EP0490453A1 - Verfahren und Apparat zur Beseitigung von Kohlenstoffmaterialien von Feststoffteilchen - Google Patents

Verfahren und Apparat zur Beseitigung von Kohlenstoffmaterialien von Feststoffteilchen Download PDF

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Publication number
EP0490453A1
EP0490453A1 EP91203247A EP91203247A EP0490453A1 EP 0490453 A1 EP0490453 A1 EP 0490453A1 EP 91203247 A EP91203247 A EP 91203247A EP 91203247 A EP91203247 A EP 91203247A EP 0490453 A1 EP0490453 A1 EP 0490453A1
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EP
European Patent Office
Prior art keywords
reactor
particles
gas
solids
riser
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EP91203247A
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English (en)
French (fr)
Inventor
Michael Christopher Phillips
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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Publication of EP0490453A1 publication Critical patent/EP0490453A1/de
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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
    • 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
    • C10G11/182—Regeneration

Definitions

  • the invention relates to a process and an apparatus for the removal of carbonaceous materials from particles containing such materials.
  • Fluid catalytic cracking (FCC) processes are used to convert relatively heavy hydrocarbon products obtained from crude oil processing into lighter hydrocarbon products.
  • the catalyst particles used in these processes become very quickly contaminated with carbonaceous materials. These hydrocarbonaceous materials have to be removed in a regeneration process in order to permit reuse of the catalyst particles.
  • the catalyst is contacted with an oxygen containing gas in a fluidized bed at a temperature suitable to burn off the carbonaceous materials, thus restoring the activity of the catalyst.
  • Suitable FCC-feeds are gas-oils boiling in the range from 250-590 °C, especially 370-540 °C.
  • heavier feeds such as atmospheric and vacuum residual oils, often mixed with gas-oils.
  • these residual feeds usually contain considerable amounts of asphaltenes, which compounds have a high tendency to form coke during the cracking operation, a larger amount of coke will be deposited on the catalyst. This holds especially when only residual feeds are used without mixing with lighter gas-oil fractions. In regenerating these heavily coked spent catalyst particles it may be difficult to burn off enough coke to provide a suitable low concentration of carbon on the regenerated catalyst.
  • regenerators are suggested in which the coke is burned to carbon monoxide, thus limiting the formation of heat in the regenerator.
  • the carbon monoxide may be used as fuel gas, for instance for the production of electricity or steam.
  • a carbon monoxide boiler may be included after the regenerator to complete combustion of carbon monoxide to carbon dioxide.
  • a disadvantage of the process as described in the above-mentioned US patent, is that the riser reactor has to be of an extremely large height in order to obtain a reasonable removal of carbonaceous materials in the first stage. This is due to the fact that the temperature of the spent catalyst particles initially is too low for a rapid combustion.
  • the process may be operated by supplying substoichiometric or excess amounts of oxygen containing gas to either or both reactor in such a way that the flue gases at the top of the reactors are substantially free of oxygen.
  • recirculation of regenerated catalyst particles from the second reactor to the first is particularly beneficial as compensation for the limited heat formation in the first reactor.
  • the ratio of the amount of particles which are removed from the second reactor and the amount of particles which are introduced again in the first reactor may vary between 0.1 and 10, and is preferably between 0.2 and 5, more preferably between 0.3 and 1.
  • the recirculated particles have to be introduced into the relatively high density phase in the first reactor. Recirculated particles may be removed via one or more outlets in the second reactor at different heights.
  • the process of the present invention is especially suitable for the regeneration of spent FCC-catalyst particles, although it also may be used for other processes, as for instance the combustion of retorted oil shale particles.
  • the amount of carbon on the FCC-catalyst particles is suitably between 0.5 and 4 %wt, preferably between 0.3 and 1.5 %wt.
  • the particles are introduced into the relatively high density phase of the first reactor.
  • the process of the present invention is suitably carried out at a temperature in the first reactor of 525 °C to 725 °C, preferably 550 to 650 °C, and at a temperature in the second reactor of 625 to 950 °C, preferably 700-800 °C.
  • the substoichiometrical amount of oxygen introduced in the first reactor may be from 20-70% of the amount necessary to burn all the carbonaceous materials, and is preferably from 40 to 60%, most preferably 50%.
  • the pressure in both reactors is suitably between 1 and 10 bar, preferably between 1.5 and 4 bar.
  • the pressure drop over the first reactor is suitably between 0.1 and 2 bar, preferably between 0.3 and 1 bar.
