JPH03504352A - Fluid catalytic cracking method and device for more effective regeneration of zeolite catalyst - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Fluid catalytic cracking method and device for more effective regeneration of zeolite catalyst The present invention relates to a method and apparatus for regenerating a fluidized cracking catalyst. For more information , the present invention provides a step-by-step method to minimize or substantially eliminate hydrothermal deactivation. The present invention relates to a method and apparatus including the regeneration and separation of flue gas from catalyst particles.

The field of catalytic cracking, especially fluidized catalyst operation, is primarily based on catalyst technology and its benefits. There has been considerable development and improvement due to the evolution of product distribution. Highly active catalysts, especially The advent of crystalline zeolite cracking catalysts has opened up a field of new operating techniques and Further new improvements in processing techniques that take advantage of media activity, selectivity and operating sensitivity are needed. It is said that

By way of background, hydrocarbon conversion catalysts commonly used in fluid catalytic cracking (FCC) units are , high activity riser conversion zone with flowable particle size (flowable catalytic cracking region), typically in a suspended or dispersed phase. However, the residence time of the hydrocarbons in each conversion zone is between 0.5 and 10 seconds, typically less than 8 seconds. be. High temperature riser hydrocarbon conversion is 538°C (1000’F) or higher stagnation of hydrocarbons in contact with the catalyst in the riser at a temperature of 0.5 to 4 seconds. Occurs during residence time, but in some cases begins to separate gaseous hydrocarbon materials from the catalyst The former such conversion is preferred. Riser rotation to limit hydrocarbon over-cracking It is particularly desirable to rapidly separate the catalyst from the hydrocarbons discharged from the oxidation zone.

A closed cyclone system is used in the fluid catalytic cracking reactor to remove carbonization from the cracking catalyst. Hydrogen products are rapidly separated, thereby preventing over-decomposition. closed cycle The Ron system is described in U.S. Pat. No. 4.50 to Haddad et al. It is also described in No. 2.947.

During the hydrocarbon conversion process, carbonaceous deposits accumulate on the catalyst particles, causing the particles to undergo hydrocarbon conversion. When removed from the process, hydrocarbon vapors are entrained. The entrained hydrocarbons are Furthermore, the stripping gas is in contact with the catalyst and has a separate catalyst stripping area. removed from the catalyst by gas. Hydrocarbon products and streams separated from the catalyst The separated materials are mixed and typically sent to a product separation step. Deactivation amount of charcoal Stripped catalyst (spent catalyst) containing prime material (hereinafter referred to as coke) ) is then sent to a catalyst regeneration operation.

In catalyst regeneration, the spent catalyst is contacted with oxygen to burn off the coke. However However, the spent catalyst contains hydrogen-containing components such as coke attached to it.

For this reason, the oxygen and hydrogen in the regenerator react to produce water, causing hydrothermal deterioration. .

In U.S. Pat. No. 4,336,160 to Dean et al. Attempts have been made to reduce hydrothermal degradation through staged regeneration.

However, the first stage of Dean et al.'s regeneration method provides an opportunity for hydrothermal deactivation. A thick floor is used.

A fluidized catalytic cracking regenerator using a fast fluidized bed riser has been developed. Like that A fast fluidized bed is described in Owen's U.S. Pat. No. 4,444, It is described in No. 722.

Medium pore zeolites such as ZSM-5 and large pore zeolites such as Zeolite Y Both are used in fluid catalytic cracking. ZSM-5 and other zeolites, e.g. For example, the combination of Y (zeolite) It is described in US Pat. No. 3,758,403.

Medium pore zeolites, especially ZSM-5, are similar to large pore zeolites such as Zeolite I-Y. Coke does not suddenly adhere to the throat. Therefore, ZSM-5 is a regenerated zeolite Y. do not have to.

It is desirable to minimize hydrothermal degradation. Furthermore, the zeolite Y-containing catalyst is regenerated. In processes that do not regenerate the ZSM-5 catalyst to any extent, the ZSM-5 catalyst particles and It is desirable to use a combination of zeolite Y catalyst particles.

The present invention burns hydrocarbons from a coke-adhered catalyst by contacting with air in stages. Fluid catalytic cracking of crystalline zeolite by removing flue gas after each combustion stage Minimize hydrothermal degradation of the catalyst. This is especially true for fluids using ZSM-5. This is an advantage in catalytic cracking methods. The present invention is designed to maintain combustion during each regeneration step. sufficient, preferably just enough for each regeneration step to sustain combustion. of air to rapidly remove flue gases produced during combustion.

Flue gases are removed from the catalyst by contacting the gas with the catalyst. It is preferable to take it out.

The first stage regeneration comprises: contacting the catalyst with a first oxygen-containing gas stream; Thereafter, by quickly separating the first flue gas stream from the catalyst, the riser Do it with a regenerator. The second regeneration stage is carried out by means of a fast fluidized bed. There, the first The catalyst from the stage contacts the second oxygen-containing gas stream. Upper part of high-speed fluidized bed The catalyst exiting from the air is quickly separated into a second flue gas stream and The medium is sent to a third stage regeneration. In the third stage, the catalyst is transferred to the third oxygen-containing waste stream. A third flue gas stream is produced which is separated from the catalyst. 1st lie The catalyst in the laser is maintained at a temperature of 538-677°C (1000-1250°F). Ru. The catalyst in the high speed fluidized bed is 28°C (50'F) higher than the temperature of the catalyst in the first riser. The temperature is maintained at a temperature of ~760'C (1400°F). The second bed catalyst 1 14°C (25°F), preferably 56°C (100'F) above the temperature of the fluidized bed The temperature is maintained at a temperature of ~871°C (1600°F).

