WO1991003528A1

WO1991003528A1 - Fluid catalytic cracking operation with a mixed catalyst system

Info

Publication number: WO1991003528A1
Application number: PCT/US1989/003844
Authority: WO
Inventors: Joseph Anthony Herbst; Hartley Owen; Paul Herbert Schipper
Original assignee: Mobil Oil Corporation
Priority date: 1989-09-06
Filing date: 1989-09-06
Publication date: 1991-03-21

Abstract

A fluid catalytic cracking method which comprises: (a) cracking a hydrocarbon feed stock in the presence of a mixed catalyst system which comprises particles of a first, amorphous cracking catalyst and/or large crystalline cracking catalyst component which requires frequent regeneration in a catalyst regeneration zone and particles of a second, shape selective crystalline silicate zeolite catalyst component which is less coke deactivated than the first catalyst component and requires less frequent regeneration than the latter, there being a sufficient difference between one or more of the characterizing physical properties of each catalyst component that the rate of circulation of particles of second catalyst component through the regeneration zone is, on the average, less than that of particles of first catalyst component, said cracking providing a product rich in C2-6 olefins; and, (b) catalytically converting C2-6 olefins obtained from step (a) to a product containing gasoline and distillate.

Description

Fluid catalytic cracking operation with a mixed catalyst system

This invention relates to a catalytic cracking process employing a mixed catalyst system and, more particularly, to such a process which emphasizes the production of light olefin for downstream conversion to distillate and other products.

In known and conventional fluidized catalytic cracking processes, a relatively heavy hydrocarbon feedstock, e.g., a gas oil, admixed with a suitable cracking catalyst, e.g., a large pore crystalline silicate zeolite such as zeolite Y, to provide a fluidized suspension is cracked in an elongated reactor, or riser, at elevated temperature to provide a mixture of lighter hydrocarbon products. The gasiform reaction products and spent catalyst are discharged from the riser into a separator, e.g., a cyclone unit, located within the upper section of an enclosed stripping vessel, or stripper, with the reaction products being conveyed to a product recovery zone and the spent catalyst entering a dense catalyst bed within the lower section of the stripper. In order to remove entrained hydrocarbon product from the spent catalyst prior to conveying the latter to a catalyst regenerator unit, an inert stripping gas, e.g., steam, is passed through the catalyst where it desorbs such hyrocarbons conveying them to the product recovery zone. The fluidized catalyst is continuously circulated between the riser and the regenerator and serves to transfer heat from the latter to the former thereby supplying the thermal needs of the cracking reaction which is endothermic.

Particular examples of such catalytic cracking processes are disclosed in M.S. Patent Nos. 3,617,497, 3,894,932, 4,309,279 and 4,368,114 (single risers) and U.S. ^patent Nos. 3,748,251,

3,849,291, 3,894,931, 3,894,933, 3,8? ,4, 3,894,935, 3,926,778, 3,928,172, 3,974,062 and 4,116,814 (multiple risers). F-4019 --2-

Several of these processes employ a mixture of catalysts having different catalytic properties as, for example, the catalytic cracking process described in U.S. Patent No. 3,894,934 which utilizes a mixture of a large pore crystalline silicate zeolite cracking catalyst such as zeolite Y and shape selective medium pore crystalline silicate zeolite such as ZSM-5. Each catalyst contributes to the function of the other to produce a gasoline product of relatively high octane rating.

In this and other fluidized catalytic cracking operations employing mixtures of large and medium pore size crystalline silicate zeolite catalysts where catalyst separated from the product effluent is conveyed to a stripper and from there to a catalyst regenerating zone, regardless of the nature of the catalyst introduction at start-up, once steady-state operation has been achieved, the two types of catalyst will become fairly uniformly mixed and will circulate throughout the system at or the same rate. This arrangement is subject to a significant disadvantage. While the large pore zeolite cracking catalyst cokes up relatively quickly and must therefore be regenerated at frequent intervals, this is not the case with the medium pore zeolite catalysts which can maintain their catalytic activity over many more cycles of operation. However, since the large and medium pore zeolite catalysts are in intimate admixture, heretofore there has been no practical means of conveying only the large pore zeolite catalyst to the catalyst regenerator unit or, what amounts to the same thing, keeping the medium pore zeolite catalyst, or at least most of it, on the average out of the regenerator.

