EP1713884B1 - Method for selective component cracking to maximize production of light olefins - Google Patents
Method for selective component cracking to maximize production of light olefins Download PDFInfo
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- EP1713884B1 EP1713884B1 EP05705923.0A EP05705923A EP1713884B1 EP 1713884 B1 EP1713884 B1 EP 1713884B1 EP 05705923 A EP05705923 A EP 05705923A EP 1713884 B1 EP1713884 B1 EP 1713884B1
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- catalyst
- reaction zone
- catalyst particles
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- cyclone
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- 150000001336 alkenes Chemical class 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 23
- 238000005336 cracking Methods 0.000 title description 11
- 238000004519 manufacturing process Methods 0.000 title description 7
- 239000003054 catalyst Substances 0.000 claims description 76
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 150000002430 hydrocarbons Chemical class 0.000 claims description 27
- 229930195733 hydrocarbon Natural products 0.000 claims description 26
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 5
- 238000005194 fractionation Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 238000005235 decoking Methods 0.000 claims 3
- 238000004523 catalytic cracking Methods 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 229930195734 saturated hydrocarbon Natural products 0.000 claims 1
- 239000007789 gas Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000571 coke Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 4
- 238000011027 product recovery Methods 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- -1 e.g. Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000010518 undesired secondary reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
Definitions
- the present invention relates to a method for fluid catalytic cracking (FCC) to maximize the yield of light olefins.
- FCC fluid catalytic cracking
- the fluid catalytic cracking (FCC) process is commonly used to crack high boiling petroleum fractions by contacting the high boiling feed with fluidized catalyst particles in a riser to produce primarily motor fuels. It also produces a certain amount of light hydrocarbons such as C 3 and C 4 compounds and -light olefins such as propylene and butylenes.
- light hydrocarbons such as C 3 and C 4 compounds
- -light olefins such as propylene and butylenes.
- the FCC process needs to be adapted to produce more of these light olefins.
- U.S. Patent No. 5,997,728 discloses a catalyst system for maximizing light olefin yields in FCC.
- the process employs a catalyst with large amounts of shape selective cracking additive.
- U.S. Patent No. 6,069,287 discloses a process for selectively producing C 2 -C 4 olefins in a FCC process from a thermally cracked naphtha stream.
- the naphtha stream is contacted with a catalyst containing from about 10 to 50 wt% of crystalline zeolite having an average pore diameter of less than about 0.7 nanometers.
- U.S. Patent No. 6,093,867 discloses a process for selectively producing C 3 olefins from a catalytically cracked or thermally cracked naphtha stream. zone, a stripping zone, a catalyst regeneration zone, and fractionation zone.
- the naphtha feed stream is contacted in the reaction zone with a catalyst containing from 10 to 50 wt. % of a crystalline zeolite having an average pore diameter less than 0.7 nanometers at reaction conditions which include temperatures ranging from 500° to 650° C. and a hydrocarbon partial pressure from 68.9 to 275.6 kPa (10 to 40 psia).
- Vapor products are collected overhead and the catalyst particles are passed through the stripping zone on the way to the catalyst regeneration zone.
- Volatile compounds are stripped with steam in the stripping zone and the catalyst particles are sent to the catalyst regeneration zone where coke is burned from the catalyst, which is then recycled to the reaction zone.
- Overhead products from the reaction zone are passed to a fractionation zone where a stream of C 3 's is recovered and a stream rich in C 4 and/or C 5 olefins is recycled to the stripping zone.
- the FCC process of the invention employs a catalyst in the form of very fine solid particles that are fluidized in a reaction zone which is in the form of a vertical riser reactor.
- the feed is contacted with the catalyst at the bottom of the vertical riser reactor and lifted with the catalyst to the top of the riser reactor, as described more fully below.
- the feed is a relatively heavy hydrocarbon fraction having a relatively high boiling point and/or molecular weight.
- the term "relatively heavy” as used herein refers to hydrocarbons having five or more carbon atoms, typically more than 8 carbon atoms.
- the feed can be a naphtha, vacuum gas oil or residue.
- the feed is a petroleum fraction having a boiling range of from 250°C to 625°C.
- the catalyst used in this invention can be any catalyst commonly used in FCC processes. These catalysts generally consist of high activity crystalline alumina silicates.
- the preferred catalyst components are zeolites, as these exhibit higher intrinsic activity and resistance to deactivation. Typical zeolites include ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48.
- a more preferred catalyst of the present invention is based upon Ultrastable Y (USY) zeolite with higher silica to alumina ratio.
- the catalysts can be used alone or in combination with zeolites having a shape selective pentasil structure, such as ZSM-5, that convert larger linear hydrocarbon compounds to smaller ones, especially larger olefins to smaller olefins.