The present invention comprises medium pore zeolite catalyst particles and large pore zeolite catalyst particles. This is particularly advantageous if a two-phase catalyst system is employed. Intermediate pore zeolite catalyst granules The particles are less likely to be fully supported than the large pore zeolite catalyst particles, thereby causing the intermediate pore particles to The large pore zeolite catalyst particles can be easily separated from the particles. This allows the second stage of playback. medium-pore zeolite catalyst particles can be separated from large-pore catalyst particles before the third stage . In this way, the large pore zeolite catalyst particles can be used for additional regeneration in the third stage. Meanwhile, the intermediate pore zeolite catalyst particles are sent to the fluid catalytic cracking reactor line. Sent directly to the Zar Conversion Area. This includes a medium pore zeolite catalyst with the highest regeneration rate. It has the advantage of minimizing exposure to hot water temperature and therefore reducing deactivation. During ~ Larger pore zeolites have a higher density compared to large pore zeolite catalyst particles. by making it louder, more irregular, or a combination of these factors. Therefore, medium-pore zeolite catalyst particles are less susceptible to elutriation than large-pore zeolite catalyst particles. Ru.

In the drawings, FIG. 1 depicts a partial cross-section of a fluid catalytic cracking (FCC) regenerator in accordance with an embodiment of the present invention. Shown schematically.

FIG. 2 shows a partial cross-section of a fluid catalytic cracking (FCC) regenerator according to a second embodiment of the present invention. A schematic diagram is shown.・Figure 3 shows the separation catalytic cracking (FC) of the third aspect of the present invention. C) Schematic representation of a cross section of the regenerator Φ portion.　　　　.

A fluid catalytic cracking (FCC) process or device is a fluid catalytic cracking (FCC) process or device in which a gas is supplied which acts as a fluid. The catalyst is used in the form of fine catalyst particles. The fluidized catalyst is A medium that circulates continuously and transfers heat from the regenerator to the hydrocarbon feedstock and reactor. Act as a thing. This fluid catalytic cracking method and the Western-style It is important to prevent spilled oil from gasoline and light products. direction? Sl:ge, including stepwise regeneration, with less elutriated catalyst particles removed at an upstream stage (and then the particles that are more susceptible to elutriation are sent to a downstream stage.

Typical cracking catalyst components are generally amorphous/sp-alumina and crystalline silica. It's Lumina. Other substances said to be useful as decomposition catalysts are Crystalline silicoaluminophosphate-h (si1i) of National Patent No. 4,440,871 coalu+m1nophosphate) and U.S. Patent No. 4.5 No. 67, Q29 crystalline metal aluminophosphate.

However, most conventional cracking catalysts currently in use are generally Large pore crystalline silicon in a suitable matrix component with or without catalytic activity. Contains lycazeolite. These zeolites have typical pore openings. Typically has an average crystallographic pore size of 7 or more. This type of typical Examples of crystalline silicate zeolite decomposition catalysts include zeolite X ( U.S. Pat. No. 2,882,244), Zeolite Y (U.S. Pat. Patent No. 3,130.007), Zeolite) ZK-5 (U.S. Patent No. 3) , 247,195), Zeolite ZK-4 (U.S. Pat. No. 3,314) , 752) and naturally occurring zeolites, such as chabazite and faujasite. , mordenite, etc. Also, United States Patent No. 4. , 50.3 ．． Also useful are the silicon-substituted and substituted zeolites described in No. 023. zeolite bae The data (Z, 'gcirite+', Bq-Lm) is the mixture used in the present invention 1. In addition, large-pore crystalline silica bute of 1-5. Ru.

two or more amorphous and/or large pore crystalline zeolite components as described above; Of course, it is also possible to use the decomposed catalyst as the first catalyst component of a mixed catalyst/media system. [Enter the concave circle. Furthermore, at least one catalyst requires frequent regeneration and the first catalyst component), the other catalyst in the system requires relatively infrequent regeneration (second catalyst component), the entire mixed catalyst system consists of two or more types of amorphous and/or large pores. It is also conceivable to make it from a crystalline silicate decomposition catalyst. Therefore, for example, Although the combined catalyst system requires frequent regeneration, the catalyst is stable under the conditions in the regenerator. Olite Y and Zeolite Y are zeolite catalysts that do not need to be regenerated frequently. It can be formed by Ito Beta. Preferred large pore crystalline silicate zeola Light components include synthetic zeolite mordenite and faujasite as well as synthetic zeolite mordenite and faujasite. Includes zeolites X and Y, especially zeolite Y1 zeolite REY, zeolite Light USY and zeolite RE-USY and mixtures thereof are preferred .

Shape-selective intermediate pore crystalline silicate zeolite constituting the second catalyst component of the mixed catalyst system Examples of catalysts include ZSM-51, ZSM-11, ZSM-12, ZS M-23, ZSM-35, ZSM-38, ZSM-48 and other similar materials be. United States Patent No. 3. No. 702,886 describes ZSM-5. ing. U.S. Reissue Patent No. 29,948 describes the X-ray diffraction of ZSM-5. Crystalline materials with patterns have been described. United States Patent No. 4°061 ．． No. 724 describes a high-silica product called silicalite J. Rika ZSM5 is described. .

ZSM-fl is described in particular detail in U.S. Patent No. 3.709.979. has been done. ZSM-12 is specifically described in U.S. Patent No. 3,832.449. is described in detail. ZSM-23 is disclosed in U.S. Patent No. 4,076. It is described in particular detail in No. 842. ZSM-351t, United States patent No. 4,016,245. ZSM-38 is American It is described in particular detail in US Pat. No. 4,046,859. ZSM-4 8 is described in particular detail in U.S. Pat. No. 4,375,373. .

Preferred shape-selective mesoporous crystalline silicate zeolas for mixed catalyst systems herein The light components are ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM -35 and ZSM-38m'', with 23M-5 being particularly preferred.

Generally, it is advantageous to use aluminosilicate zeolites in the present invention.