Thus, a principal disadvantage resulting from the use of mixed catalyst systems in known fluidized catalytic cracking operations is that the medium pore zeolite catalyst component is subjected to the harsh hydrotheππal conditions of the catalyst regenerator unit even though it does not require regeneration F-4019 •3 —

.anywhere near the rate at which the large pore zeolite cracking component must be regenerated. The medium pore zeolite is therefore needlessly subjected to hydrothermal deactivation at a much greater rate than is necessary for it to function. U.S. Patent No. 4,116,814 describes a multiple riser fluidized catalytic cracking operation utilizing a mixture of large and medium pore crystalline zeolite catalysts which differ in particle size and/or density as to facilitate their separation in a common catalyst regeneration unit. There is, however, no hint in this patent of preventing the transfer or reducing the rate of circulation of medium pore crystalline zeolite to and through the catalyst regeneration unit.

U.S. Patent No. 4,287,088 describes a process and system for the segregation of used contaminated catalyst into fractions according to particle density differences. No mention is made of mixed catalyst systems.

This invention provides a method for maximizing distillate production in a fluid catalytic cracking method which comprises : a) cracking a hydrocarbon feed stock in the presence of a mixed catalyst system which comprises particles of a first, relatively hydrothermally stable amorphous cracking catalyst and/or large crystalline cracking catalyst component which requires frequent regeneration in a catalyst regeneration zone and particles of a second, shape selective crystalline silicate zeolite catalyst component which requires less frequent regeneration than the latter, there being a sufficient difference between one or more of the characterizing physical properties of each catalyst component that the rate of circulation of particles of second catalyst component through the regeneration zone is, on the average, less than that of F-4019 -_4__

particles of first catalyst component, said cracking providing a product rich in c olefins; and, b) catalytically converting C₂_₆ olefins obtained from step (a) to a product containing gasoline and distillate. The term "catalyst" as used herein shall be understood to apply not only to a catalytically active material but to one which is composited with a suitable matrix component which may or may not itself be catalytically active.

Carrying out catalytic cracking employing the foregoing mixed catalyst system does much to overcome a major drawback of known and conventional cracking operations employing mixed catalyst systems in which both catalyst components circulate through the catalyst regeneration zone at the same rate. As applied, for example, to a fluidized catalytic cracking process in which a cracking catalyst requiring frequent regeneration such as zeolite Y is employed in combination with a shape selective medium pore crystalline silicate zeolite catalyst requiring comparatively infrequent regeneration such as ZSM-5, the present invention makes it possible to sustain relatively high levels of activity of the latter catalyst for much longer average periods than would otherwise be the case due to the reduced incidence of its exposure to the catalyst-degrading environment of the regenerator zone. This, in turn, permits the refiner to take greater advantage of the unique catalytic capabilities of ZSM-5 in a catalytic cracking operation. Fig. 1 illustrates a fluidized catalytic cracking operation carried out in a single riser cracking unit integrated with a catalyst regenerator unit and employing a mixed catalyst system in accordance with this invention to maximize production of C₂_, olefins; Fig. 2 is a flow diagram illustrating an overall process for conversion of the C^ c olefins from the process of Fig. 1 to distillate; and, F-4019 — 5 —

Fig. 3 is a flow diagram of an alternative process for obtaining maximum production of distillate in accordance with the invention.

Conventional cracking catalyst components are generally amorphous silica-alumina and crystalline silica-alumina. Other materials said to be useful as cracking catalysts are the crystalline silicoaluminophosphates of U.S. Patent No. 4,440,871 and the crystalline metal aluminophosphates of U.S. Patent No. 4,567,029. However, the major conventional cracking catalysts presently in use generally comprise a large pore crystalline silicate zeolite, generally in a suitable matrix component which may or may not itself possess catalytic activity. These zeolites typically possess an average cryst."Ographic pore dimension of 7.0 _η x 10 mm and above for their majoi pore opening. Representative crystalline silicate zeolite cracking catalysts of this type include zeolite X (U.S. Patent No. 2,882,244), zeolite Y (U.S. Patent No.

