EP2220195A1

EP2220195A1 - Systems and methods for making a middle distillate product and lower olefins from a hydrocarbon feedstock

Info

Publication number: EP2220195A1
Application number: EP08844288A
Authority: EP
Inventors: Opinder Kishan Bhan
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2007-10-31
Filing date: 2008-10-29
Publication date: 2010-08-25
Also published as: RU2010121906A; CN102159672A; WO2009058863A1

Abstract

A system comprising a riser reactor comprising a gas oil feedstock and a first catalyst under catalytic cracking conditions to yield a riser reactor product comprising a cracked gas oil product and a first used catalyst; a intermediate reactor comprising at least a portion of the cracked gas oil product and a second catalyst under high severity conditions to yield a cracked gasoline product and a second used catalyst; a regenerator to regenerate the first used catalyst to the second catalyst; and a draw-off vessel to remove undesirable gases from the second catalyst from the regenerator.

Description

SYSTEMS AND METHODS FOR MAKING A MIDDLE DISTILLATE PRODUCT AND LOWER OLEFINS FROM A HYDROCARBON FEEDSTOCK

Field of the Invention The present disclosure relates to systems and methods for making a middle distillate product and lower olefins from a hydrocarbon feedstock. Background of the Invention

The fluidized catalytic cracking (FCC) of heavy hydrocarbons to produce lower boiling hydrocarbon products such as gasoline is well known in the art. FCC processes have been around since the 1940's. Typically, an FCC unit or process includes a riser reactor, a catalyst separator and stripper, and a regenerator. A FCC feedstock is introduced into the riser reactor wherein it is contacted with hot FCC catalyst from the regenerator. The mixture of the feedstock and FCC catalyst passes through the riser reactor and into the catalyst separator wherein the cracked product is separated from the FCC catalyst. The separated cracked product passes from the catalyst separator to a downstream separation system and the separated catalyst passes to the regenerator where the coke deposited on the FCC catalyst during the cracking reaction is burned off the catalyst to provide a regenerated catalyst. The resulting regenerated catalyst is used as the aforementioned hot FCC catalyst and is mixed with the FCC feedstock that is introduced into the riser reactor.

Many FCC processes and systems are designed so as to provide for a high conversion of the FCC feedstock to products having boiling temperatures in the gasoline boiling range. There are situations, however, when it is desirable to provide for the high conversion of the FCC feedstock to middle distillate boiling range products, as opposed to gasoline boiling range products, and to lower olefins.

However, making lower olefins requires high severity and high reaction temperature reaction conditions. These conditions normally result in low middle distillate product yield and poor middle distillate product quality. It is therefore very difficult in the conventional cracking of hydrocarbons to provide simultaneously for both a high yield of lower olefins and a high yield of middle distillate products. United States Patent Application Publication 2006/0178546 discloses a process for making middle distillate and lower olefins. The process includes catalytically cracking a gas oil feedstock within a riser reactor zone by contacting under suitable catalytic cracking conditions within the riser reactor zone the gas oil feedstock with a middle distillate selective cracking catalyst that comprises amorphous silica alumina and a zeolite to yield a cracked gas oil product and a spent cracking catalyst. The spent cracking catalyst is regenerated to yield a regenerated cracking catalyst. Within an intermediate cracking reactor such as a dense bed reactor zone and under suitable high severity cracking conditions a gasoline feedstock is contacted with the regenerated cracking catalyst to yield a cracked gasoline product and a used regenerated cracking catalyst. The used regenerated cracking catalyst is utilized as the middle distillate selective catalyst. United States Patent Application Publication 2006/0178546 allows the use of a used regenerated cracking catalyst from an intermediate cracking reactor to be used as a middle distillate selective catalyst in a riser reactor zone. United States Patent Application Publication 2006/0178546 is herein incorporated by reference in its entirety.

European Patent Specification 0 096 996 B1 discloses a process for the conversion of alcohols into petrochemicals. Catalyst used in the process may be sent to a regenerator. Catalyst used in the process may also be sent to a catalyst cooler. European Patent Specification 0 096 996 B1 is herein incorporated by reference in its entirety.

United States Patent 6,290,916 discloses a method and apparatus are disclosed for removing water from a recycle gas stream in a catalyst regeneration process. A recycle gas stream contacts catalyst and the catalyst sorbs water from the recycle gas. Some of the now-dried recycle gas recirculates to the regeneration process, thereby decreasing the water content in the regeneration process. The catalyst containing sorbed water passes to a desorption zone, where water is desorbed from the catalyst and the desorbed water is rejected from the process. This method and apparatus are useful for extending the life of catalyst in catalytic hydrocarbon processes that employ continuous or semi-continuos catalyst regeneration zones. There is also disclosed a cooling bed and a cooling zone for the catalyst particles. United States Patent 6,290,916 is herein incorporated by reference in its entirety.

United States Patent 7,276,149 discloses methods of shutting down reaction systems. The reaction systems are those that use catalysts that comprise molecular sieves, particularly metalloaluminophosphate molecular sieves, especially metalloaluminophosphate molecular sieves which are susceptible to loss of catalytic activity due to contact with water molecules. The methods provide appropriate mechanisms of stopping feed to the reactor and unloading catalyst to protect against loss of catalytic activity that can occur due to contact with water molecules. There is also disclosed regenerating a catalyst and then passing the catalyst to a catalyst cooler either internal or external to the regeneration system. United States Patent 7,276,149 is herein incorporated by reference in its entirety.

There is a need in the art to increase the output of olefins. There is a further need in the art to replace the output of heavier hydrocarbons with light olefins.

There is a further need in the art to replace the output of less desirable products with more desirable products.

There is a further need in the art to simultaneously produce middle distillate and lower olefin products from a feedstock. Summary of the Invention

In one aspect, the invention provides a system comprising a riser reactor comprising a gas oil feedstock and a first catalyst under catalytic cracking conditions to yield a riser reactor product comprising a cracked gas oil product and a first used catalyst; a intermediate reactor comprising at least a portion of the cracked gas oil product and a second catalyst under high severity conditions to yield a cracked gasoline product and a second used catalyst; a regenerator to regenerate the first used catalyst to the second catalyst; and a draw-off vessel to remove undesirable gases from the second catalyst from the regenerator.

In another aspect, the invention provides a method comprising catalytically cracking a gas oil feedstock within an FCC riser reactor zone by contacting under suitable catalytic cracking conditions within said FCC riser reactor zone said gas oil feedstock with a first catalyst to yield an FCC riser reactor product comprising a cracked gas oil product and a first used catalyst; contacting a gasoline feedstock with a second catalyst within an intermediate cracking reactor operated under suitable high severity cracking conditions so as to yield a cracked gasoline product, comprising at least one lower olefin compound, and a second used catalyst; regenerating at least one of the first catalyst and the second catalyst in a regenerator to yield a regenerated catalyst; and removing at least a portion of undesirable gases from the regenerated catalyst in a draw-off vessel.

Advantages of the invention include one or more of the following: Improved systems and methods for increased output of olefins.

Improved systems and methods for increased output of propylene and/or ethylene.

Improved systems and methods for replacing the output of heavier hydrocarbons with light olefins. Improved systems and methods for replacing the output of less desirable products with more desirable products.

Improved systems and methods to simultaneously produce middle distillate and lower olefin products from a feedstock. Brief Description of the Drawings Figure 1 illustrates a hydrocarbon feedstock conversion system.