However, other skeletal elements exist partially or totally replacing aluminum. It may be advantageous to use existing zeolites. For example, such a catalyst , which can lead to higher conversion of feedstock to aromatic components, which tends to increase carbon content, thereby improving the quality of gasoline produced in this way. Improve. Special table 103-50 that may replace part or all of the skeleton aluminum 4352 (8) Examples of elements include boron, gallium, titanium and other trivalent elements heavier than aluminum. There are metals. Particular examples of such catalysts include boron, gallium and/or Includes titanium-containing zeolite beta and ZSM-5. zeolite bone These and other catalytically active Elements with properties may be bound to the zeolite by suitable methods, such as impregnation.

Separating the particles of the first catalyst component from the particles of the second catalyst component in the regenerator includes: This can be done in several ways.

The separation in the regenerator is based on the average particle density of the catalyst between the first catalyst component and the second catalyst component. This can be done by classifying the medium components, which is explained in detail below. A variety of different It can be implemented using the following method. In general, smaller, less dense catalyst particles generally , forming an upper phase in a regenerative suspension above larger and more dense catalyst particles. Conversely, larger and more dense catalyst particles tend to move downwards in the regenerator. form a phase.

the first and second catalyst components have different settling rates denoted R' and R1; Particles with a larger settling velocity precede catalyst particles with a smaller settling velocity. The characteristic physical properties of the first and second catalyst components are selected such that they are discharged from the regenerator at Ru.゛The residence time of catalyst particles in a fluidized or riser type regenerator is mainly determined by two factors. Affected by: attempting to raise the entire catalyst bed and transport it from the regenerator to the separator unit Linear velocity of the fluid stream in the riser and catalyst particles in the regenerator more slowly and opposing gravitational forces that tend to hold. Typically, in a mixed catalyst system, both catalyst components circulate through the system at the same speed. As pointed out earlier, cracking catalysts require frequent regeneration. and no intermediate pore zeolite or other catalyst components are required due to catalyst deterioration conditions in the regenerator. exposure, resulting in a shortened effective catalyst life. However, in the present invention , more of the catalyst that was not deactivated by coke was deactivated by coke. Can be discharged from the regenerator faster than the catalyst. In the regenerator, the mixed catalytic density, particle size and /or the shape may be adjusted in various ways to provide desired sedimentation characteristics.

Among the methods that can be used to increase the density of one catalyst component over another are: Each catalyst may be complexed with matrix components of substantially different densities. useful Matrix components include the following: Matrix components Particle density (g/at) Alumina 3.9-4.0 Silica 2.2-2.6 Magnesium oxide 3.6 Beryllium oxide 3.0 Barium oxide 5,7 zirconium oxide 5.6. -5.9 ・Titanium oxide 4.3-4.9 These two or three types and and/or other suitable porous matrix components, such as silica-alumina, silica Car-magnesium oxide, Silica-Thorium oxide, Silica-Alumina-Zirco oxide A wide range of densities can be achieved using embeddings such as aluminum, and specific predetermined values can be achieved as desired. You can choose.

In general, the selection of each matrix component is such that it is cycled through the regenerator at a lower speed. Catalysts with high density have a greater density than catalysts that require frequent regeneration. . For example, in the case of a mixed catalyst system containing medium-pore and large-pore crystalline silicate zeolites , if it is desired to reduce the residence time of the intermediate pore zeolite in the regenerator, The overall packing density of pore zeolite particles is 0.6 to 4.0 g including matrix components. /l, preferably 2.0 to 3.0 g/l, large pore zeolite The overall packing density of catalyst particles, including matrix and gas components, is preferably 0°4 to 1.1 g/l. A density of preferably 0.6 to 1.0 g/l is advantageous.

Again, in the case of mixtures of medium-pore and large-pore zeolite catalysts, each catalyst component Another useful method for adjusting the density of minutes is to use intermediate pore zeolite catalyst particles. The particles of the large pore zeolite catalyst adhere to the coke faster, resulting in a medium pore catalyst This is a method of compounding particles with a substance that increases their density. Examples of such substances As hydrated aluminum produces transitional alumina with greater coke deposition rate There is a na. This embodiment has several additional advantages. When coke is attached, The composite intermediate pore silicate zeolite catalyst is It is more resistant to the wear and tear that occurs. Individual catalyst particles have more collisions , and thus regulate the rate of large-pore zeolite catalyst particles passing through the regenerator. (when colliding with medium-pore zeolite catalyst particles, large-pore zeolite Olite catalyst particles will result in lower velocities. ) Furthermore, with coke Adhesive complexed intermediate pore zeolite catalyst particles tend to accumulate metals present in the feedstock. Ru.

As explained earlier, the relative sedimentation rate of each catalyst component is determined by the average particle size of the catalyst particles. It can be changed by changing the law. It contains zeolite catalyst particles It can be easily implemented when complexed with various matrix components. considerably different average grains Between two catalyst components of child size, the larger one is 12 faster than the smaller one. It tends to be discharged from the regenerator. For example, the residence time of large-pore zeolite catalyst components In contrast, it is desirable to reduce the residence time of intermediate pore zeolite catalyst particles in the regenerator. If the average particle size of the medium-pore zeolite catalyst particles is larger than that of the large-pore zeolite catalyst, Make it larger than the component. For example, the average particle size of medium pore zeolite catalyst particles is 5 00 to 70000 μm1 preferably 1000 to 25000 μm; On the other hand, the average particle size of the large-pore zeolite catalyst particles is 20 to 150 μm, preferably 5 μm. It may be 0 to 1100u.

The shape or geometry of the catalyst particles also influences the relative settling rate, with irregular shapes The more regular (i.e., the more the shape deviates from spherical) the more the particles in the regenerator Residence time becomes shorter. Irregularly shaped particles crush catalyst-matrix extrudates It can be easily and easily obtained by can.

