated to maintain the activity of the catalyst with large particle size and the heat required by cracking reaction.
2. A riser section reaction zone: the small-particle-size catalyst in the reaction zone is a main catalyst, but a proper large-particle-size catalyst is also present and accounts for 3-10 wt%; on one hand, the high circulation rate of the catalyst with large particle size can affect the selectivity and the conversion rate of the catalytic cracking reaction; on the other hand, insufficient ratio of the circulating amount of the large-particle-size catalyst affects the activity of the large-particle-size catalyst in the fluidized bed and the heat balance of the catalytic cracking reaction-regeneration system.
3. A regenerator: the mixed catalyst consisting of the catalyst with large particle size and the catalyst with small particle size is ensured to be fully mixed in the regenerator, the mixed catalyst has good fluidization quality, the heat transfer and the regeneration are realized on the premise of not influencing the transportation, and the phenomenon of 'grading' fluidization cannot occur.
4. Returning the regenerated mixed catalyst to a fluidized bed section reaction zone of the reactor: in the process, the regenerated large-particle-size catalyst is required to descend as far as possible and enter a fluidized bed section reaction zone, and the regenerated small-particle-size catalyst ascends as far as possible, so that the separation effect is improved; the following examples 3 and 4 enhance the separation effect of the large-particle size regenerated catalyst and the small-particle size regenerated catalyst by adding a draft tube and an inner member in a fluidized bed.
The 4 process loops are buckled with each other, so that the two reaction processes are coupled in one reactor.
The specific reaction process, operation conditions and beneficial effects of the invention are detailed in the examples.
Example 1
Referring to fig. 2, this embodiment provides a bi-component particle catalyst coupled fluid catalytic cracking apparatus, comprising:
the device comprises a reactor, a regenerator and a regeneration inclined pipe for connecting the reactor and the regenerator;
the reactor comprises a fluidized bed section and a lifting pipe section connected with the fluidized bed section;
the outlet of the regeneration chute is located at the dense phase to dilute phase interface of the fluidized bed section. Preferably, the regeneration chute is located at 1/3 above the fluidized bed section.
An inner component is further arranged in the fluidized bed section and comprises a guide cylinder and a gas distributor.
The structure of the device is in a high-low parallel type; the riser section of the reactor is coaxial with the fluidized bed section and is arranged in parallel with the regenerator; the lifting pipe section also comprises an outlet oil separator and a to-be-grown inclined pipe.
The embodiment also provides a dual-component particle coupling fluid catalytic cracking method using the device, which comprises the following steps:
(1) the light hydrocarbon catalytic cracking raw material 21 enters a fluidized bed reactor 2 through a gas distributor 1, and the heavy hydrocarbon catalytic cracking raw material 22 enters a riser section reactor 3 through a nozzle;
when the device stably runs, the overall proportion of large and small catalysts in the device is adjusted by controlling the two catalyst buffer tanks, and the apparent gas velocity in the fluidized bed and the lifting pipe is controlled by controlling the cracking raw material 21 and the cracking raw material 22, so that the concentration distribution of the two catalysts in the axial height of the reactor is controlled, the large-particle-size catalyst is enriched in the fluidized bed section 2, and the small-particle-size catalyst is enriched in the lifting pipe section 3. In the fluidized bed section, the large-particle-size catalyst is contacted with the light hydrocarbon catalytic cracking raw material 21 to perform a cracking reaction. In the riser section, the small particle size catalyst contacts the heavy hydrocarbon catalytic cracking feedstock 22 for cracking reactions.
(2) After the reaction is finished, the coked spent catalyst is roughly separated by an outlet oil separator 5 and then falls into a stripper 4 to be contacted with stripping steam 23, and the steam carrying unreacted oil gas passes through a cyclone separator 7 of a settling tank 6 and then leaves from an outlet 25 of the stripper; the mixed catalyst enters the regenerator 12 from the inclined tube to be regenerated 8 and is burnt and regenerated by contacting with air 24. The char flue gas exits from regenerator outlet 26 after passing through cyclone 14 in settling tank 13.
The particles in the regenerator are kept to be uniformly mixed by controlling the air flow, and the excessive regeneration heat of the catalytic cracking reaction is transferred to the cracking catalyst with insufficient regeneration heat in time.