Figure 2 illustrates an intermediate cracking reactor. Figure 3 illustrates a hydrocarbon feedstock conversion system. Detailed Description of the Invention

Figure 1 Referring now to Figure 1 , there is illustrated a process flow schematic of system 10. Gas oil feedstock passes through conduit 12 and is introduced into the bottom of FCC riser reactor 14. FCC riser reactor 14 defines an FCC riser reactor zone, or cracking reaction zone, wherein the gas oil feedstock is mixed with a catalytic cracking catalyst. Steam may also be introduced into the bottom of FCC riser reactor 14 by way of conduit 15. This steam can serve to atomize the gas oil feedstock or as a lifting fluid. Typically, when steam is used to atomize the gas oil feedstock, the amount of steam used can be in the range of from 1 to 5 or 10 weight percent of the gas oil feedstock. The catalytic cracking catalyst can be a used regenerated cracking catalyst or a regenerated cracking catalyst, or a combination of both catalysts. The used regenerated cracking catalyst is a regenerated cracking catalyst that has been used in intermediate reactor 16 in the high severity cracking of a gasoline feedstock. The used regenerated cracking catalyst passes from intermediate reactor 16 and is introduced into FCC riser reactor 14 by way of conduit 18a. Alternatively, used regenerated cracking catalyst may be sent to regenerator 20 through conduit 18b. Selector valve 19 may be used to determine how much used regenerated cracking catalyst is sent to conduit 18a and how much is sent to conduit 18b.

Regenerated cracking catalyst may also be mixed with the gas oil feedstock. The regenerated cracking catalyst passes from regenerator 20 through conduit 22. From conduit, regenerated cracking catalyst is sent to draw-off bin 80. In draw-off bin 80, inerts, gases, or other undesirable components with regenerated cracking catalyst can be removed and recycled to regenerator through conduit 82. Inerts to remove could include oxygen, nitrogen, NO_x, or other gases. The draw-off bin 80 may have a vacuum or low pressure to remove the gases from the catalyst.

The regenerated cracking catalyst is introduced by way of conduit 24 into FCC riser reactor 14 wherein it is mixed with the gas oil feedstock and/or into intermediate reactor 16 through conduit 46.

Passing through FCC riser reactor 14 that is operated under catalytic cracking conditions is a mixture of gas oil feedstock and hot catalytic cracking catalyst that forms an FCC riser reactor product comprising a mixture of a cracked gas oil product and a spent cracking catalyst. The FCC riser reactor product passes from FCC riser reactor 14 and is introduced into stripper system or separator/stripper 26.

The separator/stripper 26 can be any conventional system that defines a separation zone or stripping zone, or both, and provides means for separating the cracked gas oil product and spent cracking catalyst. The separated cracked gas oil product passes from separator/stripper 26 by way of conduit 28 to separation system 30. The separation system 30 can be any system known to those skilled in the art for recovering and separating the cracked gas oil product into the various FCC products, such as, for example, cracked gas, cracked gasoline, cracked gas oils and cycle oil. The separation system 30 may include such systems as absorbers and strippers, fractionators, compressors and separators or any combination of known systems for providing recovery and separation of the products that make up the cracked gas oil product.

The separation system 30, thus, defines a separation zone and provides means for separating the cracked gas oil product into cracked products. The cracked C2-C3 gas, cracked C4 gas, cracked gasoline and cracked gas oils respectively pass from separation system 30 through conduits 32, 33, 34, and 36. The cycle oil passes from separation system 30 through conduit 38 and is introduced into FCC riser reactor 14.

Cracked gas in conduit 32 may be primarily C2-C3 hydrocarbons, for example at least about 70, 80, or 90% C2-C3 hydrocarbons. Cracked gas in conduit 32 may be primarily a C4 hydrocarbon, for example at least about 70, 80, or 90% a C4 hydrocarbon.

Cracked gasoline in conduit 34 may be primarily C5-C9 hydrocarbons, for example at least about 70, 80, or 90% C5-C9 hydrocarbons.

Cracked gas oil in conduit 36 may be primarily C10 and heavier hydrocarbons, for example at least about 70, 80, or 90% C10 and heavier hydrocarbons.

The separated spent cracking catalyst passes from separator/stripper 26 through conduit 40 and is introduced into regenerator 20. Regenerator 20 defines a regeneration zone and provides means for contacting the spent cracking catalyst with an oxygen-containing gas, such as air, under carbon burning conditions to remove carbon from the spent cracking catalyst. The oxygen-containing gas is introduced into regenerator 20 through conduit 42 and the combustion gases pass from regenerator 20 by way of conduit 44.

The regenerated cracking catalyst passes from regenerator 20 through conduit 22. As discussed above, the regenerated cracking catalyst passes through draw-off bin 80 to remove undesirable gases. The stream of regenerated cracking catalyst passing through conduit 22 may be divided into two streams with at least a portion of the regenerated catalyst passing from regenerator 20 through conduit 22 passing through conduit 46 to the intermediate reactor 16 and with the remaining portion of the regenerated catalyst passing from regenerator 20 passing through conduit 24 to FCC riser reactor 14. To assist in the control of the cracking conditions in the FCC riser reactor 14, the split between the at least a portion of regenerated cracking catalyst passing through conduit 46 and the remaining portion of regenerated cracking catalyst passing through conduit 24 can be adjusted as required with selector valve 23.

Intermediate reactor 16 may define a dense bed fluidization zone and provides means for contacting a gasoline feedstock with the regenerated cracking catalyst contained within the intermediate reactor 16. The fluidization zone may be operated under high severity cracking conditions so as to preferentially crack the gasoline feedstock to lower olefin compounds, such as ethylene, propylene, and butylenes, and to yield a cracked gasoline product. The cracked gasoline product passes from intermediate reactor 16 through conduit 48.

Alternatively, intermediate reactor 16 may be a fast fluidized bed or riser reactor, as are known in the art.

The used regenerated cracking catalyst may pass from intermediate reactor 16 through selector valve 19 and conduit 18a and is introduced into FCC riser reactor 14, and/or used regenerated cracking catalyst may pass from intermediate reactor 16 through selector valve 19 and conduit 18b and is introduced into regenerator 20. The gasoline feedstock is introduced into the intermediate reactor 16 through conduits 50, 56, and/or 70 and steam may be introduced into the intermediate reactor 16 by way of conduit 52. The gasoline feedstock and steam are introduced into the intermediate reactor 16 so as to provide for a fluidized bed of the regenerated catalyst. A ZSM-5 additive may be added to the regenerated catalyst of the dense phase reactor 16 or introduced into the intermediate reactor 16 through conduit 54.

The cracked gasoline product of conduit 48 passes to olefin separation system 58. The olefin separation system 58 can be any system known to those skilled in the art for recovering and separating the cracked gasoline product into lower olefin product streams. The olefin separation system 58 may include such systems as absorbers and strippers, fractionators, compressors and separators or any combination of known systems or equipment providing for the recovery and separation of the lower olefin products from a cracked gasoline product. Yielded from the separation system 58 may be an ethylene product stream, propylene product stream, and butylenes product stream each of which respectively pass from the olefin separation system 58 though conduits 60, 62, and 64. Separation system 58 may also yield a cracked gasoline stream 65, which may be sent to recycle conduit 56.

Cracked gas in conduit 60 may be primarily a C2 hydrocarbon, for example at least about 70, 80, or 90% a C2 hydrocarbon. Cracked gas in conduit 62 may be primarily a C3 hydrocarbon, for example at least about 70, 80, or 90% a C3 hydrocarbon.

Cracked gas in conduit 64 may be primarily a C4 hydrocarbon, for example at least about 70, 80, or 90% a C4 hydrocarbon.

Cracked gasoline in conduit 65 may be primarily C5-C9 hydrocarbons, for example at least about 70, 80, or 90% C5-C9 hydrocarbons.

Not shown in Figure 1 is the one or more olefin manufacturing systems to which any of the lower olefin products may be passed as a polymerization feedstock to be used in the manufacture of a polyolefin.