- zeolites having a shape selective pentasil structure such as ZSM-5
- Non-zeolite catalysts such as amorphous clays or inorganic oxides can also be employed.
- the present invention maximizes selectivity of the light olefins (C 3 -C 4 olefins) by means of the FCC unit hardware design, operating conditions and catalyst formulation.
- the hardware design, operating conditions, and catalyst formulation are tailored to achieve kinetic and thermodynamic effects which favor the production of olefins.
- the catalyst formulation or the mixture of catalysts used in this invention is selected from the family of catalysts described above, such that the catalysts activity for catalytic conversion is maximized along with maximization of conversion of larger molecular weight olefins to smaller molecular weight olefins, while the tendency for resaturation of the light olefins thus produced is minimized.
- Paraffins are cracked to produce olefins.
- Olefins can react to produce naphthenes through cyclization reactions, smaller olefins through cracking reactions, and paraffins through hydrogen transfer. Olefins can also undergo isomerization.
- the naphthenes can be converted to olefins or cycloolefins.
- Aromatics can be produced by dehydrogenation of cycloolefins.
- the aromatics in turn, can be cracked, or can undergo dehydrogenation and/or alkylation to produce heavy coke, and polycyclic or heterocyclic aromatics.
- the desired reaction is the conversion of paraffins to light olefins, which is characterized by a faster reaction rate than the undesired secondary reactions.
- the reaction time by limiting the reaction time, one can terminate the undesired chain reactions quickly after the olefin production has taken place.
- the quick termination of the side reactions is achieved by having a very short residence time in the riser reactor and, more importantly, quick and efficient separation of the reaction products from the catalyst at the termination of the reaction at the end of the riser reactor.
- the system 100 includes a vertical riser reactor 101.
- the initial feed is introduced into the riser 101 through injectors 102.
- Regenerated catalyst mixes with the feed and both are carried upward in the riser wherein the cracking reaction occurs.
- Regenerated catalyst typically enters the riser at a temperature of about 650°C to 760°C and the cracking reaction in the riser occurs at a temperature in the range of about 500°C to about 600°C.
- the riser pressure is set at 68.9 to 172 kPa (10 to 25 psig), with a hydrocarbon partial pressure of 20.7 to 68.9 kPa (3 to 10 psig). Steam or other dry gas may be used as a diluent to achieve the lower hydrocarbon partial pressure.
- SCC selective component cracking
- the selected component to be recycled and re-cracked could be a range of materials such as higher carbon number olefins, or straight run products from other conversion units.
- the selected components are not mixed with the fresh feed at injector 102. Rather, these components are injected separately through a set of injection points in the riser reactor system where the conditions are ideal for cracking these components.
- the lighter selected components are injected through multiple injectors 103a upstream of the fresh feed injector 102 and at points where these components can thoroughly mix or contact the high activity, high temperature catalyst.
- Residence times range from 0.5 to 10.0 seconds, preferably 1.0 to 5.0 seconds and more preferably 1.0 to 3.0 seconds.
- the reactor effluent exits at the top of riser 101 and enters separator vessel 110 and is introduced into at least one, and preferably two, cyclone separators.
- the gas and solids are mostly separated in first cyclone 111, and the overhead from first cyclone 111 is directed to second cyclone 112 for final separation.
- the solids drop out through diplegs 113 into the stripper 114.
- the gases are sent out through outlet 118 to a main, or primary, fractionation column and downstream product separation system where various product fractions are separated through a number of fractionation steps. Some of the products are recycled back to the reaction, as mentioned above.
- a unique feature applied in this invention that helps to preserve the yield of light olefins formed in the riser reaction zone is that the cyclone 111 operates at a lower pressure than the interior of the vessel 110. This pressure differential is maintained by having the gases from the stripper vessel 114 pass through an orifice in the roof of the cyclone 111, as described, for example, in U.S. Patent No. 5,248,411 , which is herein incorporated by reference.
- the lower pressure in cyclone 111 provides complete separation of the reacting hydrocarbons from the catalyst so as to quickly terminate secondary chain reactions, and thereby preserves the yield of light olefins. Referring now to FIG.
- the catalyst particles become laden with predominantly carbonaceous material termed "coke” that is a by-product of the cracking reactions.
- the catalyst particles also contain hydrocarbons in their pores and entrain some hydrocarbons after separation from the vapor phase in the cyclones 111 and 112.
- the coke deposits deactivate the catalyst by blocking active access of the reacting species to the active sites of the catalyst.
- the catalyst activity is restored by combusting the coke with an oxygen-containing gas in a regeneration vessel 120.