3,130,007), zeolite ZK-5 (U.S. Patent No. 3,247,195), zeolite ZK-4

(U.S. Patent No. 3,314,752), synthetic mordenite, dealuminized synthetic mordenite, merely to name a few, as well as naturally occurring zeolites - ich as chabazite, faujasite, mordenite, and the like. Also useful _re the silicon-substituted zeolites described in U.S. Patent No. 4,503,023. Zeolite Beta is yet another large pore crystalline silicate which can constitute a component of the mixed catalyst system utilized herein.

It is, of course, within the scope of this invention to employ two or more of the foregoing amorphous and/or large pore crystalline cracking catalysts. It is further contemplated that th ^• mixed catalyst system can be made up solely of two or more amorphous and/or large pore crystalline silicate cracking catalysts provided at least one catalyst requires frequent regeneration and another catalyst in the system needs regeneration only on a relatively infrequent basis. Thus, for example, a mixed catalyst system in F-4019

accordance with the invention can be made up of zeolite Y, a catalyst which requires frequent regeneration but is fairly stable under the conditions prevailing in the regenerator, and zeolite Beta, a catalyst which need not be regenerated as frequently as zeolite Y and this which is needlessly subjected to degradation under the harsh conditions characteristic of most regenerating operations. Preferred large pore crystalline silicate zeolite components of the mixed catalyst composition herein include the synthetic faujasite zeolites X and Y with particular preference being accorded zeolites Y, REY, USY and RE-USY.

The shape selective medium pore crystalline silicate zeolite catalyst is exemplified by ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar materials. U.S. Patent No. 3,702,886 describing and claiming ZSM-5 is incorporated herein by reference. Also, U.S. Reissue Patent No. 29,948 describing and claiming a crystalline material with an X-ray diffraction pattern of ZSM-5 is incorporated herein by reference as is U.S. Patent No. 4,061,724 describing a high silica ZSM-5 referred to as "siAcalite" therein. ZSM-11 is more particularly described in U.S. Patent No.

3,709,979, ZSM-12 in U.S. Patent No. 3,832,449, ZSM-23 in U.S. Patent No. 4,076,842, ZSM-35 in U.S. Patent No. 4,016,245, ZSM-38 in U.S. Patent No. 4,046,859, and ZSM-48 in U.S. Patent No. 4,375,573. The preferred shape selective medium pore crystalline silicate zeolite components of the mixed catalyst system herein are ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48 with ZSM-5 being particularly preferred.

In general, the alu inosilicate zeolites are effectively employed herein. However, zeolites in which some other framework element which is present in partial or total substitution of aluminum can be advantageous. Illustrative of elements which can be substituted for part or all of the framework aluminum are boron, F-4019 — 7-

gallium, titanium and any other trivalent ^etal which is heavier than aluminum. Specific examples of such catalysts include ZSM-5 and zeolite Beta containing boron, gallium and/or titar.ium. In lieu of, or in addition to, being incorporated into the zeoA e framework these and other catalytically active elements can also be deposited upon the zeolite by any suitable procedure, e.g., impregnation. By appropriate selection of one or more characterizing physical properties, e.g., average particle size, density and/or geometry, it is possible to segregate, or separate, particles of first catalyst component from particles of second catalyst component in the reaction zone, the stripping zone or both zones. Thus, separation of particles of first catalyst component from those of second catalyst component in the stripping zone makes it possible to selectively transfer particles of first catalyst component, i.e., the one which requires frequent regeneration, to the regeneration zone and cycle particles of second catalyst component, i.e., the one which is less coke deactivated and requires relatively infrequent regeneration, to the reaction zr without going through the regeneration zone. Alternative r in addition to such separation of the catalyst components in tht, stripping zone, it is also possible to arrange the physical properties of each catalyst component such that one of them will tend on the average to remain in the reaction zone longer than the other. For example, in accordance with this invention, one or more of the characterizing physical properties of each catalyst component can be such that the first catalyst component will possess a settling rate R-, and the second catalyst component will possess a different settling rate R₂, the difference between R, and R being such as to reduce the rate of circulation of the second catalyst component through the regeneration zone.