With system 100, all of the used regenerated cracking catalyst from intermediate reactor 16 may be sent to regenerator 20 through conduit 18b, so that FCC riser reactor 14 can be operated with 100% regenerated cracking catalyst from regenerator 20 through conduit 24. Alternatively, all of the used regenerated cracking catalyst from intermediate reactor 16 may be sent to FCC riser reactor 14 through conduit 18a, so that FCC riser reactor 14 can be operated with up to 100% used regenerated cracking catalyst from intermediate reactor 16 through conduit 18a. Alternatively, a portion of the used regenerated cracking catalyst from intermediate reactor 16 may be sent to regenerator 20 through conduit 18b and a portion of the used regenerated cracking catalyst may be sent to FCC riser reactor 14 through conduit 18a, so that FCC riser reactor 14 can be operated with a customized mixture of the regenerated cracking catalyst and the used regenerated cracking catalyst, to achieve the desired process conditions. Recycling Streams

A portion, or the entire amount, of C4 gas product stream 33 may be sent to intermediate reactor by conduit 70 to increase the yield of C2 and C3 products. A portion, or the entire amount, of butylenes product stream 64 may be sent to intermediate reactor by conduits 72 and 70 to increase the yield of C2 and C3 products.

A portion, or the entire amount, of the cracked gasoline passing from separation system 30 through conduit 34 may be recycled and introduced into the intermediate reactor 16 by way of conduit 56. This recycling of the cracked gasoline product can provide for an additional conversion across the overall process system of the gas oil feedstock to lower olefins.

A portion, or the entire amount, of the cracked gas oil passing from separation system 30 through conduit 36 may be recycled and introduced into reactor 14 by way of conduit 74. This recycling of the cracked gas oil product can provide for an additional conversion across the overall process system of the gas oil feedstock to lower olefins.

Only one, or a combination of several, of the proposed recycling streams may be used to provide for additional conversion of gas oil feedstock to lower olefins.

Figure 2 Figure 2 illustrates in somewhat greater detail the intermediate reactor 16.

Intermediate reactor 16 is a vessel that defines an intermediate reaction zone 66 and a stripping zone 68. Regenerated catalyst is introduced into the intermediate reaction zone 66 by way of conduit 46, gasoline feedstock is introduced into the intermediate reaction zone 66 by way of conduits 50, 56, and/or 70, and ZSM-5 additive is introduced into the intermediate reaction zone 66 by way of conduit 54. Steam may be introduced into the stripping zone 68 by way of conduit 52 and used regenerated cracking catalyst is withdrawn from the stripping zone 68 by way of conduits 18a and/or 18b.

The systems and methods of the invention provide for the processing of a heavy hydrocarbon feedstock to selectively produce middle distillate boiling range products and lower olefins. It has been discovered that the use of an intermediate cracking reactor, which can include reactors of the type such as a dense phase reactor, or fixed fluidized bed reactor, or a riser reactor, between the catalyst regenerator and an FCC riser reactor of a conventional FCC process or unit can provide for an improved middle distillate yield and for enhanced selectivity toward the production of lower olefins.

The invention may utilize the intermediate cracking reactor to provide for the cracking of a gasoline feedstock that preferably boils in the gasoline temperature range to yield lower olefins and for the conditioning of the catalyst so that when it is used in the cracking of the FCC feedstock in the FCC riser reactor the reactor conditions are more suitable for the production of a middle distillate product.

An additional feature of the invention is that it can further include a system integrated into the process to provide for the processing of the lower olefins yielded from the intermediate cracking reactor. This olefin processing system can perform such functions as the separation of the lower olefins into specific olefin product streams, such as an ethylene product stream, a propylene product stream and/or a butylenes product stream, or any combination thereof, and the use of the lower olefins as a polymerization feed in the manufacture of polyolefins.

Figure 3

Referring now to Figure 3, there is illustrated a process flow schematic of system 110, which may be operated in a similar manner to system 10 shown in Figure 1. Gas oil feedstock passes through conduit 112 and is introduced into the bottom of FCC riser reactor 114. Steam may also be introduced into the bottom of FCC riser reactor 14 by way of conduit 115.

The used regenerated cracking catalyst passes from intermediate reactor 116 and is introduced into FCC riser reactor 114 by way of conduit 118a. Alternatively, used regenerated cracking catalyst may be sent to regenerator 120 through conduit 118b. Selector valve 119 may be used to determine how much used regenerated cracking catalyst is sent to conduit 118a and how much is sent to conduit 118b.

The regenerated cracking catalyst passes from regenerator 120 through conduit 122 and is introduced by way of conduit 124 into FCC riser reactor 114 wherein it is mixed with the gas oil feedstock. The FCC riser reactor product passes from FCC riser reactor 114 and is introduced into stripper system or separator/stripper 126.

The separated cracked gas oil product passes from separator/stripper 126 by way of conduit 128 to separation system 130. The cracked C2-C3 gas, cracked C4 gas, cracked gasoline and cracked gas oils respectively pass from separation system 130 through conduits 132, 133, 134, and 136. The cycle oil passes from separation system 130 through conduit 138 and is introduced into FCC riser reactor 114. The separated spent cracking catalyst passes from separator/stripper 26 through conduit 140 and is introduced into regenerator 120. The oxygen-containing gas is introduced into regenerator 120 through conduit 142 and the combustion gases pass from regenerator 120 by way of conduit 144.

The regenerated cracking catalyst passes from regenerator 120 through conduit 122. The regenerated cracking catalyst passes to draw-off vessel 180 where undesirable gases may be removed and sent through conduit 182 back to regenerator 120. Undesirable gases to be removed may include flue gases, CO₂, NO_x, oxygen, nitrogen, or others. Draw-off vessel 180 may remove undesirable gases with a vacuum or low pressure environment, or other systems and methods as are known in the art.

The stream of regenerated cracking catalyst passing through conduit 122 may be divided into two streams with at least a portion of the regenerated catalyst passing from regenerator 120 through conduit 122 passing through conduit 146 to the intermediate reactor 116 and with the remaining portion of the regenerated catalyst passing from regenerator 120 passing through conduit 124 to FCC riser reactor 114. To assist in the control of the cracking conditions in the FCC riser reactor 114, the split between the at least a portion of regenerated cracking catalyst passing through conduit 146 and the remaining portion of regenerated cracking catalyst passing through conduit 124 can be adjusted as required with selector valve 123.

Intermediate reactor 116 may define a dense bed fluidization zone and provides means for contacting a gasoline feedstock with the regenerated cracking catalyst contained within the intermediate reactor 116. The cracked gasoline product passes from intermediate reactor 116 through conduit 148. Alternatively, intermediate reactor 116 may be a fast fluidized bed or riser reactor, as are known in the art.

The used regenerated cracking catalyst may pass from intermediate reactor 116 through selector valve 119 and conduit 118a and is introduced into FCC riser reactor 114, and/or used regenerated cracking catalyst may pass from intermediate reactor 116 through selector valve 119 and conduit 118b and is introduced into regenerator 120. The gasoline feedstock is introduced into the intermediate reactor 116 through conduits 150 and/or 156, and steam may be introduced into the intermediate reactor 116 by way of conduit 152. A ZSM-5 additive may be added to the regenerated catalyst of the dense phase reactor 116 or introduced into the intermediate reactor 116 through conduit 154.

The cracked gasoline product of conduit 148 passes to olefin separation system 158. Yielded from the separation system 158 may be an ethylene product stream, propylene product stream, and butylenes product stream each of which respectively pass from the olefin separation system 158 though conduits 160, 162, and 164. Separation system 158 may also yield a cracked gasoline stream 165, which may be sent to recycle conduit 156.

Additional Processing Steps

A portion, or the entire amount, of C4 gas product stream 133 may be sent to reactor 180 by conduit 170 to increase the yield of C2 and C3 products. A portion, or the entire amount, of butylenes product stream 164 may be sent to reactor 180 by conduit 172 to increase the yield of C2 and C3 products.

A portion, or the entire amount, of the cracked gasoline passing from separation system 130 through conduit 134 may be introduced into reactor 180 by way of conduit 178.

A portion, or the entire amount, of the cracked gasoline passing from separation system 130 through conduit 134 may be recycled and introduced into the intermediate reactor 116 by way of conduit 156. This recycling of the cracked gasoline product can provide for an additional conversion across the overall process system of the gas oil feedstock to lower olefins. A portion, or the entire amount, of the cracked gas oil passing from separation system 130 through conduit 136 may be recycled and introduced into reactor 114 by way of conduit 174. This recycling of the cracked gas oil product can provide for an additional conversion across the overall process system of the gas oil feedstock to lower olefins.