As will be appreciated by those skilled in the art, the settling rate of a particular catalyst component is determined by the following three factors: That is, it may be due to the interaction of density, average particle size, and particle shape. cormorant. Factors can be combined so that these factors contribute to the desired result. Ru. For example, catalyst particles that are not too deactivated by coke require frequent regeneration. catalyst particles that are denser and larger in size (and more irregularly shaped at the same time) be able to. However, larger density and more Even if one of the above factors is partially can be offset by the other to give different sedimentation rates. specific catalyst components How are these factors of particle density, size and shape established for Regardless, the combined effect of these factors includes the mixed catalyst system of the present invention. It is natural that the sedimentation velocities of the components consisting of will be considerably different.

Shape-selective mesopore crystalline/licade zeolite catalysts can be used as mixed catalysts at a wide range of levels. may be present in the system. For example, the zeolite concentration of the second catalyst is (U.S. Total catalyst inventory (as in the catalytic cracking process of Patent No. 4,368,114) Exists at low levels of 0.01 to 1.0N11% based on 1nventory It may also be present as much as 25% by weight of the total catalyst system.

The reactor of the fluidized contactor (not shown) has a temperature of 482-682°C (900-1250°C). It is preferred to operate under fluid flow conditions in the range 'F). suitable source to decompose The materials are generally hydrocarbons, especially those having an initial boiling point range of at least 204°C (400'F). 50% boiling point range of at least 260°C (500°F) and at least 31 It comprises a petroleum fraction with an endpoint range of 600°F. the Hydrocarbon fractions such as gas oil, thermal oil, residual oil, cycle oil, whole top crude, Tar 5and oil, shale oil, synthetic fuel, coal cracking and hydrogenation Heavy hydrocarbon fractions derived from tar, pitch, alfalth, Hydrogenation raw materials derived from any of these are included. recognized As such, distillation of high-boiling petroleum fractions above 404°C (750°F) requires thermal Must be performed under vacuum to avoid decomposition. As used herein, boiling points are for convenience It shows the boiling point corrected for atmospheric pressure.

FIG. 1 shows a spent catalyst stream 2 from a fluid catalytic cracking reactor (not shown). show. The spent catalyst may be any fluid catalytic cracking catalyst, but preferably of particles comprising medium pore zeolite and particles comprising large pore zeolite. a combination, most preferably each comprising ZSM-5 and zeolite Y. Become. The spent catalyst stream 2 is connected to the first air stream 4 and preferably to a suitable mixed with the regenerated recycled catalyst stream 52 from standpipe 5o. It becomes a mixture. The mixture passes through the first regenerator riser 6. Preferably, The mixture was reheated with a mixture temperature of 538-677°C (1000-1250'F). Pass through riser 6 under raw conditions. The mixture is discharged from the first riser 6 and mixed It is sent to a plurality of ejection arms 14 which impart downward momentum to the object. Ejection arm 14 is housed in a riser cover 20 having an open bottom 21.

After exiting the exhaust arm 14, the mixture enters the upwardly directed combustion gas from the first catalyst bed 16. in countercurrent contact with the gas. This causes gaseous substances to be removed upwardly and away from the catalyst. , a first flue gas stream 22 is formed. The remaining catalyst from the mixture is added to the second downwardly towards the first catalyst bed 16 located in the lower portion 10 of the regenerator riser 8 Keep moving. Preferably, the bed 16 is 28°C (50°C) below the first regenerator catalyst temperature. 'F) maintained at high temperature ~760C (1400'F). The lower part 10 It has a larger inner diameter than the upper part 12 to which it is attached. 2nd air strip The catalyst bed 18 is sent to the first catalyst bed 16 via the header 19 to further promote regeneration. , thereby producing water-containing combustion gas. First flue gas stream at heat exchanger 24 Stream 18 may be preheated by indirect heat exchange with the system. flue gas 2 2 with the air stream 18, the air is heated, thereby The air becomes less dense and its ability to lift the catalyst increases. Furthermore, heat exchange Save. riser 8 to continue transport of the catalyst by removing flue gas 22 It is necessary to increase the airflow to.

This increases the amount of heat required within the riser 8. Heat exchange recovers some heat . The amount of air delivered to the first catalyst bed 16 is sufficient to sustain combustion in the bed 16. Preferably, the minimum amount is such that it can be touched without substantial hydrothermal degradation. Hydrogen is removed from the medium.

The air also removes water vapor-containing combustion gases from the catalyst bed 16.

A first portion 26 of partially regenerated catalyst is present in the air stream 18 and bed 16. The resulting combustion gases are channeled away from the first bed 16. The first portion 26 of the catalyst From the bed 16 it is passed upwardly to the upper part 12 of the second regenerator riser 8. part A second portion of the regenerated catalyst is discharged from bed 16 via discharge conduit 28. , to a fluid catalytic cracking reactor (not shown).

The first portion 26 of catalyst passes through the upper portion 12 located within the catalyst collection chamber 30. pass Portion 26 includes a plurality of holes that impart downward momentum to the catalyst from upper portion 12. It is discharged to the discharge arm 32. The ejection arm 32 is housed within the riser cover 38. The cover has an open bottom 39, and the catalyst that is fed downward is located below. countercurrent contact with the combustion gases from the second catalyst bed 34, thereby causing gaseous substances to away from the catalyst which is removed and sent downward. This removed gas is A second flue gas stream 40 exiting the bar 30 is formed with air storage in a heat exchanger 42. The ream 44 is preheated indirectly. The heat exchanger 42 is similar to the heat exchanger 24 described above. However, an air stream that conserves heat and lifts the catalyst in chamber 30 Increases Ream 44's abilities. The catalyst continues down to the second catalyst bed 34. 3rd sky The gas stream 36 is fed to the second bed via the Hesogoo 37 and is applied to the catalyst in the bed 34. Contact.