- the catalyst is stripped with steam in the stripping vessel 114 to remove the accompanying hydrocarbon vapors that would, otherwise, burn in the regenerator and represent loss of the valuable products.
- the catalyst particles which flow out of the cyclones 111 and 112 fall into the stripping section 114 of vessel 110 wherein the particles are separated of any entrained or adsorbed hydrocarbons by conventional countercurrent contact with steam.
- the stripper internals are designed to maximize contact time and surface area for mass transfer between the fluidized catalyst phase and the stripping steam phase.
- the stripped catalyst particles then drop through downflow line 115 and are carried by transfer line 116 to a square bend 117 from which they are carried upward into the middle of fluid bed 121 in regenerator 120 through outlet 122. Uniform distribution of the coke laden catalyst in the center of the regeneration bed 121 is important for regaining catalyst activity and surface area.
- the square bend transfer line possesses a unique configuration that eliminates erosion problems associated with other designs for similar dilute phase catalyst transfer, such as the use of an elbow for the horizontal to vertical turn for the transport of the spent catalyst.
- This square bend configuration results in trouble-free introduction of the spent catalyst into the center of the regenerator for uniform and thorough regeneration of the catalyst, so that catalyst activity for desired reactions is maximized for the production of light olefins.
- Oxygen containing gas e.g., air
- Oxygen containing gas is introduced in the regenerator 120 through inlet 123 under bed 121 to fluidize the bed and to oxidize coke deposits on the catalyst particles through combustion.
- Combustion gas inlet 123 is representative of a plurality of such distributors such that the oxygen containing gas is spread uniformly across the bed area so as to match the distribution of the spent catalyst from the outlet 122.
- the exhaust resulting gas is sent through cyclones to separate out any catalyst particles and then through outlet 128.
- Regenerated (i.e., decoked) catalyst particles are then withdrawn through line 131 and flow down through regenerated catalyst standpipe 130 and via regenerated catalyst feed line 133, into the riser 101.
- Line 132 serves as a vent to facilitate downflow of the catalyst particles.
- System 200 is similar to system 100 except that it includes a second riser reactor 201.
- Initial feed is introduced into riser 201 through injector 202.
- Selected components recycled from the first pass conversion can be introduced into the riser 201 at injector 203a.
- Regenerated catalyst from regenerated catalyst standpipe 130 is introduced into riser 201 via regenerated catalyst feed line 233.
- the effluent from riser reactor 201 exits at the top of the riser and is introduced into a first cyclone 211.
- the overhead from the first cyclone is introduced into a second cyclone 212.
- the solids drop through the cyclone diplegs into the stripping region 114.
- the pressure inside cyclones 211 and 212 is less than the pressure within stripping region 114.
- Fig. 5 the relationship between propylene selectivity and feed conversion with parameters of hydrocarbon partial pressure is illustrated.
- the graph shows the advantage of operating the FCC process at a lower hydrocarbon partial pressure.
- X hydrocarbon partial pressure
- X can range from 68,9 to 172 kPa (10 psig to 25 psig)
- a decrease of hydrocarbon partial pressure of 34,4 kPa (5 psig (X-5 psi)) results in dramatically improved selectivity to propylene.
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Description
- The present invention relates to a method for fluid catalytic cracking (FCC) to maximize the yield of light olefins.
- The fluid catalytic cracking (FCC) process is commonly used to crack high boiling petroleum fractions by contacting the high boiling feed with fluidized catalyst particles in a riser to produce primarily motor fuels. It also produces a certain amount of light hydrocarbons such as C3 and C4 compounds and -light olefins such as propylene and butylenes. However, the relative demand for the light olefins has been increasing. Therefore, the FCC process needs to be adapted to produce more of these light olefins.
