EP0180355B1 - Procédé de craquage catalytique avec trempe - Google Patents

Procédé de craquage catalytique avec trempe Download PDF

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Publication number
EP0180355B1
EP0180355B1 EP85307242A EP85307242A EP0180355B1 EP 0180355 B1 EP0180355 B1 EP 0180355B1 EP 85307242 A EP85307242 A EP 85307242A EP 85307242 A EP85307242 A EP 85307242A EP 0180355 B1 EP0180355 B1 EP 0180355B1
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EP
European Patent Office
Prior art keywords
catalyst
reactor
steam
quench
riser
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP85307242A
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German (de)
English (en)
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EP0180355A2 (fr
EP0180355A3 (en
Inventor
Frederick John Krambeck
Paul Herbert Schipper
Joe Edward Penick
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mobil Oil AS
ExxonMobil Oil Corp
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Mobil Oil AS
Mobil Oil Corp
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Publication date
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Publication of EP0180355A2 publication Critical patent/EP0180355A2/fr
Publication of EP0180355A3 publication Critical patent/EP0180355A3/en
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Publication of EP0180355B1 publication Critical patent/EP0180355B1/fr
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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

Definitions

  • the fluidized catalytic cracking, or FCC, process is one of the work horses of modern refineries.
  • hot catalyst contacts a relatively heavy oil feed, producing coked catalyst and cracked products.
  • the coked catalyst is regenerated by burning the coke from coked catalyst in a regenerator.
  • the catalyst is heated during the regeneration, because the coke burns.
  • the hot regenerated catalyst is recycled to contact more heavy oil feed.
  • refiners have attempted to maximize riser cracking, and minimize dense bed cracking. Generally this has been done by extending the catalyst riser and cutting down on the amount of catalyst inventory in the relatively large vessel into which the riser reactor discharged.
  • Some FCC units have attempted to practically eliminate dense bed cracking, by causing the riser reactor to discharge into a rough cut cyclone, or to discharge down toward the dense bed without agitating it, whereby substantial separation of cracked products from deactivated catalyst can be quickly obtained. Such an approach is shown in U.S. 3 785 962.
  • U.S. 4 072 600 disclosed adding Pt, Pd, etc. to the circulating catalyst inventory to promote afterburning of CO to C0 2 in the FCC regenerator.
  • the present invention provides an improved FCC process wherein a conventional fluidizable catalytic cracking catalyst and a hydrocarbon feed are charged to a reactor riser at catalytic riser cracking conditions to form catalytically cracked vapor product and spent catalyst which are discharged into a reactor vessel via a riser reactor outlet connective with a separation means to produce a catalyst lean phase comprising a majority of said cracked product, and a catalyst rich phase comprising a majority of said spent catalyst, is discharged into a dense bed of catalyst maintained below said riser outlet and said catalyst lean phase is discharged into said vessel and then withdrawn from said vessel via a vessel outlet, the improvement comprising addition of a quenching stream into said vessel above said dense bed of catalyst.
  • any conventional feed to an FCC unit can be used.
  • the feed to an FCC unit comprises gas oils, vacuum gas oils, topped crudes, etc.
  • Heavy feeds, such as tar sands, shale oil, and asphaltic fractions may be used, if the unit can tolerate the high metals concentrations and coking tendencies of these feeds.
  • the present invention is not the discovery of a new feed to an FCC unit, but a way to make better use of feeds now used for FCC units.
  • any catalyst suitable for use in an FCC unit can be used in the process of the present invention.
  • the catalyst is one of the many commercially available zeolite based catalysts, but it is also possible to obtain benefits from practicing the present invention when amorphous materials such as alumina, or amorphous silica/alumina are used as the catalyst.
  • Especially preferred catalysts are rare earth exchanged Y zeolites in an amorphous matrix.
  • the catalyst may contain one or more of the following types of promoters.
  • the present invention helps FCC units operating with conventional catalyst to operate more efficiently.
  • the riser reactor discharges directly into a rough cut cyclone, or other separation means, whereby a very quick separation of cracked products from catalyst may be contained.
  • the riser reactor discharge down into the dense bed reactor, from a relatively high distance above the dense bed catalyst level. This minimizes stirring up of the dense bed, and minimizes contact of cracked products/catalyst.
  • the riser reactor discharges directly into a dense bed of catalyst, either in a vertical up direction, or horizontally. Such an operation tends to promote dense bed cracking, and should be avoided.