(3) The regenerated catalyst enters the regeneration inclined pipe 9 from the inner component overflow weir 15 under the pushing of the differential pressure of the regenerator and the reactor, and then enters the fluidized bed-riser reactor;
most of the regenerated mixed catalyst is directly carried into the riser reactor 3 under the action of the fluidized air, and the large-particle-size catalyst enters the fluidized bed reactor 2 under the action of inertia to start new circulation.
The test result shows that the bi-component particle coupling fluid catalytic cracking process well solves the problem of mutual interference of two catalysts used in the same catalytic cracking device from the engineering aspect.
The mixture of two large difference catalysts run at different axial positions with different concentration profiles of the two catalysts. The concentration ratio is as follows: the mass ratio of the catalyst with large particle size in the fluidized bed dense-phase reactor is 70-95%, preferably 85-95%; the proportion of the large-particle-size catalyst in the riser, the stripper and the regenerator is 1-15%, preferably 3-10%.
The particle sizes of the two catalysts are as follows: the catalyst with large particle size has an average particle size of 500 to 2000 μm and a bulk density of 600 to 1300kg/m 3 (ii) a The small-particle-diameter catalyst has an average particle diameter of 40 to 200 μm, an average particle diameter of 60 to 75 μm, and a bulk density of 800 to 1300kg/m 3 。
The operation air speed of the lift pipe section is 8-25 m/s, and the preferable air speed is 10-20 m/s. The operating gas velocity of the fluidized bed reactor is 0.8-4 m/s, and the preferable gas velocity is 1.2-3.0 m/s.
The operation gas velocity of the regenerator is 0.5-1.5 m/s, preferably 0.6-1.1 m/s.
The present invention has no particular requirements on the internals 15, separation equipment such as cyclones, and other operating conditions including temperature, pressure, and excess oxygen content of the dense bed and the char pot, as is known in the art.
Example 2
Referring to fig. 3, compared with example 1, the other structures of this embodiment are unchanged, and the main difference is that the structural layout of the riser, the stripper and the regenerator is different.
Example 2 an external fluidized bed-riser reactor was used, with the stripper 4 and settler 6 placed on top of and on the same axis as the regenerator 12. The arrangement of the coaxial stripper regenerator places the stripping section of the settler inside the regenerator, contributing to the reduction of the overall height of the plant and making it possible to omit the equipment frame of the settler.
The working principle of the embodiment is basically similar to that of the embodiment 1, and is different from the embodiment 1 in that a mixture of reaction product oil gas and catalyst from a riser outlet is directly introduced into a settler 6, the reaction product oil gas passes through a cyclone separator 7 and then leaves through a stripper outlet 25, catalyst particles in the settler fall into a stripper 4, the catalyst in a stripping section is stripped and then enters a regenerator 12 through a settling tube to be burnt and regenerated with air 24, regenerated flue gas finally leaves through the cyclone separator in a regenerator settling tank 13, and the regenerated mixed catalyst enters a fluidized bed-riser reactor from a regeneration inclined tube 9 to start new circulation.
The raw materials, the type of the catalyst, the operating conditions and the beneficial effects used in example 2 are the same as those in example 1, and are not described in detail herein.
Example 3
As shown in fig. 4, if the relative density difference between the two selected catalysts is large, the concentration of the large-particle-size catalyst in the fluidized bed section is too high, and it is difficult to effectively entrain the large-particle-size catalyst into the riser section due to the mixed particles in the fluidized bed section under normal operation gas.
On the basis of the embodiment 1, the embodiment 3 establishes a guide shell 30 and an annular distributor 34 in the middle of the fluidized bed in the embodiment 1;
the guide shell is connected with the outer wall of the reactor through a rib plate, and the guide shell divides the fluidized bed reactor into a guide shell inner reaction area 32 and an annular space reaction area 33.
The gas distributor 22 is disposed just below the guide shell 21.
The working principle of the embodiment is similar to that of embodiment 1, except that in the fluidized bed section, the catalytic cracking raw material 21 enters the reaction zone 32 in the draft tube through the gas distributor 1, and forms violent turbulent contact with the cracking catalyst in the draft tube, the gas-solid two phases react in a manner of nearly complete mixing flow, then the coked cracking catalyst enters the dilute phase fluidized bed section 31 through the outlet of the draft tube, after being buffered by the dilute phase fluidized bed section 31 of 2-6 m, the large-particle-size catalyst is settled to the annular space reaction zone 33 between the fluidized bed and the draft tube under the action of gravity, and a small part of coked large particles are carried to the lifting tube section by the small-particle-size catalyst after being splashed to the vertebral plate 11 at the top of the fluidized bed. The mixed catalyst settled to the annular space enters the bottom of the guide shell again under the pushing of static pressure to start new circulation under the loosening of loosening wind of the annular distributor. In the riser, a mixed catalyst mainly composed of a small-particle size cracking catalyst is contacted with the catalytic cracking feedstock 13 and reacted in a manner close to plug flow.