The regenerated recycled catalyst stream 52 passes through the stand vibe 50 to the second Removed from bed 34, catalyst 52 is exposed to air stream 4 and as previously described. and used catalyst 2. The resulting regenerated catalyst stream 55 is transferred to a second catalyst stream 55. The catalyst is removed from the media bed 34 via the catalyst discharge conduit 54 and placed in the fluid catalytic cracking reactor (Fig. (not shown). Preferably, the bed 34 has sufficient maximum capacity to sustain combustion. A small amount of air is supplied by air stream 36. Also, the air stream 36 is , removing water-containing combustion gases from the bed 34, thereby reducing hydrothermal degradation. preferred Specifically, the second bed 34 is at a temperature of 14°C (25°F) higher than the temperature of the first catalyst bed 16. 87 pC (1600°F), most preferably 56°C below the temperature of the first catalyst bed 16 (100'F) high temperature to 871°C (1600'F).

A second portion of regenerated catalyst is removed from bed 34 via catalyst exhaust conduit 54. and sent to a fluid catalytic cracking reactor (not shown).

Removal of catalyst from first bed 16 via conduit 28 and discharge via conduit 54 The removal of more fully regenerated catalyst from the second catalyst bed 34 increases the fluid contact The flexibility of the catalytic regenerator is improved. From floor 16 via conduit 28 The removed catalyst is not exposed to the higher temperatures of the catalyst bed 34 and is therefore not subject to thermal degradation. The possibility of Additionally, in this embodiment, the catalyst exposed to the highest regeneration temperature quantity is minimal.

This embodiment includes particles comprising intermediate pore zeolites such as ZSM-5 and zeolites. For two-phase catalyst systems using particles comprising large pore zeolites such as Lite Y. is particularly advantageous. Medium pore zeolite catalyst particles are more important than large pore zeolite catalyst particles. The large pore zeolite catalyst particles are designed to be difficult to elutriate, and the large pore zeolite catalyst particles are designed to be elutriated from the bed 16. and is entrained upwardly through the upper portion 12 of the second riser 8. intermediate pore zeola The zeolite catalyst particles have different dimensions that make them more dense than the large pore zeolite catalyst particles. (measured by average particle size), or both. The particles are designed to be more difficult to elutriate than large-pore zeolite catalyst particles. No By adopting particles with a regular shape, the particle size can be increased (in the same direction as when The effect of this can be obtained. Examples of irregularly shaped particles are extruded pellets or crushed pellets. It is Rhett. An example of a regularly shaped particle is a microsphere. Therefore, irregular particles are , are more elutriated than regular shaped particles with approximately the same particle density and hydraulic diameter. Peg. Therefore, medium-pore zeolite catalyst particles that are difficult to elutriate and large-pore zeolite particles that are easy to elutriate. In the case of two-phase systems using porous zeolite catalyst particles, the first bed is The catalyst removed from 16 is removed from second bed 34 via discharge conduit 54. The difference between large-pore zeolite catalyst particles and medium-pore zeolite catalyst particles is higher than that of medium-pore zeolite catalyst particles. has a larger ratio. This minimizes hydrothermal deactivation of the intermediate pore zeolite. . Therefore, a smaller amount of this zeolite is required to achieve the same effect. Ru.

The combustion gases from the second bed 34 are exhausted as part of the second flue gas stream 40. but is sent upwardly through the collection chamber 30 to the cyclone 60. sa Ikron 60 separates gaseous substances from entrained catalyst particles and via the head conduit 62 to the plenum chamber 70 and the third flue gas stream. plenum chamber 70 via exhaust conduit 74 as chamber 72 .

Several cyclones such as Cyclone 60 can be connected in series and/or in parallel. may be placed in the chamber 30. The solids separated by the cyclone 60 are It is returned to the second catalyst bed 34 via the prep leg 61.

A second aspect of the invention, shown in FIG. 2, includes the ejector arm 32 and riser of FIG. The combination of covers 38 has been replaced by a series of closed cyclones. Figure 1 and Components with the same numbers in FIG. 2 and FIG. American Union of Haddad et al. National Patent No. 4,404. ．． No. 095 describes a stripping section for a fluid catalytic cracking reactor. The ejection arm and riser cover applied to the section are shown. Hadano U.S. Pat. No. 4,502,947 to Do et al. The closed cyclone system used is described. As shown in Figure 2, the catalyst stream 2, air stream 4 and preferably regenerated recycled catalyst stream The stream 52 is mixed and ascends through the first regenerator riser 6 to the upper portion 112. to a second regenerator riser 108 having a lower portion 110 attached to the . Flue gas stream 22 is separated from the catalyst discharged from riser 6 and mixed The remaining catalyst from the product is sent to the first catalyst bed I6. The first portion 26 of catalyst is in bed 1 6 and upwardly through the upper portion of the second riser 108. Part 2 of the catalyst The fraction is removed from bed 16 via discharge conduit 28 to a fluidized catalytic reactor (not shown). sent to ).

The first portion 26 of the catalyst is connected to the riser cycle from the upper portion 112 to the riser 120. is discharged into the inlet conduit 114. Riser Cyclone 120 is a riser cyclone A first cyclone 130 is connected to the first cyclone 130 by an overhead conduit 122 . 1st Cyclone 130 is connected to a second cyclone (not shown) by a conventional closed conduit (not shown). (without). The first cyclone 130 or the second cyclone in series (Fig. (not shown) is routed to the collector via overhead conduit 132. A second flue gas stream exiting 30 is formed.

A riser cyclone overhead conduit 122 is attached to the cyclone 120. a lower vertical conduit 124 which is inserted into an upper vertical conduit 126. It is. Conduit 126 is in turn attached to first cyclone inlet conduit 128. There is. An annular portion is formed at the opening of conduit 124 and conduit 126, and the catalyst bed 34 is A portion of these gases may be sent to upper conduit 126. Preferably, the annular portion has 1 ．． The gas flows through the annular section at a speed of 5 to 30.5 m/sea (5 to 100 ft/5ee). It is sized to fit inside. The contact separated by cyclones 120 and 130 The medium is passed through gimbles 121 and 131 to second catalyst bed 34. No. The combustion gases from the second bed 34 are not exhausted as part of the second flue gas stream; is sent to one or more cyclones 60 via an overhead conduit 62. to the plenum chamber 70 and via the exhaust conduit 74 to the third flue gas station. It is sent as ream 72. The catalyst separated by the cyclone 60 is transferred to the zipleg 6 1 and returned to the catalyst bed 34.