A variety of techniques can be used to bring about a differential in the settling rate of the catalyst components whereby the catalyst which is less coke deactivated is circulated less F-4019 -8-

frequently through the regenerator than the catalyst requiring frequent regeneration. For example, the residency time of catalyst particles in a riser is primarily dependent on two factors: the linear velocity of the fluid stream within the riser which tends to carry the entire catalyst bed/conversion products/unconverted feed up and out of the riser into the separator unit and the opposing force of gravity which tends to keep the slower moving catalyst particles within the riser. Ordinarily, in a mixed catalyst system, both catalyst components will circulate through the system at the same rate. As previously pointed out, this has proven disadvantageous to the efficiency of the system since the medium pore zeolite or other catalyst component which does not re»quire as frequent regeneration as the cracking catalyst will be needlessly subjected to the catalyst-degrading conditions of the regenerator with the result that its useful catalytic life will be shortened.

However, in accordance with this invention, it is possible to retain the less coke deactivated catalyst component within the riser, even to the point where, because of a balance between the upward velocity of this catalyst component and its settling rate, it can be made to remain more or less stationary, or suspended, at any desired level within the riser defining a zone of concentration therein. To bring about this balance or to otherwise prolong the residency time of a particular component of the mixed catalyst system within the riser, the average density, particle size and/or shape of the catalyst particles can be adjusted in a number of ways as to provide the desired settling characteristics. As a general guide, as the average particle size of the catalyst increases and/or its average particle density increases, the residency time of the catalyst will increase. Longer residency time in the riser results in lower space velocity of the catalyst particle in the riser. When the catalyst particle is the second catalyst component of the invention, such as ZSM-5, the increased residency time and reduced space velocity, in F-4019 .-9_.

the riser, has several practical advantages. Reduced effective space velocity results in increased olefins, particularly, C, and C., production. Moreover, with such increased olefin production higher octane gains are achieved.

Among the techni-ques which can be used for making one catalyst component more dense than the other is compositing e.-.ch catalyst with a matrix component of substantially different density. Useful matrix components include the following:

matrix com onent article densit ( m/ml

Combinations of two or more of these and/or other suitable porous matrix components, e.g., silica-alumina, silica-magnesia, silica-thoria, silica-alumina-zirconia, etc., can be employed for a still wider spectn I of density values from which one may select a specific predetermined value as desired.

In general, selection of each matrix component will be such that the catalyst which is to have the lower rate of circulation through the regenerator will be significantly more dense than the catalyst requiring frequent regeneration. For example, in the case of a mixed catalyst system containing medium pore and large pore crystalline silicate zeolites where it is desired to increase the residency time of the medium pore zeolite catalyst in the riser, the overall packed density of the medium pore zeolite catalyst particles inclusive of its matrix component can advantageously vary from 0.6 to 4.0 gm/ml, and preferably from 2.0 to 3.0 gm/ml, .and the overall F-4019 —10—

packed density of the large pore zeolite catalyst particles inclusive of its matrix component can advantageously vary from 0.4 to 1.1 gm/ml density, and preferably from 0.6 to 1.0 gm/ml.