  • Many older FCC units were built at a time when dense bed cracking was more highly regarded, and it is not possible to economically change the configuration of the units. It is harder to see the benefits of the present invention in such units, because a lot of hot catalyst is tossed about within the vessel containing the dense bed of catalyst, minimizing the temperature quenching effect of the steam quench.
  • the preferred riser reactor provides a residence time of less than 10 seconds, preferably on the order of 1-5 seconds, and it discharges directly into a rough cut cyclone to effect rapid separation of cracked products from catalyst.
  • the riser reactor may operate in upflow, or downflow, though an upflow riser reactor is preferred because there is much more operating experience available for such a unit.
  • the riser reactor may actually be two or more reactors in series, or in parallel. Although such riser reactor designs are contemplated for use herein, they form no part of the present invention.
  • the riser reactor discharges into a vessel designed to contain a dense bed of catalyst.
  • Conventional FCC dense bed reactor designs call for a relatively large vessel, usually several orders of magnitude larger in volume than the riser reactor, which serves to collect spent catalyst in the lower portion of the reactor.
  • the spent catalyst is withdrawn from the bottom of the reactor, usually through a stripper zone containing baffles, and removed from the reactor. Stripping steam is added at the bottom of the reactor vessel to displace easily strippable hydrocarbons from the spent catalyst, so that these strippable hydrocarbons will not be burned in the regenerator.
  • Any conventional FCC regenerator may be used in conjunction with the present invention.
  • CO afterburning regenerators are, in most situations, preferred as far as maximum efficiency in the total FCC unit is concerned, however the present invention will work equally well with CO afterburning and non-CO afterburning regenerators.
  • the regenerator is an essential portion of an FCC unit, but the regenerator section, by itself, forms no portion of the present invention.
  • An especially effective regenerator design is a stacked regenerator with a first dense bed, or coke combustor, a dilute phase transport riser and a second dense bed of hot regenerated catalyst maintained generally above the coke combustor.
  • one or more quench means are disposed within the reactor vessel into which the riser reactor discharges.
  • Steam is the preferred quenching medium.
  • Steam is preferably admitted via a radially disposed steam injection ring disposed just above the dense bed of catalyst.
  • the function of the steam quench is twofold. It reduces the temperature of the cracked products in the vapor phase above the dense bed of catalyst. It also displaces the cracked hydrocarbons from the reactor vessel, thereby decreasing the residence time of these materials in the reactor vessel.
  • the amount of steam quench injected, and the precise location of the steam quench injection point within the vessel containing the dense bed of spent catalyst, will determine the change in residence time of cracked vapors within the reactor.
  • the temperature, and amount of steam quench will determine the temperature change of cracked product within the reactor.
  • the temperature of the steam will have a significant effect on the quenching effect, or temperature reduction of cracked products. It is also possible to simply add water and let the water vaporize within the reactor, or provide enough surface area in the steam quench ring so that the water will vaporize and become steam before entering the reactor. This would give maximum cooling per weight of water added, the cooling effect being vaporization of water to steam, followed by an increase in sensible heat of the steam produced.
  • the riser reactor discharges into a primary cyclone, which makes a rough, but fairly effective, separation of catalyst from cracked products.
  • the vapor from the primary cyclone is discharged directly into a secondary cyclone which is able to effect a far more complete separation of catalyst from cracked products than could be achieved in the rough cut cyclone attached directly to the riser reactor outlet.
  • the extent of undesirable thermal cracking that goes on in a reactor may be estimated by calculating the residence time in the reactor at a given temperature. These two numbers can be used to devise an ERT or Equivalent Reaction Time at 427 ° C (800 ° F). More details about ERT are provided in U.S. 4 379 747 and U.S. 4 428 824. Another way of evaluating relative reaction velocities in thermal cracking is to compare S.F. or Soaking Factors. By definition, the ERT and SF are 1.0 at 427 ° C (800 ° F). As the temperature increases, the reaction rate increases, to 2.0 at 439 ° C (822 ° F), and so on.
  • the amount of thermal cracking will be cut about in half by reducing the residence time of the catalytically cracked product by one half, or by reducing the vapor temperature from 439 to 427°C (822 to 800 ° F), or some combination of these.
  • ERT is reduced by at least 4%.