In a third aspect of the invention, shown in FIG. 3, the ejection arm 14 and riser of FIG. - combination with cover 20 is replaced by a series of closed cyclones. 1st In Figures 3 to 3, the same numbers refer to the same functions. Haddad et al. No. 4,404.095 describes the stripping section of a fluid catalytic cracking reactor. The ejection arm and riser cover applied to the engine are shown. Hadanod's U.S. Pat. No. 4,502,947 includes A closed cyclone system is described. As shown in Figure 3, the catalyst stream 2, air stream 4 and preferably regenerated recycled catalyst stream. The system 52 is mixed and ascends through the first regenerator riser 142 to the upper section 11. a second regenerator riser 108 having a lower portion 110 attached to the second regenerator riser 108; Ru.

A closed cyclone system exhausts the riser 142, as described below. A flue gas stream 22 is separated from the collected catalyst. The remaining catalyst from the mixture is is sent to the first catalyst bed 16. The first portion 26 of the catalyst is located above the second riser 108. It is sent upwardly from the floor 16 through section 112. The second part of the catalyst is removed is removed from bed 16 via conduit 28 and into a fluid catalytic cracking reactor (not shown). Sent.

Closed cyclone system for separating flue gas from catalyst discharged from riser The system is explained below. The catalyst is transferred from the riser 142 to the riser cyclone 150. The riser cyclone inlet conduit 144 is discharged to the riser cyclone inlet conduit 144. riser cyclone 15 0 is connected to the first cyclone 160 by the riser cyclone overhead conduit 152. It is connected to the. A conventional closed conduit (not shown) connects the first cyclone 160. It may be attached to a second cyclone (not shown). First cyclone 160 or direct Overhead gas from the second cyclone in the row (not shown) is Forming a flue gas stream exiting second riser 108 via conduit 162 .

The riser cyclone over nod conduit 152 is attached to the cyclone 150. a lower vertical conduit 154 which is inserted into an upper vertical conduit 156. has been done. Conduit 156 is in turn attached to first cyclone inlet conduit 158. ing. An annular portion is formed between conduit 154 and conduit 156 to form catalyst bed 16. A portion of the gas from can be sent to upper conduit 156. Preferably, the annular portion is The dimensions are such that it passes through the annular portion at a speed of 5 to 100 ft/sec. sa The catalyst separated in Iclons 150 and 160 is separated by zip legs 151 and 1 61 to the second catalyst bed 16.

The fluid catalytic cracking catalyst is regenerated in stages, with the water-containing flue gas being catalyzed at each stage. The present invention has the advantage that hydrothermal deterioration is minimized by rapid removal from Ru. This rapid removal is facilitated by removing the flue gas from the catalyst. elutriated Intermediate pore zeolites such as ZSM-5 which have hard catalyst particles and are easily elutriated Using a two-phase catalyst system containing large pore zeolites such as Zeolite Y as catalyst particles. The present invention is particularly useful when In the present invention, a large pore zeolite catalyst is used as a third ( medium pore zeolite from large pore size zeolite catalyst before sending to regeneration stage (hottest) Separating a substantial portion of the catalyst. This allows the intermediate pore zeolite catalyst to enter the third stage. Prevents exposure to high temperatures. This means that medium pore zeolite is similar to large pore zeolite. The coke is not deactivated by the coke and therefore the first step is required to completely remove the coke. This is particularly advantageous since three higher temperatures are not required. Therefore, the same effect In order to achieve this it is necessary to use a lower concentration of mesopore zeolite.

Having shown and described particular embodiments of the method of the invention, the spirit and scope of the invention have been illustrated and described. It is clear that many modifications can be made without departing from the above. Therefore, the present invention Not to be limited by the above description, but only by the claims appended hereto. It is something.

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Claims (28)