Another useful technique for adjusting the density of each catalyst component, again in the case of a mixture of medium and large pore zeolite catalysts, is to composite the medium pore zeolite catalyst particles with a material which tends to coke ui faster than the particles of large pore zeolite catalyst, such resulting in an increase in the density of the former in situ. Illustrative of such materials are hydrated alumina which in situ forms a transition alumina which has a high coking rate. This embodiment possesses several additional advantages. In the coked-up state, the composited medium pore silicate zeolite catalyst is more resistant to attrition which results from collision with other particles in the riser. The individual catalyst particles can sustain more collisions and thus serve as a practical means of adjusting the velocity of the large pore zeolite catalyst particles through the riser (the latter in colliding with the medium pore zeolite catalyst particles will, as a result, have reduced velocity). In addition, the coked-up composited medium pore zeolite catalyst particles will tend to accumulate metals present in the feed.

As previously stated, the relative settling rate of each catalyst component can be selected by varying the average particle size of the catalyst particles. This can be readily accomplished at the time of compositing the catalyst particles with various matrix components. As between two catalyst components of significantly different average particle size, the larger will tend to remain within the riser longer than the smaller. Where it is desired to increase the residency time, say, of the medium pore zeolite catalyst particles in the riser over that of the large pore zeolite catalyst component, the average particle size of the former will usually be larger than that of the latter. So, for example, the F-4019 -11-

average particle size of the medium pore zeolite catalyst particles can be made to vary from 500 x 10^" mm to 70,000 x 10^" mm, and preferably from 1000 to 25,000 x 10 mm while the average particle size of the large pore zeolite catalyst particles can be made to

_3 vary from 20 to 150 x 10 mm, and preferably from 50 to 100 x

10 mm.

The shape, or geometric configuration, of the catalyst particles also affects their relative settling rates, the more irregular the sh^.De (i.e., the more the shape deviates from a sphere), the lor.__.r the residency time of the particles in the riser. Irregular-shaped particles can be simply and readily achieved by crushing the catalyst-matrix extrudate or using an extruded catalyst.

As will be .ppreciated by those skilled in the art, the settling rate for a particular catalyst component will result from the interaction of each of the three foregoing factors, i.e., density, average particle size and particle shape. The factors can be combined in such a way that they each contribute to the desired result. For example, the particles of the less coke deac ivated catalyst can simultaneously be made denser, larger and more irregular in shape than the catalyst particles requiring frequent regeneration. However, a differential settling rate can still be provided even if one of the foregoing factors partially offsets another as would be the case where greater density and smaller average particle size coexist in the same catalyst particle.

Regardless of how these factors of particle density, size and shape are established for a particular catalyst component, their combined effect will, of course, be such as to result in a significant differential in settling r_^. s of the components comprising the mixed catalyst system of this invention.

By varying the cross sectional geometry of the riser, it is possible to further prolong the residency time therein of the denser, larger and/or more irregularly shaped catalyst particles. F-4019 --12—

Numerous geometric configurations can be utilized to achieve this effect. So, for example, the riser can be made to flare outwardly for a part of its length. In one such arrangement, some portion of the upper section of the riser can be flared outwardly. The denser, larger and/or more irregularly shaped catalyst particles will tend to occupy the flared region of the riser as to constitute a zone of concentration therein.

The shape selective medium pore crystalline silicate zeolite catalyst can be present in the mixed catalyst system over widely varying levels. For example, the zeolite of the second catalyst component can be present at a level as low as 0.01 to 1.0 weight percent of the total catalyst inventory (as in the case of the catalytic cracking process of U.S. Patent No. 4,368,114) and can represent as much as 25 weight percent of the total catalyst system. The catalytic cracking unit is preferably operated under fluidized flow conditions at a temperature within the range of from 482°C (900°F) to 732°C (1350°F), a first catalyst component to charge stock ratio of from 2:1 to 15:1 and a first catalyst component contact time of from 0.5 to 30 seconds. Suitable charge stocks for cracking comprise the hydrocarbons generally and, in particular, petroleum fractions having an initial boiling point range of at least 204°C (400°F), a 50% point range of at least 260°C (500°F) and an end point range of at least 316°C (600°F). Such hydrocarbon fractions include gas oils, thermal oils, residual oils, cycle stocks, whole top crudes, tar sand oils, shale oils, synthetic fuels, heavy hydrocarbon fractions derived from the destructive hydrogenation of coal, tar, pitches, asphalts, hydrotreated feedstocks derived from any of the foregoing, and the like. As will be recognized, the distillation of higher boiling petroleum fractions above 399°C (750°F) must be carried out under vacuum in order to avoid thermal cracking. The boiling temperatures utilized herein are expressed in terms of convenience of the boiling point corrected to atmospheric pressure. F-4019 -13-