  • the pressure drop over the second reactor is suitably between 1 and 5 bar, preferably 1.5 and 4 bar.
  • the second reactor to be used in the process according to the present invention is preferably a staged fluidized bed.
  • the process of the present invention is especially suitable for the regeneration of spent FCC-catalyst particles.
  • the feed for the FCC-process is suitably a hydrocarbon fraction boiling between 250 and 590 °C, especially between 370 and 540 °C.
  • Preferred feeds are atmospheric and vacuum residual fractions and socalled synthetic feed, such as coal oils, bitumen, shale oils and high boiling fractions thereof.
  • the boiling range is between 250 and 600 °C, or higher, and preferably a substantial amount boils above 450 °C.
  • the conversion conditions include a temperature in the range from about 425 °C to about 625 °C, preferably from about 510 °C to about 610 °C.
  • Cracking conditions also preferably include a pressure in the range from about atmospheric to about 4 atmospheres or more, particularly preferably about 2 atmospheres to about 3 atmospheres.
  • a catalyst/hydrocarbon weight ratio of about 2 to about 50, preferably 3 to about 10 is usually quite suitable.
  • a hydrocarbon weight hourly space velocity in the cracking operation of about 5 to about 50 per hour is preferably used.
  • the cracking zone employed may be of conventional design and may use dilute-phase fluidized solids contact, riser-type entrained solids contact, dense-bed fluidized solids contact, countercurrent contact, a moving, packed bed of solids or a combination thereof, between the feed hydrocarbons and the catalyst particles. Catalyst fluidization, entrainment, etc. may be assisted by gases such as steam or nitrogen. Conventional spent solids stripping means for removing volatiles from the spent solids may also suitably be employed.
  • the particulate solids to be used in the cracking process may optionally be catalytically active or may simply act as a heat carrier and sorbent for the hydrocarbons.
  • the particulate solids employed must be suitably attrition resistant and refractory to the high temperatures and to steaming which are characteristic of the process, so that the particles can be circulated for a practical period of time in a fluidized system.
  • Conventional particulate cracking catalysts and heat transfer solids can be used in the present process.
  • Suitable cracking catalysts may include a zeolitic crystalline aluminosilicate component.
  • Particulate solids other than active, acidic cracking catalyst may alternatively or additionally be circulated in the cracking system.
  • alumina particles may be included in the particulate solids inventory for the control of sulphur oxides and/or particles containing a highly active combustion promoting metal, such as a Croup VIII noble metal, may be mixed with the catalyst or heat carrier particles.
  • particles having a heat carrying capacity but low intrinsic acidic cracking activity may be circulated either alone or mixed with more active and acidic cracking catalyst to provide heat for either acidic or essentially thermal cracking of the hydrocarbons.
  • coke containing particles which result from cracking of hydrocarbons are regenerated in two steps: (1) an entrained bed step, in which particles and regeneration gas move in cocurrent, upward flow; and a (2) fluidized bed step, in which particles and regeneration gas move in generally countercurrent flow.
  • the first regeneration zone in which particles are partially regenerated in entrained flow in upwardly moving gases, may suitably be defined by any vessel, conduit, reactor or the like capable of containing the upwardly moving gases and solids at the temperatures and pressures employed in the first regeneration stage.
  • Riser-type vessels or transfer line vessels of the type used conventionally in carrying out riser-cracking in fluidized catalytic cracking systems are suitable for use as the first regeneration zone in the present process.
  • the vessels or conduit used to provide the riser-type regeneration zone can be sized in length and cross-sectional area to provide the desired gas and solids flow rates and residence times in order to create the relatively high density phase in the lower part of the zone, and a relatively low density phase in the upper part of the zone.
  • Suitable measures to create the differences in density are introduction of sufficient amounts of gas at a certain height, or decreasing the cross-sectional area, thus increasing the gas velocity.
  • the cross-sectional area of the relatively high density phase zone is suitably between 4-100 times as large as the cross-sectional area of the relatively low density zone, preferably 5-50, more preferably 9-25.
  • the riser reactor is preferably equipped with means for introducing molecular oxygen into the entraining gas stream at a plurality of vertically spaced levels in the first regeneration zone.
  • the second regeneration zone in which fluidized particles move generally downwardly, countercurrent to upwardly moving gases, may likewise be defined by any vessel, conduit, reactor or the like capable of containing the fluidized particles in flowing gases at the temperatures and pressures used in the second, fluidized stage of regeneration.