- For example,
U.S. Patent No. 5,997,728 discloses a catalyst system for maximizing light olefin yields in FCC. The process employs a catalyst with large amounts of shape selective cracking additive. -
U.S. Patent No. 6,069,287 discloses a process for selectively producing C2-C4 olefins in a FCC process from a thermally cracked naphtha stream. The naphtha stream is contacted with a catalyst containing from about 10 to 50 wt% of crystalline zeolite having an average pore diameter of less than about 0.7 nanometers. -
U.S. Patent No. 6,093,867 discloses a process for selectively producing C3 olefins from a catalytically cracked or thermally cracked naphtha stream. zone, a stripping zone, a catalyst regeneration zone, and fractionation zone. The naphtha feed stream is contacted in the reaction zone with a catalyst containing from 10 to 50 wt. % of a crystalline zeolite having an average pore diameter less than 0.7 nanometers at reaction conditions which include temperatures ranging from 500° to 650° C. and a hydrocarbon partial pressure from 68.9 to 275.6 kPa (10 to 40 psia). Vapor products are collected overhead and the catalyst particles are passed through the stripping zone on the way to the catalyst regeneration zone. Volatile compounds are stripped with steam in the stripping zone and the catalyst particles are sent to the catalyst regeneration zone where coke is burned from the catalyst, which is then recycled to the reaction zone. Overhead products from the reaction zone are passed to a fractionation zone where a stream of C3's is recovered and a stream rich in C4 and/or C5 olefins is recycled to the stripping zone. - Other patents describing FCC processes for producing higher yields of light olefins include
U.S. Patent Nos. 6,106,697 ,6,118,035 ,6,313,366 and6,538,169 , for example. - Document
US 5,248,411 shows a process for the fluid catalytic cracking of hydrocarbons, wherein the reaction mixture comprising the feed and a fluidized particulate catalyst are conveyed to a cyclone separation system within an interior space that has a stripping region and an upper region, wherein different pressures are provided in said two regions. Further processes for the fluid catalytic cracking of hydrocarbons are known fromUS 4,749,471 ,EP 0654518 ,US 5,234,578 ,US 5,279,727 andUS 4,623,446 . - There is yet a need for a FCC method that is able to maximize production of light olefins more efficiently and selectively.
- According to the present invention, the aforementioned need is met by a process as defined in claim 1. Preferred embodiments of the present invention are laid down in the dependent claims.
- Various embodiments are described below with reference to the drawings wherein:
-
FIG. 1 is a schematic illustration of reactions occurring in an FCC process; -
FIG. 2 is a diagrammatic illustration of an FCC system employing the invention employing a single riser reaction zone; -
FIG. 3 is a diagrammatic illustration of an alternative FCC system employing dual riser reaction zones; -
FIG. 4 is a graph illustrating pressure differential versus product recovery efficiency; and, -
FIG. 5 is a graph illustrating C3H6 selectivity versus feed conversion. - The FCC process of the invention employs a catalyst in the form of very fine solid particles that are fluidized in a reaction zone which is in the form of a vertical riser reactor. The feed is contacted with the catalyst at the bottom of the vertical riser reactor and lifted with the catalyst to the top of the riser reactor, as described more fully below.
- The feed is a relatively heavy hydrocarbon fraction having a relatively high boiling point and/or molecular weight. The term "relatively heavy" as used herein refers to hydrocarbons having five or more carbon atoms, typically more than 8 carbon atoms. For example, the feed can be a naphtha, vacuum gas oil or residue. Typically, the feed is a petroleum fraction having a boiling range of from 250°C to 625°C.
- The catalyst used in this invention can be any catalyst commonly used in FCC processes. These catalysts generally consist of high activity crystalline alumina silicates. The preferred catalyst components are zeolites, as these exhibit higher intrinsic activity and resistance to deactivation. Typical zeolites include ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48. A more preferred catalyst of the present invention is based upon Ultrastable Y (USY) zeolite with higher silica to alumina ratio. The catalysts can be used alone or in combination with zeolites having a shape selective pentasil structure, such as ZSM-5, that convert larger linear hydrocarbon compounds to smaller ones, especially larger olefins to smaller olefins. Non-zeolite catalysts such as amorphous clays or inorganic oxides can also be employed.
- The present invention maximizes selectivity of the light olefins (C3-C4 olefins) by means of the FCC unit hardware design, operating conditions and catalyst formulation. The hardware design, operating conditions, and catalyst formulation are tailored to achieve kinetic and thermodynamic effects which favor the production of olefins. The catalyst formulation or the mixture of catalysts used in this invention is selected from the family of catalysts described above, such that the catalysts activity for catalytic conversion is maximized along with maximization of conversion of larger molecular weight olefins to smaller molecular weight olefins, while the tendency for resaturation of the light olefins thus produced is minimized.
- Referring to
FIG. 1 , various reactions which occur in FCC are diagrammatically illustrated. Paraffins are cracked to produce olefins. Olefins, however, can react to produce naphthenes through cyclization reactions, smaller olefins through cracking reactions, and paraffins through hydrogen transfer. Olefins can also undergo isomerization. The naphthenes can be converted to olefins or cycloolefins. Aromatics can be produced by dehydrogenation of cycloolefins. The aromatics, in turn, can be cracked, or can undergo dehydrogenation and/or alkylation to produce heavy coke, and polycyclic or heterocyclic aromatics. - The desired reaction is the conversion of paraffins to light olefins, which is characterized by a faster reaction rate than the undesired secondary reactions. Thus, by limiting the reaction time, one can terminate the undesired chain reactions quickly after the olefin production has taken place. The quick termination of the side reactions is achieved by having a very short residence time in the riser reactor and, more importantly, quick and efficient separation of the reaction products from the catalyst at the termination of the reaction at the end of the riser reactor.