Reactor 180 may be used to convert hydrocarbon streams into C2 and C3 product streams, such as lower olefins. Reactor 180 processes one or more streams 170, 172, 178, and/or 186, and may separate the reactor product into C2 stream 182, C3 stream 184, and C4 and heavier stream 186. C4 and heavier stream 186 may be recycled through reactor 180 to increase the yield of C2 stream 182 and/or C3 stream 184.

Reactor 180 may be any suitable reactor type used to convert hydrocarbon streams into C2 and C3 product streams, such as lower olefins. One suitable type of reactor that may be used is a propylur reactor. Propylur reactors are disclosed in U.S. Patent 5,981 ,819 and U.S. Patent Application Publication 2003/0149322. U.S. Patent 5,981 ,819 and U.S. Patent Application Publication 2003/0149322 are herein incorporated by reference in their entirety. Catalysts

A gas oil feedstock may be introduced into the bottom of an FCC riser reactor where it is mixed with hot cracking catalyst such as a regenerated cracking catalyst or a used regenerated cracking catalyst or a combination of both catalysts. The starting catalytic cracking catalyst used and regenerated to ultimately become the regenerated cracking catalyst can be any suitable cracking catalyst known in the art to have cracking activity at the elevated temperatures contemplated by the invention.

Preferred catalytic cracking catalysts include fluidizable cracking catalysts comprised of a molecular sieve having cracking activity dispersed in a porous, inorganic refractory oxide matrix or binder. The term "molecular sieve" as used herein refers to any material capable of separating atoms or molecules based on their respective dimensions. Molecular sieves suitable for use as a component of the cracking catalyst include pillared clays, delaminated clays, and crystalline aluminosilicates. Normally, it is preferred to use a cracking catalyst that contains a crystalline aluminosilicate. Examples of such aluminosilicates include Y zeolites, ultrastable Y zeolites, X zeolites, zeolite beta, zeolite L, offretite, mordenite, faujasite, and zeolite omega. Suitable crystalline aluminosilicates for use in the cracking catalyst are X and Y zeolites, for example Y zeolites.

U.S. Pat. No. 3,130,007, the disclosure of which is hereby incorporated by reference in its entirety, describes Y-type zeolites having an overall silica-to-alumina mole ratio between about 3.0 and about 6.0, with a typical Y zeolite having an overall silica-to-alumina mole ratio of about 5.0. It is also known that Y-type zeolites can be produced, normally by dealumination, having an overall silica-to-alumina mole ratio above about 6.0.

The stability and/or acidity of a zeolite used as a component of the cracking catalyst may be increased by exchanging the zeolite with hydrogen ions, ammonium ions, polyvalent metal cations, such as rare earth-containing cations, magnesium cations or calcium cations, or a combination of hydrogen ions, ammonium ions and polyvalent metal cations, thereby lowering the sodium content until it is less than about 0.8 weight percent, preferably less than about 0.5 weight percent and or less than about 0.3 weight percent, calculated as Na₂O. Methods of carrying out the ion exchange are known in the art.

The zeolite or other molecular sieve component of the cracking catalyst is combined with a porous, inorganic refractory oxide matrix or binder to form a finished catalyst prior to use. The refractory oxide component in the finished catalyst may be silica-alumina, silica, alumina, natural or synthetic clays, pillared or delaminated clays, mixtures of one or more of these components and the like. The inorganic refractory oxide matrix may comprise a mixture of silica-alumina and a clay such as kaolin, hectohte, sepiolite and attapulgite. A finished catalyst may contain between about 5 weight percent to about 40 weight percent zeolite or other molecular sieve and greater than about 20 weight percent inorganic, refractory oxide. In general, the finished catalyst may contain between about 10 to about 35 weight percent zeolite or other molecular sieve, between about 10 to about 30 weight percent inorganic, refractory oxide, and between about 30 to about 70 weight percent clay.

The crystalline aluminosilicate or other molecular sieve component of the cracking catalyst may be combined with the porous, inorganic refractory oxide component or a precursor thereof by any suitable technique known in the art including mixing, mulling, blending or homogenization. Examples of precursors that may be used include alumina, alumina sols, silica sols, zirconia, alumina hydrogels, polyoxycations of aluminum and zirconium, and peptized alumina. In one suitable method of preparing the cracking catalyst, the zeolite is combined with an alumino- silicate gel or sol or other inorganic, refractory oxide component, and the resultant mixture is spray dried to produce finished catalyst particles normally ranging in diameter between about 40 and about 80 microns. If desired, however, the zeolite or other molecular sieve may be mulled or otherwise mixed with the refractory oxide component or precursor thereof, extruded and then ground into the desired particle size range. Normally, the finished catalyst will have an average bulk density between about 0.30 and about 0.90 gram per cubic centimeter and a pore volume between about 0.10 and about 0.90 cubic centimeter per gram.

When the process is operated in the middle distillate selective mode (or diesel mode) of operation, a middle distillate selective cracking catalyst may be used. A middle distillate selective cracking catalyst is similar to the above-described preferred cracking catalyst in that it comprises a molecular sieve dispersed in a porous, inorganic refractory oxide binder, but it has some significant differences over the typical cracking catalyst, which such differences are hereafter described in more detail. The middle distillate cracking catalyst may exhibit catalytic properties that provide for the selective cracking of a gas oil feedstock to yield a cracked gas oil product that preferentially includes middle distillate boiling range products such as those in the diesel boiling range, such as from 23O⁰C. to 35O⁰C.

The middle distillate selective cracking catalyst may comprise zeolite or other molecular sieve component, an alumina component and an additional porous, inorganic refractory matrix or binder component. The middle distillate selective cracking catalyst can be prepared by any method known to those skilled in the art that provide for a catalytic cracking catalyst having the desired composition. More specifically, the middle distillate selective cracking catalyst can comprise alumina in the amount in the range of from 40 wt. % to 65 wt. %, for example from 45 wt. % to 62 wt. %, or from 50 wt. % to 58 wt. %, with the weight percent being based on the total weight of the middle distillate selective cracking catalyst, a porous inorganic refractory oxide matrix component providing a matrix surface area, and a zeolite or other molecular sieve component providing a zeolitic surface area. The alumina component of the middle distillate selective cracking catalyst can be any suitable type of alumina and from any suitable source. Examples of suitable types of aluminas are those as disclosed in U.S. Pat. No. 5,547,564 and U.S. Pat. No. 5,168,086, which are herein incorporated by reference in their entirety, and include, for example, alpha alumina, gamma alumina, theta alumina, eta alumina, bayerite, pseudoboehmite and gibbsite.

The matrix surface area within the middle distillate selective cracking catalyst that is provided by the porous inorganic refractory oxide matrix component may be in the range of from 20 to 90 square meters per gram of middle distillate selective cracking catalyst. The zeolitic surface area within the middle distillate selective cracking catalyst that is provided by the zeolite or other molecular sieve component may be less than 140 square meters per gram. In order for the middle distillate selective cracking catalyst to have the desired catalytic property of preferentially providing for the yield of middle distillate such as diesel, the portion of the surface area of the middle distillate selective cracking catalyst that is contributed by the zeolite or other molecular sieve component, i.e. the zeolitic surface area, may be less than 130 square meters per gram, for example less than 110 square meters per gram, or, less than 100 square meters per gram. The zeolite or other molecular sieve component of the middle distillate selective cracking catalyst are those aluminosilicates selected from the group consisting of Y zeolites, ultrastable Y zeolites, X zeolites, zeolite beta, zeolite L, offretite, mordenite, faujasite, and zeolite omega. The zeolitic surface area within the middle distillate selective cracking catalyst may be as low as 20 square meters per gram, but, generally, the lower limit is greater than 40 square meters per gram. The lower limit for the zeolitic surface area within the middle distillate selective cracking catalyst may exceed 60 square meters per gram, or, the zeolitic surface area may exceed 80 square meters per gram. Thus, for example, the portion of the surface area of the middle distillate selective cracking catalyst contributed by the zeolite or other molecular sieve component, i.e. the zeolitic surface area, can be in the range of from 20 square meters per gram to 140 square meters per gram, or in the range of from 40 square meters per gram to 130 square meters per gram.