  • the second regeneration zone comprises a vertically elongated vessel having a length and diameter suitably adjusted for providing gas and solids residence times and solids fluidization according to the parameters of the process.
  • the vessel employed should be equipped with some sort of means for impeding back-mixing such as barriers, baffles, solids or gas dispersing means, redistribution means, or the like.
  • perforated plates, bars, screens, packing material, or other suitable internals may be used to impede back-mixing.
  • the catalyst entrainment-regeneration gas introduced, in addition to the desired amount of molecular oxygen, may include such relatively inert gases as nitrogen, steam, carbon monoxide, carbon dioxide, etc.
  • the composition of the entraining gases will, of course, vary along the gas flow path through the regeneration zone, as the gases pass from the upstream end to the downstream end of the riser reactor.
  • the amount of entraining gas and its pressure and superficial velocity in the riser are maintained at levels such that the particles present in the riser are entrained upwardly through the riser.
  • a solids residence time in the relatively low density phase zone of the riser reactor of about 3 to 6 seconds and a gas residence time of about 2 to 4 seconds are generally suitable.
  • the entraining gas when recovered from the riser reactor, it has a sufficiently high fuel value to have utility as a fuel gas.
  • the utility of the effluent gas from the riser reactor as a fuel gas will depend primarily on the carbon monoxide content of the gas. This may vary according to the oxygen and steam partial pressures, the total pressure, the gas and solids residence times and the exact temperature maintained in the riser reactor.
  • the amount of molecular oxygen (free oxygen) introduced into the first stage regeneration zone is preferably controlled to provide the desired degree of coke burn off in the entrained bed reactor, whether all the oxygen is introduced at the downstream end of the reactor or some is introduced further along the entraining gas path.
  • the entraining gas exiting the first regeneration zone should generally have an oxygen concentration of not more than 0.5 volume percent.
  • the effluent gas contains not more than 0.1 volume percent molecular oxygen.
  • the first and second reactors suitably have separate flue systems.
  • the particles are subject to a second stage of regeneration in a fluidized bed, wherein the particles moved generally downwardly in countercurrent flow relative to a fluidizing stream of gases.
  • a second stage of regeneration particles are passed into the upper end of a generally vertically extending regeneration zone, in which the particles are fluidized by an upwardly flowing stream of gases.
  • Coke-free, regenerated particles are withdrawn from the lower end of the regeneration zone for reintroduction into, the cracking process of which a part is recirculated to the first reactor.
  • the invention also relates to an apparatus for the removal of carbonaceous materials from particles containing such materials.
  • Figure 1 representing an apparatus according to the invention, comprising a first, riser-type reactor (1) comprising a normally vertical, elongated reactor provided with solids inlet means (2) and gas inlet means (3) at the lower part of the reactor, means for separating solids and gas (4) having an inlet (5) connected with the upper part of the first reactor, and having a gas (6) and a solids outlet (7), a second, fluidized bed reactor (8), comprising a normally vertical reactor connected with the solids outlet (7) of the gas/solids separation means and provided with gas inlet means (9) at the lower part of the reactor and with solid outlet means (10), the first and the second reactor being connected with means (11) for the recirculation of solids from the second reactor to the first reactor.
  • the lower part of the riser reactor has a larger diameter than the upper part of the reactor, as is shown in Figure 1. Further details on this feature have been described above. Also conical reactors may be used.
  • one or more additional gas inlet means (12) are present above the lower part of the reactor.
  • the solids outlet means of the gas/solids separation means are connected with the upper part of the second reactor.
  • one or more cyclones may be used.
  • the solids outlet means of the second reactor are preferably present at the lower part of the reactor.
  • the second, fluidized bed-type reactor is preferably provided with internals (13) making it possible to create a staged fluidized bed. Plates, gauges, trays etc. may be used.
  • the solids recirculation means is preferably provided with a valve, making adjustment of the recirculation ratio possible.
  • the second reactor may be provided with a separated gas outlet at the upper part of the reactor, or the gas outlet may be combined with the gas outlet of the gas/solids separation means as for instance has been described in European patent application No. 0206399.
  • the second reactor may be provided with heat exchanging means in the lower part of the reactor.
  • a cooling heat exchange device is provided at the bottom of the reactor as for instance has been described in European patent application No. 340852.