[Claims] 1. A method for regenerating a spent fluid catalytic cracking catalyst stream, the method comprising: Particles of cracking catalyst that require relatively frequent regeneration as the first catalyst component and The second catalyst component contains particles of catalyst that require less regeneration than the first catalyst component. and at least one physical property of the particles of the first catalyst component is such that at least one physical property of the particles of the second catalyst component is At least one physical property is sufficiently different to allow separation of these catalyst components. a spent fluid catalytic cracking catalyst stream with a first oxygen-containing stream; producing a mixture; sending the mixture through a first regenerator riser at catalyst regeneration conditions; A first flue gas stream is separated from the discharged mixture and the remainder of the mixture is sent to a second recycle. feeding a first catalyst bed located in the lower portion of the generator riser; regenerating the catalyst in the first bed by contacting the first bed with a second oxygen-containing stream; process, Upstreaming the first portion of partially regenerated catalyst from the first bed to the upper portion of the second riser feeding the partially regenerated second portion downwardly from the first bed; separating a second flue gas from the exhausted first portion of the partially regenerated catalyst; sending the remainder of the portion to a second catalyst bed located in a collection chamber; regenerating the catalyst in the second bed by contacting the second bed with a third oxygen-containing stream; process, removing a first portion of regenerated catalyst from a second bed; and a step of removing a first portion of regenerated catalyst from a second bed; comprising a step of extracting a third flue gas from the gas phase, The first catalyst portion of the first bed is sent to the upper portion of the second riser, requiring more frequent regeneration. The required catalyst comprises large pore zeolite catalyst particles and requires less regeneration. The catalyst comprises intermediate pore zeolite catalyst particles, and the intermediate pore zeolite catalyst particles are less susceptible to elutriation than large-pore zeolite catalyst particles, and are partially elutriated from the first catalyst bed. A second portion of partially regenerated catalyst is added to a second portion of partially regenerated catalyst from the first catalyst bed. Large pore zeolite catalyst particles versus large pore zeolite catalyst particles of medium pore zeolite catalyst particles larger than 1 part has a proportion; Thereby, the medium pore zeolite catalyst particles are transferred to the large pore zeolite catalyst particles before regeneration in the second bed. separated from the light catalyst and then directly into the riser conversion zone of the fluid catalytic cracking reactor. How to be sent. 2. The mixture passes through the first riser at regeneration conditions including a mixture temperature of 538-677°C. and maintain the first bed at a temperature between 28°C and 760°C above the mixture temperature; Claim 1, wherein the temperature is maintained at a temperature of 14°C to 871°C higher than the first bed temperature. Method described. 3. The average particle density of medium-pore zeolite catalyst particles is the average particle density of large-pore zeolite catalyst particles. The method according to claim 1 or 2, wherein the particle density is greater than the particle density. 4. The average particle size of medium-pore zeolite catalyst particles is the average particle size of large-pore zeolite catalyst particles. 4. A method according to claim 1, 2 or 3, wherein the particle size is larger than the particle size. 5. Medium-pore zeolite catalyst particles tend to be more irregular than large-pore zeolite catalyst particles. The method according to any one of claims 1 to 4. 6. The mixture discharged from the first riser radiates from the upper discharge end of the first riser. It is sent downward by contacting a plurality of first arms extending in a shape, and a plurality of The first arm resides within the first riser cover and extends upward within the first riser cover. the first by contacting the conveyed gas stream and the discharged mixture in countercurrent flow. separating the flue gas streams and thereby extracting the first flue gas from the discharged mixture; 6. The method according to any one of claims 1 to 5, for removing. 7. The first portion of the catalyst discharged from the second riser is at the upper discharge end of the second riser. It is sent downward by contacting a plurality of second arms extending radially from the , the plurality of second arms are within the second riser cover, and the plurality of second arms are within the second riser cover. contacting the upwardly directed gas stream and the discharged first portion in countercurrent flow; to separate the second flue gas stream, thereby exhausting the second flue gas stream. 7. The method of claim 6, wherein the method is removed from the first portion. 8. A closed sialon system directs the second flue gas stream from the second riser. 2. A method according to claim 1, further comprising separating from the first portion of the discharged catalyst. 9. A closed cyclone system directs the first flue gas stream from the first riser. 2. A method as claimed in claim 1, characterized in that it is separated from the discharged mixture. 10. A closed cyclone system directs the first flue gas stream to the first riser. 9. The method according to claim 8, wherein the mixture is separated from the discharged mixture. 11. sending the second and third oxygen-containing streams to the first and second catalyst beds, respectively; indirect heat exchange with the first and second flue gas streams, respectively, before Claim further comprising the step of heating the second and third oxygen-containing streams by The method described in item 1. 12. A portion of the second regenerated catalyst is recycled from the second bed to the first regenerator riser. The method of claim 1, further comprising the step of: 13. A portion of the second regenerated catalyst is removed from the lower portion of the second catalyst bed and then 1 regenerator riser and another portion of the 2nd regenerated catalyst to the 2nd catalyst bed. 13. The method of claim 12, wherein the method is performed by removing the material from a lower portion of the container. 14. Cyclonic separation of gaseous substances in the upper part of the collection chamber 14. The method of claim 13, further comprising producing a third flue gas. 15. Large-pore zeolites include zeolite X, zeolite Y, zeolite REY, and zeolite Olite USY, zeolite RE-USY, mordenite and mixtures thereof The intermediate pore zeolite is selected from the group consisting of ZSM-5, ZSM-11, Z SM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48? 2. The method of claim 1, wherein the method is selected from the group consisting of: 16. The large pore zeolite is Zeolite Y, and the medium pore zeolite is ZSM-5. 16. The method of claim 15. 17. Fluidized contact comprising ZSM-5-containing catalyst particles and zeolite Y catalyst particles A method for regenerating spent fluid catalytic cracking catalyst from a catalytic cracking reactor, the method comprising: mixing the spent catalyst with a second portion of regenerated catalyst and a first oxygen-containing stream; under regeneration conditions including a step of producing a mixture by sending the mixture through the first regenerator riser; a second regenerator riser which has a larger internal diameter than the upper part. step of separating a first portion of flue gas from the discharged mixture; The mixture is passed through the riser cover to the first riser located at the lower part of the second riser. directing downwardly into a catalyst bed, contacting the first bed with a second oxygen-containing gas stream; , in the first bed at a temperature of at least 28°C above the mixture temperature to 760°C. a step of regenerating a catalyst by maintaining a first portion of the partially regenerated catalyst; Partially regenerated catalyst sent from the upper part of the first bed to the upper part of the second riser from the lower part of the first bed, the ZSM-5 catalyst was removed from the zeolite The second part of the first bed catalyst is substantially less susceptible to elutriation than the medium flow, and the second part of the first bed catalyst A process having a ratio of ZSM-5 to zeolite Y greater than Cheng, discharging the first portion from the second riser into an enlarged