- Referring now to
FIG. 2 , a FCCsystem 100 is illustrated for the selective component cracking of the invention. Thesystem 100 includes avertical riser reactor 101. The initial feed is introduced into theriser 101 throughinjectors 102. Regenerated catalyst mixes with the feed and both are carried upward in the riser wherein the cracking reaction occurs. - Regenerated catalyst typically enters the riser at a temperature of about 650°C to 760°C and the cracking reaction in the riser occurs at a temperature in the range of about 500°C to about 600°C.
- Low hydrocarbon partial pressure in the riser favors light olefin production. The riser pressure is set at 68.9 to 172 kPa (10 to 25 psig), with a hydrocarbon partial pressure of 20.7 to 68.9 kPa (3 to 10 psig). Steam or other dry gas may be used as a diluent to achieve the lower hydrocarbon partial pressure.
- In order to maximize the production of light olefins, certain selected components of the product of the first pass conversion are recycled to the riser reactor for further cracking. This mode of operation is termed selective component cracking ("SCC"). The selected component to be recycled and re-cracked could be a range of materials such as higher carbon number olefins, or straight run products from other conversion units. The selected components are not mixed with the fresh feed at
injector 102. Rather, these components are injected separately through a set of injection points in the riser reactor system where the conditions are ideal for cracking these components. The lighter selected components are injected through multiple injectors 103a upstream of thefresh feed injector 102 and at points where these components can thoroughly mix or contact the high activity, high temperature catalyst. - Optimization of the reaction residence time is an important feature of the invention. Longer residence time allows for more thorough cracking, but also increases the secondary reactions that reduce the yield of light olefins. Residence times range from 0.5 to 10.0 seconds, preferably 1.0 to 5.0 seconds and more preferably 1.0 to 3.0 seconds.
- The reactor effluent exits at the top of
riser 101 and entersseparator vessel 110 and is introduced into at least one, and preferably two, cyclone separators. The gas and solids are mostly separated in first cyclone 111, and the overhead from first cyclone 111 is directed tosecond cyclone 112 for final separation. The solids drop out throughdiplegs 113 into thestripper 114. The gases are sent out throughoutlet 118 to a main, or primary, fractionation column and downstream product separation system where various product fractions are separated through a number of fractionation steps. Some of the products are recycled back to the reaction, as mentioned above. - A unique feature applied in this invention that helps to preserve the yield of light olefins formed in the riser reaction zone is that the cyclone 111 operates at a lower pressure than the interior of the
vessel 110. This pressure differential is maintained by having the gases from thestripper vessel 114 pass through an orifice in the roof of the cyclone 111, as described, for example, inU.S. Patent No. 5,248,411 , which is herein incorporated by reference. The lower pressure in cyclone 111 provides complete separation of the reacting hydrocarbons from the catalyst so as to quickly terminate secondary chain reactions, and thereby preserves the yield of light olefins. Referring now toFIG. 4 , it can be seen that when cyclone 111 are operating at a negative pressure, i.e., when the pressure in cyclone 111 is lower than the pressure invessel 110, the product recovery efficiency is almost 100%. When the pressure differential is zero, i.e., whenvessel 110 and cyclone 111 are at the same pressure, the efficiency of product recovery is 97%. When cyclone 111 is at a pressure only 0.4 psi higher than the pressure invessel 110, the product recovery efficiency drops to below 80%. The lower cyclone pressure prevents the reacting gases from flowing down with the separated catalyst solids through the diplegs and into the interior ofvessel 110. Otherwise, the reacting gases would remain in contact with the catalyst and the slower secondary reactions would have additional time to proceed and reduce selectivity for olefins. - During the course of reaction in the
riser reactor 101, the catalyst particles become laden with predominantly carbonaceous material termed "coke" that is a by-product of the cracking reactions. The catalyst particles also contain hydrocarbons in their pores and entrain some hydrocarbons after separation from the vapor phase in thecyclones 111 and 112. The coke deposits deactivate the catalyst by blocking active access of the reacting species to the active sites of the catalyst. The catalyst activity is restored by combusting the coke with an oxygen-containing gas in aregeneration vessel 120. However, before the regeneration step, the catalyst is stripped with steam in the strippingvessel 114 to remove the accompanying hydrocarbon vapors that would, otherwise, burn in the regenerator and represent loss of the valuable products. - Referring now again to
FIG. 2 , the catalyst particles which flow out of thecyclones 111 and 112, fall into the strippingsection 114 ofvessel 110 wherein the particles are separated of any entrained or adsorbed hydrocarbons by conventional countercurrent contact with steam. The stripper internals are designed to maximize contact time and surface area for mass transfer between the fluidized catalyst phase and the stripping steam phase. The stripped catalyst particles then drop throughdownflow line 115 and are carried bytransfer line 116 to asquare bend 117 from which they are carried upward into the middle offluid bed 121 inregenerator 120 throughoutlet 122. Uniform distribution of the coke laden catalyst in the center of theregeneration bed 121 is important for regaining catalyst activity and surface area. The square bend transfer line possesses a unique configuration that eliminates erosion problems associated with other designs for similar dilute phase catalyst transfer, such as the use of an elbow for the horizontal to vertical turn for the transport of the spent catalyst. This square bend configuration results in trouble-free introduction of the spent catalyst into the center of the regenerator for uniform and thorough regeneration of the catalyst, so that catalyst activity for desired reactions is maximized for the production of light olefins. - Oxygen containing gas, e.g., air, is introduced in the