The ratio of the zeolitic surface area to the matrix surface area within the middle distillate cracking catalyst is a property thereof which is important in providing for a catalyst having the desired cracking properties. The ratio of zeolitic surface area to matrix surface area, thus, may be in the range of from 1 :1 to 2:1 , for example, from 1.1 :1 to 1.9:1 , or, from 1.2:1 to 1.7:1. Considering these ratios, the portion of the surface area of the middle distillate selective cracking catalyst contributed by the porous inorganic refractory oxide matrix component, i.e., the matrix surface area, is generally in the range of from 20 square meters per gram to 80 square meters per gram. One suitable range for the matrix surface area is from 40 square meters per gram to 75 square meters per gram, or, the range is from 60 square meters per gram to 70 square meters per gram. One method by which the process conditions within the FCC riser reactor may be controlled and a desired product mix is provided is through the addition of a ZSM-5 additive into the intermediate cracking reactor, as opposed to its addition into the FCC riser reactor. The ZSM-5 additive may be introduced into the intermediate cracking reactor, in particular, when a dense phase reactor is used, into the dense phase reaction zone thereof, along or concurrently with the regenerated catalyst that is a middle distillate selective cracking catalyst. When a ZSM-5 additive is used along with the middle distillate selective cracking catalyst in the intermediate cracking reactor, an improvement in the yield of the lower olefins such as propylene and butylenes can be achieved. Thus, it is desirable to introduce into the intermediate cracking reactor, particularly when the regenerated catalyst that is being introduced therein is a middle distillate selective cracking catalyst, ZSM-5 additive in an amount upwardly to 30 weight percent, for example upwardly to 20 weight percent, or upwardly to 18 weight percent, of the regenerated catalyst being introduced into the intermediate cracking reactor. Thus, when ZSM-5 additive is introduced into the intermediate cracking reactor, the amount may be in the range of from 1 to 30 weight percent of the regenerated cracking catalyst being introduced into the intermediate cracking reactor, for example from 3 to 20 weight percent, or, from 5 to 18 weight percent.

The ZSM-5 additive is a molecular sieve additive selected from the family of medium pore size crystalline aluminosilicates or zeolites. Molecular sieves that can be used as the ZSM-5 additive include medium pore zeolites as described in "Atlas of Zeolite Structure Types," Eds. W. H. Meier and D. H. Olson, Butterworth-Heineman, Third Edition, 1992, which is hereby incorporated by reference in its entirety. The medium pore size zeolites generally have a pore size from about 0.5 nm, to about 0.7 nm and include, for example, MFI, MFS, MEL, MTW, EUO, MTT, HEU, FER, and TON structure type zeolites (IUPAC Commission of Zeolite Nomenclature). Non- limiting examples of such medium pore size zeolites, include ZSM-5, ZSM-12, ZSM- 22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, silicalite, and silicalite 2. One suitable zeolite is ZSM-5, which is described in U.S. Pat. Nos. 3,702,886 and 3,770,614, which are herein incorporated by reference in their entirety. ZSM-11 is described in U.S. Pat. No. 3,709,979; ZSM-12 in U.S. Pat. No.

3,832,449; ZSM-21 and ZSM-38 in U.S. Pat. No. 3,948,758; ZSM-23 in U.S. Pat. No. 4,076,842; and ZSM-35 in U.S. Pat. No. 4,016,245. Other suitable molecular sieves include the silicoaluminophosphat.es (SAPO), such as SAPO-4 and SAPO-11 which is described in U.S. Pat. No. 4,440,871 ; chromosilicates; gallium silicates, iron silicates; aluminum phosphates (ALPO), such as ALPO-11 described in U.S. Pat. No.

4,310,440; titanium aluminosilicates (TASO), such as TASO-45 described in EP-A No. 229,295; boron silicates, described in U.S. Pat. No. 4,254,297; titanium aluminophosphates (TAPO), such as TAPO-11 described in U.S. Pat. No. 4,500,651 ; and iron aluminosilicates. All of the above patents are incorporated herein by reference in their entirety. The ZSM-5 additive may be held together with a catalytically inactive inorganic oxide matrix component, in accordance with conventional methods.

U.S. Pat. No. 4,368,114 describes in detail the class of zeolites that can be suitable ZSM-5 additives, and such patent is incorporated herein by reference. System Operations and Conditions

In the case of the use of an FCC riser reactor that is vertically arranged, lift gas or lift steam may also be introduced into the bottom of the FCC riser reactor along with the gas oil feedstock and the hot cracking catalyst. The regenerated cracking catalyst that is yielded from the catalyst regenerator has a higher temperature than the used regenerated cracking catalyst that is yielded from the intermediate cracking reactor. Also, the used regenerated cracking catalyst has deposited thereon as a result of its use in the intermediate cracking reactor a certain amount of coke. A particular catalyst or combination of catalysts may be used to help control the conditions within the FCC riser reactor to provide for certain desired cracking conditions required to provide a desired product or mix of products.

The mixture of gas oil feedstock and hot cracking catalyst, and, optionally, lift gas or steam, passes through the FCC riser reactor wherein cracking takes place. The FCC riser reactor defines a catalytic cracking zone and provides means for providing a contacting time to allow the cracking reactions to occur. The average residence time of the hydrocarbons in the FCC riser reactor generally can be in the range of upwardly to about 5 to 10 seconds, but usually is in the range of from 0.1 to 5 seconds. The weight ratio of catalyst to hydrocarbon feed (catalyst/oil ratio) generally can be in the range of from about 2 to about 100 and even as high as 150. More typically, the catalyst-to-oil ratio can be in the range of from 5 to 100. When steam is introduced into the FCC riser reactor with the gas oil feedstock, the steam- to-oil weight ratio can be in the range of from 0.01 to 5, and, more, typically, it is in the range of from 0.05 to 1.5.

The temperature in the FCC riser reactor generally can be in the range of from about 400° C. to about 600° C. More typically, the FCC riser reactor temperature can be in the range of from 450° C. to 550° C. The FCC riser reactor temperatures may tend to be lower than those of typical conventional fluidized catalytic cracking processes; because, the inventive process is to provide for a high yield of middle distillates as opposed to the production of gasoline as is often sought with conventional fluidized catalytic cracking processes. The control of certain of the process conditions within the FCC riser reactor may be controlled by adjusting the ratio of regenerated cracking catalyst from the catalyst regenerator to used regenerated cracking catalyst from the intermediate cracking reactor that is introduced into the bottom of the FCC riser reactor.

The mixture of hydrocarbons and catalyst from the FCC riser reactor pass as an FCC riser reactor product comprising cracked gas oil product and spent cracking catalyst to a stripper system that provides means for separating hydrocarbons from catalyst and defines a stripper separation zone wherein the cracked gas oil product is separated from the spent cracking catalyst. The stripper system can be any system or means known to those skilled in the art for separating FCC catalyst from a hydrocarbon product. In a typical stripper operation, the FCC riser reactor product, which is a mixture of cracked gas oil product and spent cracking catalyst passes to the stripper system that includes cyclones for separating the spent cracking catalyst from the vaporous cracked gas oil product. The separated spent cracking catalyst enters the stripper vessel from the cyclones where it is contacted with steam to further remove cracked gas oil product from the spent cracking catalyst. The coke content on the separated spent cracking catalyst is, generally, in the range of from about 0.5 to about 5 weight percent (wt. %), based on the total weight of the catalyst and the carbon. Typically, the coke content on the separated spent cracking catalyst is in the range of from or about 0.5 wt. % to or about 1.5 wt. %.