catalyst collection chamber; the first portion from the second riser to the second catalyst bed located in the lower portion of the collection chamber. The process of sending it downward, the second flue gas stream to the first portion before discharging the first portion from the second riser; The process of taking it out from contacting the second bed with a third oxygen-containing gas stream to bring the second bed below the first bed temperature; The catalyst is grown in the second bed by maintaining the temperature at least 14°C higher to 871°C. A step of regenerating a second portion of the regenerated catalyst from the second bed to the first riser helicycle. The process of removing a first portion of regenerated catalyst from a second bed; a third flue gas stream; from the gas phase of the collection chamber above the second floor. A method comprising: 18. A method for regenerating a spent fluid catalytic cracking catalyst stream, the method comprising: mixing the spent catalyst stream with the first oxygen-containing stream to form a mixture; process, sending the mixture through a first regenerator riser under catalyst regeneration conditions; discharging the mixture from the riser; Separate the first flue gas stream from the discharged process and send the remainder of the mixture to the second regeneration feeding a first catalyst bed located in the lower part of the riser; regenerating the catalyst in the first bed by contacting the first bed with a second oxygen-containing stream; process, and the first flue gas stream before contacting the second oxygen-containing stream with the first catalyst bed; heating the second oxygen-containing stream by indirect heat exchange with A method comprising: 19. A first portion of the catalyst is sent upwardly from the first bed to the upper portion of the second riser; The process of removing a second portion of catalyst from one bed downwards, from the second riser to the catalyst collection chute. a step of discharging the first part into the chamber, and a second flue gas stream from the discharged first part; the stream is separated and the remainder of the first portion is sent to a second catalyst bed located in a collection chamber. step, catalyzing the catalyst in the second bed by contacting the second bed with a third oxygen-containing stream. The process of regenerating the second flue gas stream before contacting the third oxygen-containing stream with the second catalyst bed; heating the third oxygen-containing stream by indirect heat exchange with discharging a portion of the regenerated catalyst from the second bed and venting the collection chamber; Removing a third flue gas stream from the phase 19. The method of claim 18, further comprising: 20. Before regenerating the catalyst in the first bed, the large pore zeolite catalyst is replaced with a medium pore zeolite catalyst. Claims that separate the particles and then send them directly to the riser conversion zone of the fluid catalytic cracking reactor The method described in item 1. 21. An apparatus for regenerating a spent fluid catalytic cracking catalyst stream, the apparatus comprising: comprising particles of first and second catalyst components, wherein the particles of the first catalyst component are first and second catalyst components; particles of the second catalyst component based on at least one different physical property of the particles of the second component; The spent catalyst stream and the first oxygen-containing stream are separated from the a first regenerator riser for passing the mixture of streams under catalyst regeneration conditions; , means for discharging the mixture from the first riser, a second regenerator riser, A first flue gas stream is separated from the discharged mixture and the remainder of the mixture is sent to a second recycle. a first means for feeding a first catalyst bed located in a lower portion of the bioreaser; Contacting the catalyst in the first bed with a second oxygen-containing stream, thereby regenerating the first bed catalyst. means to live, means for conveying a first portion of catalyst upwardly from a first bed to an upper portion of a second riser; and a conduit for withdrawing a second portion of catalyst downwardly from the first bed. means for discharging the first portion from the second riser into the catalyst collection chamber; Separating the second flue gas from the discharged first part and disposing the remainder of the first part in a collection chamber. a second means for transporting the catalyst in the second bed to a third oxygen-containing stage; means for contacting the catalyst with the catalyst, thereby regenerating the second bed catalyst; a conduit for removing a portion of the regenerated catalyst from the second bed; and means for removing the third flue stream from the gas phase of the collection chamber; A device comprising: 22. the second and second flue gas streams by indirect heat exchange with the first and second flue gas streams; Claim 2 further comprising means for heating the third oxygen-containing stream. The device according to item 1. 23. A first means for separating and delivering the catalyst from the flue gas is discharged from the first riser. having a plurality of downward arms extending in a radial shape and an open bottom surrounding the arms; 22. The apparatus of claim 21, further comprising a first riser cover. 24. A second means for separating and delivering the catalyst from the flue gas discharges from the second riser. An open bottom is formed by surrounding a plurality of downward arms extending in a radial shape and a second arm. 24. The apparatus of claim 23, further comprising a second riser cover having a second riser cover. 25. A second means for separating and delivering the catalyst from the flue gas is attached to the second riser. 24. The apparatus of claim 23, comprising a closed cyclone system. 26. A first means for separating and delivering the catalyst from the flue gas is attached to the first riser. 26. The apparatus of claim 25, comprising a closed cyclone system. 27. A first means for separating and delivering the catalyst from the flue gas is attached to the first riser. 24. The apparatus of claim 23, comprising a closed cyclone system. 28. ZSM-5 catalyst particles and zeolite Y catalyst particles from fluid catalytic cracking reactor an apparatus for regenerating a spent fluid catalytic cracking catalyst stream comprising So, Under regeneration conditions, the spent catalyst, the regenerated recycled catalyst and the first oxygen-containing a first regenerator riser for passing the mixture of reams; a second regenerator riser comprising an upper portion and a lower portion; from the first riser to the lower part of the second regenerator riser and the mixture from the first riser to the second regenerator riser. means for feeding a first catalyst bed located in the lower portion of the riser; means for separating a first portion of flue gas from the discharged mixture, the means for separating a first portion of the flue gas from the discharged mixture; means comprising a riser cover surrounding the means for conveying contacting the catalyst in the first bed with a second oxygen-containing gas stream, thereby means for regenerating the catalyst from the upper part of the first bed to the upper part of the second riser. means for delivering the first portion and removing the second portion of the catalyst from the lower portion of the first bed; means to an enlarged catalyst collection chamber comprising an upper portion and a lower portion, the first portion being connected to the second portion; discharge from the riser into an expanded catalyst collection chamber and collect the first portion from the second riser. means for feeding a second catalyst bed located in the lower part of the collection chamber; a second flue gas stream from the first section before discharging the first section from the second riser; means for removing the gas, the catalyst is contacted with a third oxygen-containing gas stream in a second bed; a means for regenerating the second bed catalyst, thereby providing a means for regenerating the regenerated recycled catalyst. a conduit for recycling from the second floor to the first riser; a conduit for removing a first portion of regenerated catalyst from a second bed, a conduit above the second bed; Means for removing third flue gas from the gas phase of the collection chamber It consists of ZSM-5 catalyst particles are significantly less elutriated than zeolite Y catalyst particles and are The second part of the catalyst is a larger ZSM-5 zeolite Y than the first part of the first bed catalyst. A device designed to have a proportion of