regenerator 120 throughinlet 123 underbed 121 to fluidize the bed and to oxidize coke deposits on the catalyst particles through combustion.Combustion gas inlet 123 is representative of a plurality of such distributors such that the oxygen containing gas is spread uniformly across the bed area so as to match the distribution of the spent catalyst from theoutlet 122. The exhaust resulting gas is sent through cyclones to separate out any catalyst particles and then throughoutlet 128. - Regenerated (i.e., decoked) catalyst particles are then withdrawn through
line 131 and flow down through regeneratedcatalyst standpipe 130 and via regeneratedcatalyst feed line 133, into theriser 101.Line 132 serves as a vent to facilitate downflow of the catalyst particles. - Referring now to
FIG. 3 , analternative embodiment 200 of the FCC system is illustrated.System 200 is similar tosystem 100 except that it includes asecond riser reactor 201. Initial feed is introduced intoriser 201 through injector 202. Selected components recycled from the first pass conversion can be introduced into theriser 201 atinjector 203a. Regenerated catalyst from regeneratedcatalyst standpipe 130 is introduced intoriser 201 via regeneratedcatalyst feed line 233. The effluent fromriser reactor 201 exits at the top of the riser and is introduced into a first cyclone 211. The overhead from the first cyclone is introduced into asecond cyclone 212. The solids drop through the cyclone diplegs into the strippingregion 114. As described above, the pressure insidecyclones 211 and 212 is less than the pressure within strippingregion 114. - Referring now to
Fig. 5 , the relationship between propylene selectivity and feed conversion with parameters of hydrocarbon partial pressure is illustrated. The graph shows the advantage of operating the FCC process at a lower hydrocarbon partial pressure. For hydrocarbon partial pressure X, wherein X can range from 68,9 to 172 kPa (10 psig to 25 psig), it can be seen that a decrease of hydrocarbon partial pressure of 34,4 kPa (5 psig (X-5 psi)) results in dramatically improved selectivity to propylene. Accordingly, it is a feature of the invention to conduct the FCC process at a hydrocarbon partial pressure of no more than 68,9 kPa (10 psig), preferably no more than 48,2 kPa (7 psig) and more preferably no more than 34,4 kPa (5 psig).
Claims (5)
- A process for the fluid catalytic cracking of hydrocarbons comprising:a) contacting a primary feed of relatively heavy hydrocarbons having five or more carbon atoms with a fluidized particulate catalyst in a reaction zone under catalytic cracking conditions including a temperature of from 500°C to 600°C, a pressure of from 68,9 kPa to 172 kPa (10 to 25 psig), a residence time of from 0.5 seconds to 10.0 seconds and a hydrocarbon partial pressure of from 20,7 kPa to 68,9 kPa (3 psig to 10 psig), to convert at least some of the heavy hydrocarbons to light olefins having from 3 to 4 carbon atoms;b) conveying a reaction mixture containing spent catalyst particles and a gaseous stream containing the light olefins and other reaction products to a cyclone separation system within a containment/separation vessel directly connected to the reaction zone, at least part of said cyclone separation system being positioned within an interior space enclosed by the vessel, said interior space including a stripping region and an upper region in which the at least part of the cyclone separation system is positioned, said cyclone separation system including at least one cyclone connected directly to the reaction zone and having an interior first pressure and said stripping region having a second pressure, said interior first pressure being at least 3,4 hPa (0,05 psig) lower than the second pressure;c) separating the spent catalyst particles from the gaseous fluid within said at least one cyclone, said gaseous fluid being ejected as effluent from the separation vessel through an exit port and said spent catalyst particles being transferred to the stripping region;d) contacting said spent catalyst particles with a stripping gas to remove entrained hydrocarbons, said stripping gas with entrained hydrocarbons being moved through the at least one cyclone through the exit port, and transferring the stripped catalyst particles to a regeneration zone for decoking, wherein the step of transferring the stripped catalyst particles to the regeneration zone comprises conducting the catalyst particles through a square bend transfer line, and decoking at least a portion of the stripped catalyst to provide regenerated catalyst, and wherein the regeneration zone includes a fluidized bed and the stripped catalyst particles are introduced in the vicinity of the center of the fluidized bed, and wherein the decoking step includes contacting the stripped catalyst particles in the fluidized bed of the regeneration zone with an oxidizing gas,e) transferring at least a portion of regenerated catalyst to the reaction zone upstream of the primary feed injection point, andf) injecting at least a second feed component into said reaction zone separately from said primary feed, said second feed component comprising a recycled portion of the effluent from the separation vessel, said recycled portion of the effluent being separated from the effluent downstream of the separation vessel by fractionation, wherein the second feed component comprises a hydrocarbon fraction which is lighter than the saturated hydrocarbons of the primary feed and which is introduced in the reaction zone through multiple points upstream of the position at which the primary feed is introduced.