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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)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP91203247A 1990-12-13 1991-12-10 Verfahren und Apparat zur Beseitigung von Kohlenstoffmaterialien von Feststoffteilchen Withdrawn EP0490453A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9027038 1990-12-13
GB909027038A GB9027038D0 (en) 1990-12-13 1990-12-13 Process and apparatus for removal of carbonaceous materials from particles containing such materials

Publications (1)

Publication Number Publication Date
EP0490453A1 true EP0490453A1 (de) 1992-06-17

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EP (1) EP0490453A1 (de)
JP (1) JPH04322747A (de)
AU (1) AU8892191A (de)
CA (1) CA2057239A1 (de)
GB (1) GB9027038D0 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2072606A1 (de) * 2007-12-21 2009-06-24 BP Corporation North America Inc. System und Verfahren zum Regenerieren eines Katalysators in einer Fluid-Catalytic-Cracking-Einheit
US7699975B2 (en) 2007-12-21 2010-04-20 Uop Llc Method and system of heating a fluid catalytic cracking unit for overall CO2 reduction
US7699974B2 (en) 2007-12-21 2010-04-20 Uop Llc Method and system of heating a fluid catalytic cracking unit having a regenerator and a reactor
US7767075B2 (en) 2007-12-21 2010-08-03 Uop Llc System and method of producing heat in a fluid catalytic cracking unit
US7811446B2 (en) 2007-12-21 2010-10-12 Uop Llc Method of recovering energy from a fluid catalytic cracking unit for overall carbon dioxide reduction
US7935245B2 (en) 2007-12-21 2011-05-03 Uop Llc System and method of increasing synthesis gas yield in a fluid catalytic cracking unit
EP3040401A1 (de) * 2014-12-30 2016-07-06 Shell Internationale Research Maatschappij B.V. Reaktorsystem zur umwandlung sauerstoffhaltiger verbindungen zu olefinen und verfahren zur verwendung davon

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2784602B1 (fr) * 1998-10-20 2002-04-12 Eurecat Europ Retrait Catalys Procede de traitement d'un catalyseur ou d'un adsorbant en lit fluidise
BRPI0905257B1 (pt) * 2009-12-28 2018-04-17 Petroleo Brasileiro S.A. - Petrobras Processo de craqueamento catalítico fluido com emissão reduzida de dióxido de carbono

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2210654A1 (de) * 1972-12-19 1974-07-12 Mobil Oil
US4822761A (en) * 1986-05-13 1989-04-18 Ashland Oil, Inc. Method and apparatus for cooling fluid solid particles used in a regeneration system
US4849091A (en) * 1986-09-17 1989-07-18 Uop Partial CO combustion with staged regeneration of catalyst
US4917790A (en) * 1989-04-10 1990-04-17 Mobil Oil Corporation Heavy oil catalytic cracking process and apparatus
US5011592A (en) * 1990-07-17 1991-04-30 Mobil Oil Corporation Process for control of multistage catalyst regeneration with full then partial CO combustion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2210654A1 (de) * 1972-12-19 1974-07-12 Mobil Oil
US4822761A (en) * 1986-05-13 1989-04-18 Ashland Oil, Inc. Method and apparatus for cooling fluid solid particles used in a regeneration system
US4849091A (en) * 1986-09-17 1989-07-18 Uop Partial CO combustion with staged regeneration of catalyst
US4917790A (en) * 1989-04-10 1990-04-17 Mobil Oil Corporation Heavy oil catalytic cracking process and apparatus
US5011592A (en) * 1990-07-17 1991-04-30 Mobil Oil Corporation Process for control of multistage catalyst regeneration with full then partial CO combustion

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2072606A1 (de) * 2007-12-21 2009-06-24 BP Corporation North America Inc. System und Verfahren zum Regenerieren eines Katalysators in einer Fluid-Catalytic-Cracking-Einheit
US7699975B2 (en) 2007-12-21 2010-04-20 Uop Llc Method and system of heating a fluid catalytic cracking unit for overall CO2 reduction
US7699974B2 (en) 2007-12-21 2010-04-20 Uop Llc Method and system of heating a fluid catalytic cracking unit having a regenerator and a reactor
US7767075B2 (en) 2007-12-21 2010-08-03 Uop Llc System and method of producing heat in a fluid catalytic cracking unit
US7811446B2 (en) 2007-12-21 2010-10-12 Uop Llc Method of recovering energy from a fluid catalytic cracking unit for overall carbon dioxide reduction
US7921631B2 (en) 2007-12-21 2011-04-12 Uop Llc Method of recovering energy from a fluid catalytic cracking unit for overall carbon dioxide reduction
US7932204B2 (en) 2007-12-21 2011-04-26 Uop Llc Method of regenerating catalyst in a fluidized catalytic cracking unit
US7935245B2 (en) 2007-12-21 2011-05-03 Uop Llc System and method of increasing synthesis gas yield in a fluid catalytic cracking unit
EP3040401A1 (de) * 2014-12-30 2016-07-06 Shell Internationale Research Maatschappij B.V. Reaktorsystem zur umwandlung sauerstoffhaltiger verbindungen zu olefinen und verfahren zur verwendung davon

Also Published As

Publication number Publication date
JPH04322747A (ja) 1992-11-12
AU8892191A (en) 1992-06-18
CA2057239A1 (en) 1992-06-14
GB9027038D0 (en) 1991-02-06

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EP0490453A1 (de) Verfahren und Apparat zur Beseitigung von Kohlenstoffmaterialien von Feststoffteilchen

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