The separated spent cracking catalyst is then passed to a catalyst regenerator that provides means for regenerating the separated spent cracking catalyst and defines a regeneration zone into which the separated spent cracking catalyst is introduced and wherein carbon that is deposited on the separated spent cracking catalyst is burned in order to remove the carbon to provide a regenerated cracking catalyst having a reduced carbon content. The catalyst regenerator typically is a vertical cylindrical vessel that defines the regeneration zone and wherein the spent cracking catalyst is maintained as a fluidized bed by the upward passage of an oxygen-containing regeneration gas, such as air.

The temperature within the regeneration zone is, in general, maintained in the range of from about 621° C. to 760° C, and more, typically, in the range of from 677° C. to 715° C. The pressure within the regeneration zone typically is in the range of from about atmospheric to about 345 kPa, for example from about 34 to 345 kPa. The residence time of the separated spent cracking catalyst within the regeneration zone is in the range of from about 1 to about 6 minutes, and, typically, from about 2 to about 4 minutes. The coke content on the regenerated cracking catalyst is less than the coke content on the separated spent cracking catalyst and, generally, is less than 0.5 wt. %, with the weight percent being based on the weight of the regenerated cracking catalyst excluding the weight of the coke content. The coke content of the regenerated cracking catalyst will, thus, generally, be in the range of from about 0.01 wt. % to or about 0.5 wt. %, for example the coke concentration on the regenerated cracking catalyst may be less than 0.3 wt. %, or less than 0.1 wt. %.

The regenerated cracking catalyst from the catalyst regenerator is passed to the intermediate cracking reactor, which can be as noted above a dense phase reactor, or a fixed fluidized bed reactor, or a riser reactor, that provides means for contacting a gasoline feedstock with the regenerated cracking catalyst and which defines a reaction or cracking zone wherein the gasoline feedstock is contacted with the regenerated cracking catalyst under suitable high severity cracking conditions, either with or without the presence of steam.

The type of intermediate cracking reactor may be a dense phase reactor, a fast fluidized bed reactor, or a riser reactor. The dense phase reactor can be a vessel that defines two zones, including an intermediate reaction or cracking or dense phase reaction zone, and a stripping zone. Contained within the intermediate reaction zone of the vessel is regenerated cracking catalyst that is fluidized by the introduction of the gasoline feedstock and, optionally, steam, which is introduced into the stripping zone. One suitable dense phase reactor design includes a dense phase reactor vessel that defines the intermediate reaction zone and the stripping zone that are in fluid communication with each other with the stripping zone located below the intermediate reaction zone. To provide for a high steam velocity within the stripping zone, as compared to its velocity within the intermediate reaction zone, the cross sectional area of the stripping zone may be less than the cross sectional area of the intermediate reaction zone. The ratio of the stripping zone cross sectional area to the intermediate reaction zone cross sectional area can be in the range of from 0.1 :1 to 0.9:1 , for example from 0.2:1 to 0.8:1 , or, from 0.3:1 to 0.7:1.

The geometry of the dense phase reactor vessel may be such that it is generally cylindrical in shape. The length-to-diameter ratio of the stripping zone is such as to provide for the desired high steam velocity within the stripping zone and to provide enough contact time within the stripping zone for the desired stripping of the used regenerated catalyst that is to be removed from the dense phase reactor vessel. Thus, the length-to-diameter dimension of the stripping zone can be in the range of from 1 :1 to 25:1 , for example, from 2:1 to 15:1 , or, from 3:1 to 10:1. The dense phase reactor vessel may be equipped with a catalyst introduction conduit that provides regenerated catalyst introduction means for introducing the regenerated cracking catalyst from the catalyst regenerator into the intermediate reaction zone of the dense phase reactor vessel. The dense phase reactor vessel is further equipped with a used regenerated catalyst withdrawal conduit that provides used regenerated catalyst withdrawal means for withdrawing used regenerated catalyst from the stripping zone of the dense phase reactor vessel. The gasoline feedstock is introduced into the intermediate reaction zone by way of a feed introduction conduit providing means for introducing a gasoline feedstock into the intermediate zone of the dense phase reactor, and the steam is introduced into the stripping zone by way of a steam introduction conduit providing means for introducing steam into the stripping zone of the dense phase reactor. The cracked gasoline product is withdrawn from the intermediate reaction zone by way of a product withdrawal conduit providing means for withdrawing a cracked gasoline product from the intermediate zone of the dense phase reactor. The intermediate cracking reactor can be operated or controlled independently from the operation or control of the FCC riser reactor. This independent operation or control of the intermediate cracking reactor provides the benefit of an improved overall, i.e., across the entire process system including the FCC riser reactor as well as the intermediate cracking reactor, conversion of the gas oil feedstock into the desired end-products of middle distillate and the lower olefins of ethylene, propylene and butylenes. With the independent operation of the intermediate cracking reactor, the severity of the FCC riser reactor cracking conditions can be reduced to thereby provide for a higher yield of middle distillate or other desired products in the gas oil reactor product, and the severity of the intermediate cracking reactor can be controlled to optimize the yield of lower olefins or other desired products. One way of controlling the operation of the intermediate cracking reactor is by the introduction of steam along with the gasoline feedstock into the intermediate cracking reactor. Thus, the dense phase reaction zone is operated under such reaction conditions as to provide for a cracked gasoline product and, for example, to provide for a high cracking yield of lower olefins. The high severity cracking conditions can include a temperature within the dense phase or intermediate reaction zone that is in the range from about 482° C. to about 871° C, for example, the temperature is in the range of from 510° C. to 871° C, or, from 538° C. to 732° C. The pressure within the intermediate reaction zone can be in the range of from about atmospheric to about 345 kPa, for example, from about 34 to 345 kPa. Steam may be introduced into the stripping zone of the intermediate cracking reactor and to be contacted with the regenerated cracking catalyst contained therein and in the intermediate reaction zone. The use of steam in this manner provides, for a given gas oil conversion across the system, an increase in the propylene yield and butylene yield. It has generally been understood by those skilled in the art that in conventional gas oil reactor cracking processes low severity gas oil reactor cracking conditions result in less lower olefins yield relative to high severity gas oil reactor cracking conditions. The use of steam in the intermediate cracking reactor may provide further enhancements in the yield of lower olefins therefrom.

The use of the steam is particularly desirable; because, for a given gas oil conversion across the process system, and in the cracking of the gasoline feedstock in the intermediate cracking reactor, it can provide for an improved selectivity toward lower olefin yield with an increase in propylene and butylenes yield. Thus, when steam is used, the weight ratio of steam to gasoline feedstock introduced into the intermediate cracking reactor, with gasoline being introduced into the reaction zone and steam being introduced into the stripping zone, can be in the range of upwardly to or about 15:1 , for example, the range may be from 0.1 :1 to 10:1 , or, the weight ratio of steam to gasoline feedstock may be in the range of from 0.2:1 to 9:1 , or, from 0.5:1 to 8:1.