- The process of claim 1, wherein the catalyst comprises one or more zeolitic material selected from the group consisting of USY, ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and ZSM-48.
- The process of claim 1, wherein the primary feed comprises a petroleum fraction having a boiling range of from 250°C to 625°C.
- The process of claim 1, wherein the reaction zone comprises a vertically oriented riser reactor wherein the primary feed is introduced into the riser reactor at a position in the vicinity of a bottom portion of the riser reactor and exits the reaction zone at a top portion of the riser reactor.
- The process of claim 1, wherein the transferred portion of regenerated catalyst is conducted through a stand pipe and recycled to the reaction zone.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US53890604P | 2004-01-23 | 2004-01-23 | |
PCT/US2005/001724 WO2005073347A1 (en) | 2004-01-23 | 2005-01-19 | System and method for selective component cracking to maximize production of light olefins |
Publications (2)
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EP1713884A1 EP1713884A1 (en) | 2006-10-25 |
EP1713884B1 true EP1713884B1 (en) | 2018-09-26 |
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EP05705923.0A Active EP1713884B1 (en) | 2004-01-23 | 2005-01-19 | Method for selective component cracking to maximize production of light olefins |
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US (1) | US20050161369A1 (en) |
EP (1) | EP1713884B1 (en) |
JP (1) | JP2007518866A (en) |
KR (1) | KR100985288B1 (en) |
CN (1) | CN1910264A (en) |
AU (1) | AU2005207859B2 (en) |
BR (1) | BRPI0506971B1 (en) |
CA (1) | CA2553783C (en) |
MX (1) | MXPA06008184A (en) |
NO (1) | NO337658B1 (en) |
WO (1) | WO2005073347A1 (en) |
ZA (1) | ZA200606044B (en) |
Families Citing this family (7)
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KR101503069B1 (en) | 2008-10-17 | 2015-03-17 | 에스케이이노베이션 주식회사 | Production of valuable aromatics and olefins from FCC light cycle oil |
US8137631B2 (en) * | 2008-12-11 | 2012-03-20 | Uop Llc | Unit, system and process for catalytic cracking |
US9452404B2 (en) * | 2012-07-12 | 2016-09-27 | Lummus Technology Inc. | Fluid cracking process and apparatus for maximizing light olefins or middle distillates and light olefins |
RU2728777C1 (en) | 2016-09-16 | 2020-07-31 | ЛАММУС ТЕКНОЛОДЖИ ЭлЭлСи | Catalytic cracking method with suspended catalyst and device for maximizing yield of light olefin and other applications |
FR3090684B1 (en) * | 2018-12-19 | 2021-08-27 | Ifp Energies Now | Conversion of a crude oil into a fluidized bed, with zones of different contact times |
CN114222806A (en) * | 2019-08-05 | 2022-03-22 | 沙特基础全球技术有限公司 | Multiple dense phase risers for maximizing light olefin yield for naphtha catalytic cracking |
CN111408323A (en) * | 2020-04-17 | 2020-07-14 | 董国亮 | Reaction regeneration device for reducing catalyst pipeline stress and lining abrasion |
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US4968406A (en) * | 1988-10-29 | 1990-11-06 | Mobil Oil Corporation | Increasing feed volume throughput in FCC process |
US5506365A (en) * | 1987-12-30 | 1996-04-09 | Compagnie De Raffinage Et De Distribution Total France | Process and apparatus for fluidized-bed hydrocarbon conversion |
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US4749471A (en) * | 1983-09-06 | 1988-06-07 | Mobil Oil Corporation | Closed FCC cyclone process |
US4588558A (en) * | 1983-09-06 | 1986-05-13 | Mobil Oil Corporation | Closed FCC cyclone system |