Referring now to Figure 1, a hydrocarbon feed 2 such as gas oil boiling at from 316°C (600°F) up to 649°C (1200°F) is conveyed following preheating to the bottom portion of riser 4 for admixture with hot regenerated catalyst, predominantly made up of zeolite Y, introduced by standpipe 6 provided with flov. control valve 8. A suspension of catalyst in hydrocarbon vapors at a temperature of at least 510°C (950°F), but more usually at a temperature of at least 538°C (1000°F), is thus formed in the lower portion of riser 4 for flow upwardly therethrough under hydrocarbon conversion conditions. The suspension initially formed in the riser can be retained during flow through the riser for a first catalyst component residence time in the range of from 0.5 to 15 seconds.

Further up riser 4, the catalyst-hydrocarbon suspension encounters an outwardly flared region 5 which contains a large percentage of the ZSM-5 catalyst particles of the mixed catalyst system. The ZSM-5 catalyst particles occupying this region possess a combination of density, average particle size and shape such that the linear velocity of the suspension in this region which would tend to carry the ZSM-5 catalyst particles up and out of the riser is in approximate balance with the settling rate of these particles. Such being the case, the ZSM-5 catalyst particles, or at least the bulk of them, remain more or less stationary, or suspended, in region 5 of riser 4 where they catalyze a variety of other conversions involving the hydrocarbons present in this region including selective cracking to light olefins such as C, g olefins, oligomerization, alkylation, isomerization, aromatization, etc., the result of which is to provide a gasoline product of increased RON and MON. Meanwhile, the particles of spent catalyst zeolite Y, being less dense, smaller and/or more regular in shape than the ZSM-5 catalyst particles, continue past region 5 together with the gasiform products of conversion and are ultimately discharged from the top of the riser into one or more cyclonic F-4019 ^■14—

separation zones adjacent the riser discharge as represented by cyclone separator 14. There may be a plurality of such cyclone separator combinations comprising first and second cyclonic separation means attached to or spaced apart from the riser discharge for separating catalyst particles from hydrocarbon vapors. Separated hydrocarbon vapors are conveyed from separator 14 to a plenum chamber 16 for withdrawal therefrom by conduit 18. These hydrocarbon vapors together with gasiform material separated by stripping gas as defined below are passed by conduit 18 to fractionation equipment (not shown). Spent zeolite Y catalyst particles separated from hydrocarbon vapors in the cyclonic separation means is passed by diplegs represented by dipleg 20 to a dense fluid bed of separated catalyst 22. Catalyst bed 22 is maintained as a downwardly moving fluid bed of catalyst countercurrent to rising gasiform material. The catalyst passes downwardly through a stripping zone 24 immediately therebelow and countercurrent to rising stripping gas introduced to a lower portion thereof by conduit 26. Baffles 28 are provided in the stripping zone to improve the stripping operation. The spent catalyst is maintained in stripping zone 24 for a period of time sufficient to effect a higher temperature desorption of feed-deposited compounds which are then carried overhead by the stripping gas. The stripping gas with desorbed hydrocarbons passes through one or more cyclonic separating means 32 wherein entrained catalyst fines are separated and returned to catalyst bed 22 by dipleg 34. Riser 4 may terminate in an upper enlarged portion of the catalyst collecting vessel with the commonly known bird cage discharge device or an open end "T" connection may be fastened to the riser discharge which is not directly connected to the cyclonic catalyst separation means. The cyclonic separation means may be spaced apart from the riser discharge so that an initial catalyst separation is effected by a change in velocity and direction of the discharged suspension so that vapors less encumbered with catalyst F-4019 -15-