  • the amount of quench added should be sufficient to reduce thermal cracking enough to increase the yield of gasoline and light fuel oil products at least 0.5%, and preferably 1 to 2%, or more.
  • reactor riser 4 is in actuality the reactor where well over 90 percent of the desired catalytic cracking reactions occur. Ideally, 100 percent of the reactions would take place in reactor riser 4, and no reaction whatever would take place in reactor 1. In time, refiners may revise their vocabulary to refer to riser 4 as the reactor, and vessel 1 as a spent catalyst/cracked product separation means, but such usage would be confusing to those skilled in the FCC arts.
  • Dense bed 20, with upper surface or interface level 17 is the collection of catalyst from the diplegs of the cyclones within reactor 1.
  • the dense bed/dilute phase interface 17 may be below the catalyst diplegs, as shown in the drawing, or the dense bed level may be raised, or the diplegs extended, so that the diplegs are immersed within the dense bed of catalyst 20.
  • Catalytically cracked products are removed from reactor 1 via lines 9 and 13 into reactor outlet plenum 14 and then sent via line 10 to product recovery means not shown.
  • product recovery means not shown.
  • primary cyclone 2 secondary cyclone 6 and third stage cyclone 8.
  • second inlet line 13 to plenum 14 is intended to show that other third stage cyclones will be present.
  • the spent catalyst which collects as dense bed 20 in the bottom of reactor 1 is subjected to stripping to remove easily strippable hydrocarbon vapors from the spent catalyst before it is sent to a catalyst regenerator, not shown.
  • This steam stripping of spent catalyst which is conventional, is conducted at reactor stripper 21.
  • a steam supply, shown as line 30, admits steam via either line 22 and/or 24 to lower and upper stripper steam rings, respectively.
  • inlet 5 to cyclone 6 would resemble an inverted funnel which was radially aligned with, and above outlet 3 of primary cyclone 2, as shown in Figure 2.
  • closed cyclones Such a configuration is not, strictly speaking, "closed”, because it is still possible, and very desirable, for cracked hydrocarbon products, and quench steam, to enter inlet 5 in the annular space between outlet 3 and inlet 5.
  • a characteristic of "closed cyclone" configuration is that 90% of the cracked vapor product will pass from the primary cyclone outlet and enter the secondary cyclone inlet in less than 1 second, preferably in less than 0.5 second.
  • Quench steam ring 27 shown in the drawing would reduce the residence time of cracked products in space 15, but would do little or nothing towards reducing the temperature of the cracked products, because of the large amount of hot spent catalyst present. In such a circumstance, it may be beneficial to move the quench steam ring to an elevation equal to, or slightly above the reactor riser outlet, so that steam quench will have a noticeable cooling effect on reactor vapors. In some circumstances, a combination of steam quench via quench ring 27 shown in the drawing and another quench ring located above the riser reactor outlet, and not shown in the drawing, would be beneficial.
  • the two illustrative embodiments which follow do not represent commercial or laboratory tests. They are based on computer simulations of commercial operation, and are believed to be accurate predictors of what will happen in commercial operation.
  • the feedstock used was similar to the Joliet Sour Heavy Gas Oil described hereafter.
  • reactor vessel temperature refers to the vapor outlet temperature, measured at the top of the reactor. The reason the reactor vessel temperature did not change much was because in the open cyclone configuration, corresponding roughly to the one shown in the drawing, the steam is in contact with significant amounts of hydrocarbon exiting the vessel and some catalyst.
  • the reduction in vapor residence time in the dilute phase portion of reactor vessel 1 is estimated to be about 10-15%, or a reduction of about 4 to 6 seconds residence time.
  • reactor vessel temperature refers to the temperature at the top of the reactor vessel, which is not the same thing as the temperature of the vapor leaving the reactor.
  • the vapor leaving the unquenched reactor would have a temperature of about 535.0 ° C (995 ° F).
  • the supercooling of the reactor vessel dilute phase temperature by quench steam was due to the fact that the closed cyclone configuration resulted in significantly less cracked vapor and entrained catalyst being discharged into the dilute phase within reactor vessel 1.
  • the quench steam was far more effective in cooling down this greatly reduced weight of material, in the closed cyclone configuration case, than when the quench steam was being inundated by vast amounts of cracked vapors and spent catalyst, as in the open cyclone configuration discussed in conjunction with Table III.
  • the separator comprises a primary cyclone attached to the riser outlet, and wherein a secondary cyclone is provided at an elevation above the dense bed and connective with the vessel outlet, and the quench is added to the vessel at an elevation intermediate the dense bed and the secondary cyclone.