Used regenerated cracking catalyst is removed from the intermediate cracking reactor and utilized as hot cracking catalyst mixed with the gas oil feedstock that is introduced into the FCC riser reactor and/or sent to the regenerator to be regenerated. One aspect of using the used regenerated cracking catalyst in the FCC riser reactor is that it provides for the partial deactivation of the regenerated catalyst prior to its use as hot cracking catalyst in the FCC riser reactor. What is meant by partial deactivation is that the used regenerated cracking catalyst will contain a slightly higher concentration of carbon than the concentration of carbon that is on the regenerated cracking catalyst. This partial deactivation of the regenerated cracking catalyst may provide for a preferred product yield when the gas oil feedstock is cracked within the riser reactor zone. The coke concentration on the used regenerated cracking catalyst is greater than the coke concentration on the regenerated cracking catalyst, but it is less than that of the separated spent cracking catalyst. The coke content of the used regenerated catalyst can be greater than 0.1 wt. % and even greater than 0.5 wt. %. For example, the coke content of the used regenerated catalyst may be in the range of from about 0.1 wt. % to about 1 wt. %, or from 0.1 wt. % to 0.6 wt. %. Another benefit provided by the use of the intermediate cracking reactor is associated with the used regenerated cracking catalyst having a temperature that is lower than the temperature of the regenerated cracking catalyst. This lower temperature of the used regenerated cracking catalyst in combination with the partial deactivation, as discussed above, may provide further benefits in a preferential product yield from the cracking of the gas oil feedstock. To assist in providing for the control of the process conditions within the FCC riser reactor and to provide for a desired product mix, the regenerated cracking catalyst can be divided into at least a portion that is passed to the intermediate cracking reactor and a remaining portion of the regenerated cracking catalyst that is mixed with the gas oil feedstock to be introduced into the FCC riser reactor. The at least a portion of the regenerated cracking catalyst introduced into the intermediate cracking reactor can be in the range of upwardly to 100 percent (%) of the regenerated cracking catalyst yielded from the catalyst regenerator depending upon the requirements of the process and the desired product yields. Specifically, however, the at least a portion of regenerated cracking catalyst will represent from about 10% to 100% of the separated regenerated catalyst withdrawn from the catalyst regenerator. Also, the at least a portion of regenerated cracking catalyst can be from about 30% to about 90%, or from 50% to 95% of the separated regenerated catalyst that is withdrawn from the catalyst regenerator. In controlling the reaction conditions within the FCC riser reactor, as already noted, a combination or mixture of used regenerated cracking catalyst from the intermediate cracking reactor and the regenerated cracking catalyst from the catalyst regenerator is introduced into the FCC riser reactor with the gas oil feedstock. The relative amount of the used regenerated cracking catalyst to the regenerated cracking catalyst is adjusted so as to provide for the desired gas oil cracking conditions within the FCC riser reactor zone; but, generally, the weight ratio of the used regenerated cracking catalyst to the regenerated cracking catalyst is in the range of from 0.1 :1 to 100:1 , for example, from 0.5:1 to 20:1 , or, from 1 :1 to 10:1. For a system operated at steady state, the weight ratio of used regenerated cracking catalyst-to-regenerated cracking catalyst approximates the weight ratio of the at least a portion of regenerated cracking catalyst passing to the intermediate cracking reactor to the remaining portion of regenerated cracking catalyst that is mixed with the gas oil feedstock introduced into the FCC riser reactor, and, thus, the aforementioned ranges are also applicable to such weight ratio. It is notable that it is not a desired aspect of the inventive process to introduce spent cracking catalyst into the intermediate cracking reactor for a variety of reasons. For instance, the spent cracking catalyst has much higher carbon content than the regenerated cracking catalyst and, thus, its activity does not favor the yielding of the more desirable lower olefins. The regenerated cracking catalyst introduced into the intermediate cracking reactor to be more than 50 weight percent of the sum weight of the regenerated cracking catalyst and spent cracking catalyst that is introduced into the intermediated cracking reactor. The amount of spent cracking catalyst introduced into the intermediate cracking reactor may be minimized and may be less than 20 weight percent of the sum weight of the regenerated cracking catalyst and spent cracking catalyst that is introduced into the intermediate cracking reactor, for example, less than 10 weight percent, or, less than 5 weight percent.

The combination of one or more of the above described process variables and operating conditions allows for the control of the conversion of the gas oil feedstock. Generally, it is desired for the gas oil feedstock conversion to be in the range of from 30 to 90 weight percent, for example, from 40 to 90 weight percent. What is meant by gas oil feedstock conversion is the weight amount of hydrocarbons contained in the gas oil feedstock that has a boiling temperature greater than 221° C. that is converted in the FCC riser reactor to hydrocarbons having a boiling temperature less than 221° C. divided by the weight amount of hydrocarbons contained in the gas oil feedstock having a boiling temperature greater than 221° C. As earlier noted, the process may be operated so as to provide for the preferential or selective yielding of middle distillate boiling range products and lower olefins.

Gas Oil Feedstock Mixtures

The gas oil feedstock may have two or more portions. The first portion of the gas oil feedstock charged to the process may be any heavy hydrocarbon feedstock that may be or is typically charged to a fluidized catalytic cracking unit that boil in the boiling range of from 200° C. to 800° C, including, for example, gas oils, resid, or other hydrocarbons. In general terms, hydrocarbon mixtures boiling in the range of from 345° C. to 760° C. can make particularly suitable feedstock first portions. Examples of the types of refinery feed streams that can make suitable gas oil feedstock first portions include vacuum gas oils, coker gas oil, straight-run residues, thermally cracked oils and other hydrocarbon streams.

The percentage of the first portion may be 100 percent, or from about 60 to about 99 percent, for example from about 70 to about 95 percent, or from about 80 to about 90 percent, with the balance being other feedstock portions, such as oils derived from vegetables and/or animals. Gasoline Feedstock Mixtures

The gasoline feedstock may have two or more portions. The first portion of the gasoline feedstock charged to the dense phase reaction zone may be any suitable hydrocarbon feedstock having a boiling temperature that is in the gasoline boiling temperature range. Generally, the gasoline feedstock first portion comprises hydrocarbons boiling in the temperature range of from about 32° C. to about 204° C. Examples of refinery streams that may be used as the gasoline feedstock first portion include straight run gasolines, naphthas, catalytically cracked gasolines, and coker naphthas.

The percentage of the first portion may be 100 percent, or from about 60 to about 99 percent, for example from about 70 to about 95 percent, or from about 80 to about 90 percent, with the balance being other feedstock portions, such as oils derived from vegetables and/or animals. Illustrative Embodiments:

In one embodiment of the invention, there is disclosed a system comprising a riser reactor comprising a gas oil feedstock and a first catalyst under catalytic cracking conditions to yield a riser reactor product comprising a cracked gas oil product and a first used catalyst; a intermediate reactor comprising at least a portion of the cracked gas oil product and a second catalyst under high severity conditions to yield a cracked gasoline product and a second used catalyst; a regenerator to regenerate the first used catalyst to the second catalyst; and a draw-off vessel to remove undesirable gases from the second catalyst from the regenerator. In some embodiments, the system also includes a recycle conduit to send at least a portion of the cracked gasoline product to the intermediate reactor, for example the cracked gasoline product comprising C4 hydrocarbons. In some embodiments, the system also includes a separator to separate the cracked gas oil product from the riser reactor into a plurality of streams. In some embodiments, the system also includes a second separator to separate the cracked gasoline product from the intermediate reactor into a plurality of streams. In some embodiments, the system also includes a third separator for separating said riser reactor product into said cracked gas oil product and said first used catalyst. In some embodiments, the system also includes a regenerator for regenerating said first used catalyst to yield a first regenerated catalyst. In some embodiments, the second catalyst comprises the first regenerated catalyst. In some embodiments, the first catalyst comprises the second used catalyst. In some embodiments, the separator comprises a separation system for separating the cracked gas oil product into at least two of a cracked gas stream, a cracked gasoline stream, a cracked gas oil stream, and a cycle oil stream. In some embodiments, the second separator comprises a second separation system for separating the cracked gasoline product into at least two of a ethylene stream, a propylene stream, a butylene stream, and a cracked gasoline stream. In some embodiments, the second recycle conduit is to send at least a portion of the cracked gasoline stream and/or the butylene stream to the intermediate reactor. In some embodiments, the system also includes a propylur reactor adapted to convert at least a portion of the cracked gas oil product and/or at least a portion of the cracked gasoline product into a cracked gas product. In some embodiments, the cracked gas product comprises at least 70% by volume C2 and C3 gases. In some embodiments, the intermediate reactor comprises a fast fluidized bed reactor, a riser reactor, or a dense bed reactor. In some embodiments, the draw-off vessel removes at least one of oxygen, nitrogen, CO2, NOx, and flue gases. In some embodiments, the draw-off vessel removes at least one undesirable gas and recycles the gas to the regenerator.