fines may then pass through one or more cyclonic separation means before passing to a product separation step. In any of these arrangements, gasiform materials comprising stripping gas, hydrocarbon vapors and desorbed sulfur compounds are passed from the cyclonic separation means represented by separator 32 to a plenum chamber 16 for removal with hydrocarbon product? of the cracking operation by conduit 18. Gasiform material comprising hydrocarbon vapors is passed by conduit 18 to a product fractionation step not shown. Hot, stripped spent zeolite Y catalyst particles at an elevated temperature is withdrawn from a lower portion of the stripping zone by conduit 36 provided with valve 38 for transfer to a fluid bed, zeolite Y being regenerated in a catalyst regeneration zone.

Spent zeolite Y catalyst particles attain a relatively high level of hydrocarbonaceous material which is subsequently removed therefrom by regeneration with oxygen-containing regeneration gases. The stripped catalyst particles are passed by conduit 36 provided with flow control valve 38 to a catalyst regeneration unit represented by regenerator 46 containing a dense fluid bed of catalyst 4£. Regeneration gas such as air is introduced to the lower portion of regenerator 46 by air distributor 50 supplied by conduit 52. Cyclone separators 54 provided with diplegs 56 separate entrained catalyst particles from flue gases and return the separated catalyst to the fluid bed of catalyst. Flue gases pass from the cyclones into a plenum chamber and are removed therefrom by conduit 58. Hot regenerated zeolite Y catalyst is returned to the bottom of riser 4 by conduit 6 as discussed above to participate in another cycle of conversion.

From the foregoing, it will be appreciated that due to their ability to reside in riser 4 as a somewhat stationary, or suspended, zone of concentration in region 5 thereof, the ZSM-5 particles circulate through regenerator unit 46 far less frequently than the spent zeolite Y catalyst particles. As a result, the ZSM-5 F-4019 •16-

catalyst particles are retained in the catalyst inventory at a relatively high level of activity therein for a longer average period of time than would be the case were the settling rate of the particles the same as, or similar to, that of the zeolite Y catalyst particles. This, turn, permits riser 4 to be operated under more severe conditions promoting maximum conversion of charge stock to C₂_t olefins, conversion of the latter providing maximum distillate production for a given amount of feed.

As shown in Fig. 2, the product of the fluid catalytic cracking operation of Fig. 1 containing substantial quantities of C₇_₆ olefins is fractionated and the fraction containing the C₂_, olefin is converted to gasoline and distillate in a known type of operation, for example, that described in U.S. Patent No. 4,227,992. Following fractionation of the product effluent, the distillate (diesel) fraction is subjected to a hydrotreating procedure, also of a known type, to provide a finished diesel product: see, for example, U.S. Patent No. 3,980,550.

In the alternative process scheme shown in Fig. 3, the C₇ saturated hydrocarbon fraction from crude distillation is used as feed in a known type of (M-2) aromatization conversion process to provide a product rich in aromatics. Meanwhile, the gas oil and/or resid fraction from crude distillation and hydrotreated feedstocks derived therefrom are employed as feed for the mixed catalyst system fluidized cracking process illustrated in Fig. 1 to produce large quantities of C_n-6 olefins. The latter are then converted as in the process of U.S. Patent No. 4,227,992, supra, to gasoline and distillate range hydrocarbons. The C₂_, saturates resulting from the gasoline/distillate conversion can be cycled to the M-2 aromatics forming unit to alkylate the product therein, the latter being conveyed as co-feed to the gasoline/distillate conversion unit. As before, the distillate fraction recovered from the gasoline/distillate conversion zone is subjected to conventional hydrotreating to provide a high quality distillate product in high yield relative to the amount of crude initially processed. F-4019 -17-

Having thus provided a general discussion of the present invention and described specific embodiments in support thereof, it is to be understood that no undue restrictions are to be imposed by reason thereof except as provided by the following claims.