In the embodiment 3, the circulation of the mixed catalyst in the fluidized bed reactor is enhanced by setting the guide cylinder, so that the reaction efficiency of gas phase and solid phase is enhanced; the concentration distribution difference of the two large-difference catalysts in the fluidized bed-riser reactor can be strengthened by reasonably arranging the height of the guide shell and the position of the regeneration inclined tube.
The ratio of the diameter of the guide shell to the diameter of the fluidized bed reactor in the above example 3 is 0.6 to 0.85, the height of the guide shell is determined according to the height of the dense bed layer in the fluidized bed reactor, the ratio of the height of the guide shell to the total height of the fluidized bed reactor is preferably 0.2 to 0.8, the height of the dilute phase space is preferably maintained at least at 2m, and the ratio of the diameter of the gas distributor to the diameter of the guide shell in the above example 2 is 0.5 to 1.5. The operating air speed in the guide shell is kept at 1.5-5 m/s;
the annular distributor in the embodiment 3 is arranged between the fluidized bed and the guide cylinder, the structure and the installation position of the annular distributor are not specifically required, the apparent gas velocity in the annular space is maintained at 0.2-0.8 m/s, and the gas velocity in the annular space can be reduced or the annular distributor can be eliminated for an easily fluidized mixed particle system. The outlet of the inclined regenerating pipe is arranged at the junction of the dense phase zone and the dilute phase zone of the bed layer and the height of the outlet is higher than 2/3 of the height of the fluidized bed.
The raw materials, the type of the catalyst, the operating conditions and the beneficial effects used in example 3 are the same as those in example 1, and are not described again here.
Example 4
As shown in fig. 5, the present embodiment is based on the embodiments 1 and 3, and the main structure is the same as the embodiment 1 and 3, and the main difference is that an inner member vertebral plate 41 is arranged in the annular space between the guide cylinder and the outer wall of the fluidized bed. The surface of the conical inner component is provided with sieve pores, and the diameter of the conical section is gradually increased from bottom to top.
The working principle of this embodiment is basically similar to that of embodiment 3, except that the reaction gas in the annular space gradually increases in diameter expansion in the process of flowing upwards after passing through the mesh of the vertebral plate of the inner member, when the mixed regenerated catalyst from the regenerated inclined tube passes through the inner member, the small-particle-size catalyst is easily brought out of the annular space by the high gas velocity in the lifting tube, and the large-particle-size catalyst is more influenced by gravity and tends to fall from the pores of the vertebral plate of the inner member.
The mixing degree of the two catalysts in the guide shell is effectively reduced by setting the conical inner member, and the concentration distribution difference of the large-difference bi-component catalyst in the fluidized bed-riser reactor is strengthened.
In the above embodiment, the conical inner member is set up below the outlet of the regeneration inclined tube, the height of the conical inner member is 0.1-0.5 m, and the lower end opening of the conical inner member is 0.3-1.5 m, preferably 0.6-1.2 m below the outlet of the draft tube.
As shown in FIG. 5, the cone angle of the conical inner member should be 30-120 degrees, preferably 60 degrees. The conical surface of the conical inner member is provided with the openings, the gas velocity of the through holes when the reaction oil gas in the annular space passes through the inner member is 0.3-2.5 m/s, and the invention does not make specific requirements on the size and the opening rate of the openings on the conical inner member.