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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)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Claims (10)

1. Katalytisches Wirbelschichtcrackverfahren, bei dem ein herkömmlicher fluidisierbarer kata- lytischer Crackkatalysator und eine Kohlenwasserstoffzufuhr unter katalytischen Risercrackbedingun- gen einem Riserreaktor zugeführt werden, um ein katalytisch gecracktes Dampfprodukt und verbrauch- ten Katalysator zu bilden, die über den Riserreaktorauslaβ in ein ReaktorgefâB abgegeben werden, das mit einem Separator in Verbindung steht, um eine katalysatorarme Phase, die den Hauptteil des gecrack- ten Produktes umfaβt, und eine katalysatorreiche Phase zu erzeugen, die den Hauptanteil des ver- brauchten Katalysators umfaβt, die katalysatorreiche Phase in das dichte Bett des Katalysators abgegeben wird, das unter dem RiserauslaB gehalten wird, und die katalysatorarme Phase in das GefâB abgegeben wird und danach über den Gefäßauslaß aus dem GefâB abgezogen wird, wobei die Verbesserung die Zugabe eines Abschreckstroms in dieses GefâB oberhalb des dichten Katalysatorbettes umfaBt.
2. Verfahren nach Anspruch 1, worin der Abschreckstrom aus der Gruppe von Wasser, Dampf und verdampfbaren, verflüssigbaren Kohlenwasserstoffen ausgewâhlt ist.
3. Verfahren nach Anspruch 1, worin der Abschreckstrom Dampf ist.
4. Verfahren nach Anspruch 3, worin die Menge des dem GefâB zugeführten Abschreckdampfes, als Gew.-% der Kohlenwasserstoffzufuhr ausgedrückt, 0,1 bis 20 Gew.-% betrâgt.
5. Verfahren nach Anspruch 4, worin 0,5 bis 5 Gew.-% Dampf zum Abschrecken zugesetzt werden.
6. Verfahren nach einem der vorstehenden Ansprüche, worin der Separator zumindest einen Zyklon- separator umfaBt, der an den RiserreaktorauslaB verbunden ist.
7. Verfahren nach Anspruch 6, worin die Menge und die Temperatur des Abschreckzusatzes zum Re- aktor ausreichend sind, um das thermische Cracken um mindestens 50% zu verringern, gemessen durch die âquivalente Reaktionszeit bei 427°C (800°F).
8. Verfahren nach einem der Ansprüche 1 bis 5, worin der Separator einen nach unten abgebenden Ri- serreaktorauslaß umfaBt, der 3 bis 20 Meter oberhalb des dichten Katalysatorbettes angeordnet ist.
9. Verfahren nach Anspruch 7, worin die Menge und die Temperatur des Abschreckzusatzes zum Re- aktor ausreichend sind, um das thermische Cracken um mindestens 4% zu verringern, gemessen durch die âquivalente Reaktionszeit bei 427°C (800°F).
10. Verfahren nach einem der Ansprüche 1 bis 7, worin der Separator einen primâren Zyklon umfaßt, der an den Riserauslaß verbunden ist, und worin in einer Höhe oberhalb des dichten Bettes und in Verbindung mit dem GefâBauslaB ein sekundârer Zyklon vorgesehen ist, und die Abschreckung dem Gefäß in einer Höhe zwischen dem dichten Bett und dem sekundâren Zyklon zugeführt wird.
EP85307242A 1984-10-30 1985-10-10 Procédé de craquage catalytique avec trempe Expired EP0180355B1 (fr)

Applications Claiming Priority (2)

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US66653384A 1984-10-30 1984-10-30
US666533 1984-10-30

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EP0180355A2 EP0180355A2 (fr) 1986-05-07
EP0180355A3 EP0180355A3 (en) 1986-07-02
EP0180355B1 true EP0180355B1 (fr) 1989-04-05

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EP (1) EP0180355B1 (fr)
JP (1) JPS61113686A (fr)
AU (1) AU586985B2 (fr)
DE (1) DE3569261D1 (fr)
ES (1) ES8609440A1 (fr)
ZA (1) ZA857398B (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4909993A (en) * 1984-05-21 1990-03-20 Mobil Oil Corporation Closed cyclone FCC catalyst separation apparatus
US5055177A (en) * 1984-05-21 1991-10-08 Mobil Oil Corporation Closed cyclone FCC catalyst separation method and apparatus
US5039397A (en) * 1984-05-21 1991-08-13 Mobil Oil Corporation Closed cyclone FCC catalyst separation method and apparatus
US4793915A (en) * 1987-01-15 1988-12-27 Mobil Oil Corporation Short contact time fluid catalytic cracking process
US5098672A (en) 1987-08-11 1992-03-24 Stone & Webster Engineering Corp. Particulate solids cracking apparatus and process
CA2017116C (fr) * 1990-03-26 1996-11-12 James Francis Mosby Craquage catalytique avec capacite de refroidissement

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4043899A (en) * 1976-02-27 1977-08-23 Mobil Oil Corporation Method and means for separating gasiform materials from finely divided catalyst particles
US4043893A (en) * 1976-03-31 1977-08-23 Erico Products, Inc. Electrical contact
US4194965A (en) * 1978-02-02 1980-03-25 Mobil Oil Corporation Fluid catalytic cracking
US4478708A (en) * 1983-10-11 1984-10-23 Farnsworth Carl D Method and apparatus for separating fluidized solid particles suspended in gasiform material
US4555328A (en) * 1984-01-19 1985-11-26 Mobil Oil Corporation Method and apparatus for injecting liquid hydrocarbon feed and steam into a catalytic cracking zone

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ES548260A0 (es) 1986-09-01
DE3569261D1 (en) 1989-05-11
ZA857398B (en) 1987-05-27
ES8609440A1 (es) 1986-09-01
EP0180355A2 (fr) 1986-05-07
AU4816785A (en) 1986-05-08
JPS61113686A (ja) 1986-05-31
AU586985B2 (en) 1989-08-03
EP0180355A3 (en) 1986-07-02

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