Claims

F-4019 -18-CLAIMS:

1. A fluid catalytic cracking method which is undertaken in a unit including a riser zone and a regeneration zone wherein a cracking catalyst is introduced into a bottom portion of the riser zone and out of the riser zone which method comprises: a) providing as the cracking catalyst a mixed catalyst composition comprising a first catalyst component md a second catalyst component, the first catalyst component being selected from an amorphous cracking catalyst, large pore crystalline zeolite cracking catalyst component and mixtures thereof and requiring frequent regeneration in a catalyst regeneration zone, the second component comprising particles of a material and crystalline silicate zeolite catalyst component which is less coke deactivated than the first catalyst component under fluid catalytic conditions and requiring less frequent regeneration than the first catalyst component, the material having a greater coking rate than the first component, the greater coking rate of the material imparting a greater density, particle size or both to second catalytic component compared to first catalytic component, there being a difference between density and particle size of articles of each catalyst component effective to cause the rate of circulation of paAides of the second catalyst component through the riser zone to be less than that of particles of first catalyst component, whereby the resident time of particles of the second catalyst component in the riser is greater than the residence time of particles of the first catalyst component in the riser; and, cracking a hydrocarbon feedstock, under fluid catalytic cracking conditions, in the presence of mixed catalyst and producing a product rich in C₂-C^ olefins; and b) catalytically converting C₂~C,- olefins obtained from step (a) to a product containing gasoline and distillate. F-4019 -19-

2. The method of claim 1 wherein the characterizing physical properties of the first catalyst component are such as to impart a settling rate R-, thereto and the characterizing physical properties of the second catalyst component are such as to impart a different settling rate R . thereto, there being a sufficient difference between R-, and R₂ that the rate of circulation of the second catalyst component through the regeneration zone is, on the average, less than that of the first catalyst component.

3. The method of claim 2 wherein the first catalyst component is at least one large pore crystalline silicate zeolite cracking catalyst and the second catalyst component is zeolite Beta which contains at least one framework element other than aluminum in partial cr total exchange with the aluminum and zeolite Beta which contains at least one catalytically active element deposited therein.

4. The method of claim 3 wherein the framework element other than aluminum and the catalytically active element are each selected from boron, titanium and gallium.

5. The method of claim 2 wherein the first catalyst component is at least one member of the group consisting of zeolite X, Y, REY, USY, RE-USY, mordenite, faujasite and mixtures thereof and the second catalyst component comprises zeolite Beta.

6. The method of claim 5 wherein zeolite beta contains a framework element other than aluminum.

7. The method of claim 2 wherein the first catalyst component is at least one member selected from amorphous cracking catalyst and large pore crystalline silicate cracking catalyst and the second catalyst component is a shape selective medium pore crystalline silicate zeolite.

8. The method of claim 7 wherein the shape selective medium pore crystalline silicate zeolite is at least one member of the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48. F-4019 -20-

9. The method of claim 8 wherein the shape selective medium pore crystalline silicate zeolite contains at least one framework element other than aluminum; and silicate further contains at least one catalytically active element deposited thereon.

10. The method of claim 8 wherein the framework element other than aluminum and the catalytically active element εre each selected from the group consisting of boron, titanium and gallium.

11. The method of claim 2 wherein the average particle size of the first catalyst component ranges from 20 to 150 x 10^" mm and the average particle size of the second catalyst component ranges from 500 to 70,000 x 10^" mm.

12. The method of claim 2 wherein the average packed density of the first catalyst component ranges from 0.6 to 1.0 gm/ml and the average packed density for the second catalyst component ranges from 2.0 to 3.0 gm/ml.

13. The method of claim 2 which includes passing the first catalyst component to the regeneration zone for coke removal therefrom.

14. The method of claim 1 wherein the second component is a shape selective zeolite.

15. The method of claim 2 wherein the average particle size of the second catalyst component is larger than the average particle size of the first catalyst component.

16. The method of claim 2 wherein the density of the second catalyst component is larger than the density of the first catalyst component.

17. The method of claim 2 wherein the shape of the second catalyst component particles is more irregular than the shape of the first catalyst component particles.

6276h/0613h