US20050161369A1 - System and method for selective component cracking to maximize production of light olefins - Google Patents

System and method for selective component cracking to maximize production of light olefins Download PDF

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Publication number
US20050161369A1
US20050161369A1 US11/039,125 US3912505A US2005161369A1 US 20050161369 A1 US20050161369 A1 US 20050161369A1 US 3912505 A US3912505 A US 3912505A US 2005161369 A1 US2005161369 A1 US 2005161369A1
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zsm
reaction zone
catalyst
cyclone
catalyst particles
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US11/039,125
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Dalip Soni
Leonce Castagnos
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CB&I Technology Inc
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ABB Lummus Global Inc
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Priority to US11/039,125 priority Critical patent/US20050161369A1/en
Assigned to ABB LUMMUS GLOBAL, INC. reassignment ABB LUMMUS GLOBAL, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CASTAGNOS, LEONCE F., SONI, DALIP S.
Publication of US20050161369A1 publication Critical patent/US20050161369A1/en
Abandoned legal-status Critical Current

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    • 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 system and 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. Pat. 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. Pat. 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. Pat. No. 6,093,867 discloses a process for selectively producing C 3 olefins from a catalytically cracked or thermally cracked naphtha stream.
  • the naphtha stream is introduced into a process unit comprised of a reaction 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 about 10 to 50 wt. % of a crystalline zeolite having an average pore diameter less than about 0.7 nanometers at reaction conditions which include temperatures ranging from about 500° to 650° C. and a hydrocarbon partial pressure from about 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.
  • a process for the fluid catalytic cracking of hydrocarbons comprises contacting a feed of heavy/high boiling hydrocarbons with a particulate catalyst in a reaction zone under fluidized catalytic cracking conditions to convert at least some of the hydrocarbons to light olefins having from 3 to 4 carbon atoms, conveying spent catalyst and a gaseous fluid containing the light olefins and other products of conversion to a cyclone separation system within a containment/separation vessel, the containment/separation vessel enclosing an interior space having a stripping region and an upper region in which the cyclone separation system that is directly connected to the riser reaction zone is positioned, wherein the cyclone separation system includes a first cyclone having an interior first pressure and said stripping region having a second pressure, the interior first pressure being at least about 0.05 psi lower than the stripping region second pressure.
  • the gaseous hydrocarbon products are separated from the catalyst particles in the cyclone separation system and flow to the product separation or fractionation section downstream of the separation vessel.
  • the catalyst particles are then transferred to the stripping region.
  • the spent catalyst particles are contacted with a stripping gas to remove entrained hydrocarbons, the stripping gas with entrained hydrocarbons being moved through the cyclone and through the exit port.
  • the stripped catalyst particles are then transferred to a regeneration zone for decoking, and the decoked or regenerated catalyst particles are then transferred back to the reaction zone.
  • 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
  • FIG. 5 is a graph illustrating C 3 H 6 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.
  • the feed can be a naphtha, vacuum gas oil or residue.
  • the feed is a petroleum fraction having a boiling range of from about 250° C. to about 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-X, ZSM-Y, 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 usually 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 about 10 to 25 psig, with a hydrocarbon partial pressure of about 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 103 a upstream of the fresh feed injector 102 and at points where these components can thoroughly mix or contact the high activity, high temperature catalyst.
  • 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.
  • Preferred residence times range from 0.5 to 10.0 seconds, more preferably 1.0 to 5.0 seconds and most 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. Pat. 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 203 a .
  • 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-5 psi hydrocarbon partial pressure

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
US11/039,125 2004-01-23 2005-01-18 System and method for selective component cracking to maximize production of light olefins Abandoned US20050161369A1 (en)

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EP (1) EP1713884B1 (pt)
JP (1) JP2007518866A (pt)
KR (1) KR100985288B1 (pt)
CN (1) CN1910264A (pt)
AU (1) AU2005207859B2 (pt)
BR (1) BRPI0506971B1 (pt)
CA (1) CA2553783C (pt)
MX (1) MXPA06008184A (pt)
NO (1) NO337658B1 (pt)
WO (1) WO2005073347A1 (pt)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014011759A1 (en) * 2012-07-12 2014-01-16 Lummus Technology Inc. Fluid catalytic cracking process and apparatus for maximizing light olefins or middle distillates and light olefins
WO2018053110A1 (en) * 2016-09-16 2018-03-22 Lummus Technology Inc. Fluid catalytic cracking process and apparatus for maximizing light olefin yield and other applications

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KR101503069B1 (ko) * 2008-10-17 2015-03-17 에스케이이노베이션 주식회사 유동층 접촉 분해 공정의 경질 사이클 오일로부터 고부가 방향족 및 올레핀을 제조하는 방법
US8137631B2 (en) * 2008-12-11 2012-03-20 Uop Llc Unit, system and process for catalytic cracking
FR3090684B1 (fr) * 2018-12-19 2021-08-27 Ifp Energies Now Conversion d’un brut pétrolier en lit fluidisé, avec zones de différents temps de contact
US12060528B2 (en) 2019-08-05 2024-08-13 Sabic Global Technologies B.V. Multiple dense phase risers to maximize light olefins yields for naphtha catalytic cracking
CN111408323A (zh) * 2020-04-17 2020-07-14 董国亮 一种降低催化剂管道应力以及衬里磨损的反应再生装置

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Publication number Priority date Publication date Assignee Title
WO2014011759A1 (en) * 2012-07-12 2014-01-16 Lummus Technology Inc. Fluid catalytic cracking process and apparatus for maximizing light olefins or middle distillates and light olefins
KR20150038043A (ko) * 2012-07-12 2015-04-08 루머스 테크놀로지 인코포레이티드 경질 올레핀 또는 중간 유분을 최대화하기 위한 유동상 촉매 분해 공정 및 장치 그리고 경질 올레핀
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
EA028567B1 (ru) * 2012-07-12 2017-12-29 Ламмус Текнолоджи Инк. Способ и установка флюид-каталитического крекинга для максимального увеличения выхода легких олефинов или средних дистиллятов и легких олефинов
US10184088B2 (en) 2012-07-12 2019-01-22 Lummus Technology Inc. Fluid catalytic cracking process and apparatus for maximizing light olefins or middle distillates and light olefins
KR102115859B1 (ko) 2012-07-12 2020-05-28 루머스 테크놀로지 엘엘씨 경질 올레핀 또는 중간 유분을 최대화하기 위한 유동상 촉매 분해 공정 및 장치 그리고 경질 올레핀
WO2018053110A1 (en) * 2016-09-16 2018-03-22 Lummus Technology Inc. Fluid catalytic cracking process and apparatus for maximizing light olefin yield and other applications
US10351786B2 (en) 2016-09-16 2019-07-16 Lummus Technology Inc. Fluid catalytic cracking process and apparatus for maximizing light olefin yield and other applications

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CA2553783C (en) 2013-03-26
EP1713884B1 (en) 2018-09-26
NO20063753L (no) 2006-08-22
ZA200606044B (en) 2007-12-27
JP2007518866A (ja) 2007-07-12
MXPA06008184A (es) 2007-01-26
CA2553783A1 (en) 2005-08-11
EP1713884A1 (en) 2006-10-25
CN1910264A (zh) 2007-02-07
AU2005207859A1 (en) 2005-08-11
AU2005207859B2 (en) 2010-01-07
WO2005073347A1 (en) 2005-08-11
KR100985288B1 (ko) 2010-10-04
NO337658B1 (no) 2016-05-30
BRPI0506971B1 (pt) 2020-12-08
BRPI0506971A (pt) 2007-07-03
KR20070018836A (ko) 2007-02-14

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