The raw materials, the type of the catalyst, the operating conditions and the beneficial effects used in example 4 are the same as those in example 1, and are not described again here.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A method for coupling two-component particle catalyst with fluid catalytic cracking is characterized by comprising the following steps:
utilizing the concentration distribution difference of two catalysts with different particle sizes in different regions of the fluidized bed-riser reactor in the axial direction to enrich the large-particle-size catalyst in a fluidized bed section reaction zone of the reactor for light hydrocarbon fluidized catalytic reaction, and enrich the small-particle-size catalyst in a riser section reaction zone of the reactor for heavy hydrocarbon catalytic cracking;
in a regenerator, the mixed spent catalyst is contacted with air and then is uniformly mixed in a fluidization mode and is burnt for regeneration; leading out the regenerated mixed catalyst from the dense phase section of the regenerator and returning the regenerated mixed catalyst to the fluidized bed-riser reactor;
for the coupled reaction of heavy hydrocarbon catalytic cracking and light hydrocarbon catalytic cracking,
the small-particle-size catalyst is a heavy hydrocarbon catalytic cracking catalyst taking Y-type zeolite as a main active component; the average particle size is distributed in the range of 40-200 mu m, the average particle size is 60-75 mu m, and the bulk density is 800-1300 kg/m 3 ；
The large-particle-size catalyst is a light hydrocarbon fluidized catalytic reaction taking a ZSM-5 type zeolite molecular sieve, a CRP catalyst or a CEP catalyst as a main active component, the average particle size of the large-particle-size catalyst is 500-2000 mu m, and the bulk density of the large-particle-size catalyst is 600-1300 kg/m 3 。
2. The method of claim 1, wherein the difference in concentration profiles of different regions in the axial direction is:
in the fluidized bed section reaction zone, the large-particle-size catalyst accounts for 70-95 wt%;
in a reaction zone of the lift pipe section, the large-particle-size catalyst accounts for 1-15 wt%;
the ratio of the large-particle-size catalyst in the stripping section and the regenerator is consistent with that in the reaction zone of the lifting pipe section.
3. The method of claim 2, wherein the catalyst with large particle size accounts for 85-95 wt% in the reaction zone of the fluidized bed section;
in the reaction zone of the lift pipe section, the large-particle-size catalyst accounts for 3-10 wt%.
4. The method of claim 2, wherein the difference in concentration distribution of the large and small particle size catalysts in different regions in the axial direction is achieved by controlling the operating gas velocity.
5. The method according to claim 4, wherein the operating gas velocity is controlled to be 0.8 to 4.0m/s in the fluidized bed section reaction zone;
and controlling the operating gas velocity to be 8-22 m/s in the reaction zone of the lift pipe section.
6. The method according to claim 5, wherein the operating gas velocity is controlled to be 1.5-3.5 m/s in the fluidized bed section reaction zone;
and controlling the operating gas velocity to be 10-20 m/s in the reaction zone of the lift pipe section.
7. The method of claim 5, wherein the light hydrocarbon fluidized catalytic reaction comprises a light hydrocarbon catalytic cracking reaction, a gasoline deep olefin-reducing upgrading reaction, a catalytic gasoline aromatization reaction, a catalytic gasoline catalytic cracking reaction, a catalytic gasoline catalytic desulfurization reaction, and a catalytic cracking reaction of C4 light hydrocarbons.
8. An apparatus for implementing the method of any one of claims 1-7, comprising: the device comprises a reactor, a regenerator and a regeneration inclined pipe for connecting the reactor and the regenerator;
the reactor comprises a fluidized bed section and a lifting pipe section connected with the fluidized bed section;
the outlet of the regeneration chute is located at the dense phase to dilute phase interface of the fluidized bed section above 1/3 in the fluidized bed section.
9. The apparatus of claim 8, wherein an internals is further provided within the fluidized bed section; the inner component comprises a guide cylinder, a gas distributor or an annular distributor;
the guide cylinder is coaxial with the fluidized bed section, and the ratio of the diameter of the guide cylinder to the diameter of the fluidized bed section is 0.6-0.85; the ratio of the height of the guide shell to the total height of the fluidized bed section is 0.2-0.8;
the annular distributor is arranged below the region between the fluidized bed and the guide cylinder;
the gas distributor is arranged right below the guide shell.
10. The device of claim 9, wherein the inner member further comprises a tapered inner member;
the surface of the conical inner member is provided with sieve pores, and the diameter of the conical section is gradually increased from bottom to top; the regeneration inclined pipe is positioned in an annular space between the guide cylinder and the outer wall of the fluidized bed and below an outlet of the regeneration inclined pipe;
the height of the conical inner member is 0.1-0.5 m, the lower end opening of the conical inner member is located 0.3-1.5 m below the outlet of the guide cylinder, and the conical angle of the conical inner member is 30-120 degrees.
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Inventor after: Lu Chunxi Inventor after: Jin Weixing Inventor after: E Chenglin Inventor after: Fan Yiping Inventor before: Lu Chunxi Inventor before: Jin Weixing Inventor before: E Chenglin Inventor before: Fan Yiping Inventor before: Wang Longyan |