US4623446A (en) * | 1984-05-21 | 1986-11-18 | Mobil Oil Corporation | Closed cyclone FCC catalyst separation with stripping gas injection and direct steam injection |
US5271826A (en) * | 1988-03-03 | 1993-12-21 | Mobil Oil Corporation | Catalytic cracking of coke producing hydrocarbons |
US5234578A (en) * | 1988-08-26 | 1993-08-10 | Uop | Fluidized catalytic cracking process utilizing a high temperature reactor |
CA1327177C (en) * | 1988-11-18 | 1994-02-22 | Alan R. Goelzer | Process for selectively maximizing product production in fluidized catalytic cracking of hydrocarbons |
CA2052709C (en) * | 1990-11-30 | 2002-12-17 | Ting Y. Chan | Apparatus for withdrawing stripper gas from an fccu reactor vessel |
US5279727A (en) * | 1991-12-27 | 1994-01-18 | Amoco Corporation | Open-bottomed cyclone with solids separation tube and method |
US5389239A (en) | 1993-11-22 | 1995-02-14 | Texaco Inc. | Control method for direct-coupled FCC riser cyclone |
US6106697A (en) | 1998-05-05 | 2000-08-22 | Exxon Research And Engineering Company | Two stage fluid catalytic cracking process for selectively producing b. C.su2 to C4 olefins |
US6313366B1 (en) * | 1998-05-05 | 2001-11-06 | Exxonmobile Chemical Patents, Inc. | Process for selectively producing C3 olefins in a fluid catalytic cracking process |
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US5944982A (en) * | 1998-10-05 | 1999-08-31 | Uop Llc | Method for high severity cracking |
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-
2005
- 2005-01-18 US US11/039,125 patent/US20050161369A1/en not_active Abandoned
- 2005-01-19 JP JP2006551243A patent/JP2007518866A/en active Pending
- 2005-01-19 MX MXPA06008184A patent/MXPA06008184A/en active IP Right Grant
- 2005-01-19 EP EP05705923.0A patent/EP1713884B1/en active Active
- 2005-01-19 KR KR1020067014571A patent/KR100985288B1/en active IP Right Grant
- 2005-01-19 BR BRPI0506971-8A patent/BRPI0506971B1/en not_active IP Right Cessation
- 2005-01-19 CA CA2553783A patent/CA2553783C/en active Active
- 2005-01-19 WO PCT/US2005/001724 patent/WO2005073347A1/en not_active Application Discontinuation
- 2005-01-19 CN CNA2005800030167A patent/CN1910264A/en active Pending
- 2005-01-19 AU AU2005207859A patent/AU2005207859B2/en not_active Ceased
-
2006
- 2006-07-21 ZA ZA200606044A patent/ZA200606044B/en unknown
- 2006-08-22 NO NO20063753A patent/NO337658B1/en not_active IP Right Cessation
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US4422925A (en) * | 1981-12-28 | 1983-12-27 | Texaco Inc. | Catalytic cracking |
US5506365A (en) * | 1987-12-30 | 1996-04-09 | Compagnie De Raffinage Et De Distribution Total France | Process and apparatus for fluidized-bed hydrocarbon conversion |
US4968406A (en) * | 1988-10-29 | 1990-11-06 | Mobil Oil Corporation | Increasing feed volume throughput in FCC process |
Also Published As
Publication number | Publication date |
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AU2005207859B2 (en) | 2010-01-07 |
AU2005207859A1 (en) | 2005-08-11 |
WO2005073347A1 (en) | 2005-08-11 |
NO20063753L (en) | 2006-08-22 |
KR100985288B1 (en) | 2010-10-04 |
US20050161369A1 (en) | 2005-07-28 |
CA2553783A1 (en) | 2005-08-11 |
NO337658B1 (en) | 2016-05-30 |
KR20070018836A (en) | 2007-02-14 |
CN1910264A (en) | 2007-02-07 |
BRPI0506971A (en) | 2007-07-03 |
EP1713884A1 (en) | 2006-10-25 |
CA2553783C (en) | 2013-03-26 |
JP2007518866A (en) | 2007-07-12 |
ZA200606044B (en) | 2007-12-27 |
BRPI0506971B1 (en) | 2020-12-08 |
MXPA06008184A (en) | 2007-01-26 |
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