In one embodiment of the invention, there is disclosed a method comprising catalytically cracking a gas oil feedstock within an FCC riser reactor zone by contacting under suitable catalytic cracking conditions within said FCC riser reactor zone said gas oil feedstock with a first catalyst to yield an FCC riser reactor product comprising a cracked gas oil product and a first used catalyst; contacting a gasoline feedstock with a second catalyst within an intermediate cracking reactor operated under suitable high severity cracking conditions so as to yield a cracked gasoline product, comprising at least one lower olefin compound, and a second used catalyst; regenerating at least one of the first catalyst and the second catalyst in a regenerator to yield a regenerated catalyst; and removing at least a portion of undesirable gases from the regenerated catalyst in a draw-off vessel. In some embodiments, the method also includes recycling at least a portion of one or more of the cracked gas oil product streams to the intermediate cracking reactor. In some embodiments, the method also includes separating said cracked gasoline product into a plurality of cracked gasoline product streams; and recycling at least a portion of one or more of the cracked gasoline product streams to the intermediate cracking reactor. In some embodiments, the method also includes regenerating said first used catalyst to yield a regenerated first catalyst. In some embodiments, the method also includes using at least a portion of said second used catalyst as said first catalyst. In some embodiments, the method also includes using at least a portion of said regenerated first catalyst as said second catalyst. In some embodiments, the method also includes separating at least one lower olefin compound from said cracked gasoline product streams, and using said lower olefin compound as an olefin feed to a polyolefin manufacturing system. In some embodiments, the method also includes introducing into said intermediate cracking reactor a ZSM-5 additive. In some embodiments, said suitable catalytic cracking conditions are such as to provide for a conversion of said gas oil feedstock in the range of from 40 to 90 weight percent of the total gas oil feedstock. In some embodiments, the method also includes separating said cracked gasoline product into a plurality of cracked gasoline product streams; and sending at least a portion of one or more of the cracked gasoline product streams to a propylur reactor. In some embodiments, the propylur reactor converts at least about 70% by volume of the one or more of the cracked gasoline product streams to a C2-C3 product stream. The process may include the integration of the intermediate cracking reactor with a system for separating the cracked gasoline product into at least one lower olefin product, or a system for manufacturing a polyolefin, or a combination of both such systems. It is the enhanced production of lower olefins provided by the process that makes it beneficial to integrate the FCC riser reactor and intermediate cracking reactor of the system with the further processing of the cracked gasoline product.

Specifically, the increased yield of lower olefins through the use of steam and/or ZSM- 5 additive in the intermediate cracking reactor provides the incentive to integrate the aforementioned process steps. Thus, the cracked gasoline product, comprising at least one lower olefin compound, such as, ethylene, propylene, or butylene, may further be passed to a separation system for separating the cracked gasoline product into a lower olefin product comprising at least one lower olefin compound. The lower olefin product may further be used as a feedstock to a polyolefin manufacturing system whereby the lower olefin is polymerized under suitable polymerization conditions preferably in the presence of any suitable polymerization catalyst known to those skilled in the art.

Those of skill in the art will appreciate that many modifications and variations are possible in terms of the disclosed embodiments of the invention, configurations, materials and methods without departing from their spirit and scope. Accordingly, the scope of the claims appended hereafter and their functional equivalents should not be limited by particular embodiments described and illustrated herein, as these are merely exemplary in nature.

Claims

C L A I M S

1. A system comprising: a riser reactor comprising a gas oil feedstock and a first catalyst under catalytic cracking conditions to yield a riser reactor product comprising a cracked gas oil product and a first used catalyst; an intermediate reactor comprising at least a portion of the cracked gas oil product and a second catalyst under high severity conditions to yield a cracked gasoline product and a second used catalyst; a regenerator to regenerate the first used catalyst to the second catalyst; and a draw-off vessel to remove undesirable gases from the second catalyst from the regenerator.

2. The system of claim 1 , further comprising a recycle conduit to send at least a portion of the cracked gasoline product to the intermediate reactor, for example the cracked gasoline product comprising C4 hydrocarbons.

3. The system of one or more of claims 1 -2, further comprising a separator to separate the cracked gas oil product from the riser reactor into a plurality of streams.

4. The system of one or more of claims 1 -3, further comprising a second separator to separate the cracked gasoline product from the intermediate reactor into a plurality of streams.

5. The system of one or more of claims 1 -4, further comprising a third separator for separating said riser reactor product into said cracked gas oil product and said first used catalyst.

6. The system of one or more of claims 1 -5, further comprising a regenerator for regenerating said first used catalyst to yield a first regenerated catalyst.

7. The system of claim 6, wherein the second catalyst comprises the first regenerated catalyst.

8. The system of one or more of claims 1 -7, wherein the first catalyst comprises the second used catalyst.

9. The system of one or more of claims 3-8, wherein the separator comprises a separation system for separating the cracked gas oil product into at least two of a cracked gas stream, a cracked gasoline stream, a cracked gas oil stream, and a cycle oil stream.

10. The system of one or more of claims 4-9, wherein the second separator comprises a second separation system for separating the cracked gasoline product into at least two of a ethylene stream, a propylene stream, a butylene stream, and a cracked gasoline stream.

11. The system of claim 10, wherein the second recycle conduit is to send at least a portion of the cracked gasoline stream and/or the butylene stream to the intermediate reactor.

12. The system of one or more of claims 1 -11 , further comprising a propylur reactor adapted to convert at least a portion of the cracked gas oil product and/or at least a portion of the cracked gasoline product into a cracked gas product.

13. The system of claim 12, wherein the cracked gas product comprises at least 70% by volume C2 and C3 gases.

14. The system of one or more of claims 1 -13, wherein the intermediate reactor comprises a fast fluidized bed reactor, a riser reactor, or a dense bed reactor.

15. The system of one or more of claims 1 -14, wherein the draw-off vessel removes at least one of oxygen, nitrogen, CO2, NOx, and flue gases.

16. The system of one or more of claims 1 -15, wherein the draw-off vessel removes at least one undesirable gas and recycles the gas to the regenerator.

17. A method comprising: catalytically cracking a gas oil feedstock within an FCC riser reactor zone by contacting under suitable catalytic cracking conditions within said FCC riser reactor zone said gas oil feedstock with a first catalyst to yield an FCC riser reactor product comprising a cracked gas oil product and a first used catalyst; contacting a gasoline feedstock with a second catalyst within an intermediate cracking reactor operated under suitable high severity cracking conditions so as to yield a cracked gasoline product, comprising at least one lower olefin compound, and a second used catalyst; regenerating at least one of the first catalyst and the second catalyst in a regenerator to yield a regenerated catalyst; and removing at least a portion of undesirable gases from the regenerated catalyst in a draw-off vessel.

18. The method of claim 17, further comprising recycling at least a portion of one or more of the cracked gas oil product streams to the intermediate cracking reactor.

19. The method of one or more of claims 17-18, further comprising separating said cracked gasoline product into a plurality of cracked gasoline product streams; and recycling at least a portion of one or more of the cracked gasoline product streams to the intermediate cracking reactor.

20. The method of one or more of claims 17-19, further comprising regenerating said first used catalyst to yield a regenerated first catalyst.

21. The method of one or more of claims 17-20, further comprising using at least a portion of said second used catalyst as said first catalyst.

22. The method of one or more of claims 20-21 , further comprising using at least a portion of said regenerated first catalyst as said second catalyst.

23. The method of one or more of claims 19-22, further comprising separating at least one lower olefin compound from said cracked gasoline product streams, and using said lower olefin compound as an olefin feed to a polyolefin manufacturing system.

24. The method of one or more of claims 17-23, further comprising introducing into said intermediate cracking reactor a ZSM-5 additive.

25. The method of one or more of claims 17-24, wherein said suitable catalytic cracking conditions are such as to provide for a conversion of said gas oil feedstock in the range of from 40 to 90 weight percent of the total gas oil feedstock.

26. The method of one or more of claims 17-25, further comprising separating said cracked gasoline product into a plurality of cracked gasoline product streams; and sending at least a portion of one or more of the cracked gasoline product streams to a propyl u r reactor.

27. The method of claim 26, wherein the propylur reactor converts at least about 70% by volume of the one or more of the cracked gasoline product streams to a C2-

C3 product stream.