EP0282371B1 - Verfahren und Vorrichtung für das katalytische Kracken von Kohlenwasserstoffeinsätzen - Google Patents

Verfahren und Vorrichtung für das katalytische Kracken von Kohlenwasserstoffeinsätzen Download PDF

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Publication number
EP0282371B1
EP0282371B1 EP88400305A EP88400305A EP0282371B1 EP 0282371 B1 EP0282371 B1 EP 0282371B1 EP 88400305 A EP88400305 A EP 88400305A EP 88400305 A EP88400305 A EP 88400305A EP 0282371 B1 EP0282371 B1 EP 0282371B1
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EP
European Patent Office
Prior art keywords
catalyst
stripping
regenerated catalyst
spent catalyst
spent
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Expired - Lifetime
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EP88400305A
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English (en)
French (fr)
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EP0282371A1 (de
Inventor
Jean-Louis Mauleon
Jean-Bernard Sigaud
Bernard Chapotel
Léonard Seglin
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Total Marketing Services SA
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Compagnie de Raffinage et de Distribution Total France SA
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Priority to AT88400305T priority Critical patent/ATE67233T1/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

Definitions

  • the present invention relates to catalytic cracking of hydrocarbon charges. It relates more particularly to improvements made to the separation of effluents from the cracking reaction and from the spent catalyst.
  • the regenerated catalyst (at a temperature generally above 600 ° C.) and the feed to be treated are brought into continuous contact in a vertical or inclined tubular reactor.
  • the latter when operating in ascending mode, is often designated by specialists by the English term “riser”, and designated by the term “dropper” when operating in descending mode.
  • the load usually preheated to a temperature of 80 to 400 ° C and injected at a pressure between 0.7.105 and 3.5.105 relative Pascals, vaporizes, then cracks on contact with the active sites of the catalyst, while ensuring the pneumatic transport of the grains thereof, the desired average size of which is approximately 70 ⁇ m.
  • the hydrocarbon vapors After a contact time of the order of 0.1 to 10 seconds, the hydrocarbon vapors, at a temperature of the order of 475 to 575 ° C, are separated from the spent catalyst using a separator ballistics disposed at the outlet of the tubular reactor.
  • This separator is located in an area at the top of which the vapors rise hydrocarbons which, after recovery of the catalyst fines by a cyclone, are sent to the fractionation device.
  • the catalyst grains fall by gravity at the bottom of this zone into a medium in a dense fluidized bed where, in order to be completely separated from the hydrocarbons still present in the pores, they are stripped with steam.
  • the stripped catalyst grains are then discharged to a regenerator, in which the catalytic activity is restored by combustion of the coke deposited during the cracking reaction.
  • the heat of combustion is distributed between the catalyst (around 70%) and the regeneration fumes.
  • the regenerated catalyst is recycled to the reaction zone, where the fraction of the heat of combustion of the coke transmitted to the catalyst in the regenerator is used to vaporize the charge, provide the reaction heat (endothermic) and compensate for the various thermal losses, ensuring thus the thermal equilibrium of the unit.
  • the average cycle time for the catalyst is approximately 15 minutes.
  • the FCC process is therefore implemented in such a way that the cracking unit is in thermal equilibrium, all the necessary heat being provided by the combustion of the coke deposited during the cracking reaction on the catalyst grains.
  • the couple "preheating temperature of the charge-circulation of the regenerated catalyst" is thus adjusted so as to obtain the desired reaction temperature throughout the reaction zone and, in particular, at the outlet of the reactor.
  • the object of the present invention is to substantially improve the quality of the separation of the effluents from the cracking reaction and that of the stripping of the catalyst, so as to limit the losses of hydrocarbon residues and to regenerate spent catalyst containing substantially only the coke necessary to ensure the thermal balance of the unit.
  • a device ballistics of a type known per se makes it possible to orient the grains of catalyst downwards, while the hydrocarbon vapors rise upwards and are, after separation of the fines using a cyclonic system, sent to the fractionation zone. This operation, which is most often carried out in a dilute fluidized phase, ensures separation that is both rapid and effective between a large portion of the hydrocarbon vapors and the catalyst grains.
  • a stripping operation during which the displacement and recovery of the gaseous hydrocarbons entrained in the suspension of catalyst are ensured by backwashing using a gaseous fluid such as water vapor. It is necessary that the contacting is effective and that any back-mixing is minimized.
  • the actual stripping takes place in the dense phase, in an enclosure generally characterized by a high height to diameter ratio. This enclosure is often provided with internal baffles, to promote contact of the catalyst suspension with the stripping fluid.
  • the desorption of the heaviest hydrocarbons trapped on the catalyst is favored by keeping the partial pressure of the hydrocarbons in the vapor phase as low as possible relative to their bubble pressure, therefore by a high temperature and a low pressure.
  • very polar stripping fluids such as water vapor, more strongly absorbed than hydrocarbons, tends to favor the desorption of hydrocarbons.
  • the stripping reaction either by desorption or by displacement of the entrained hydrocarbons, is relatively rapid. It is therefore useless to want to seek a better stripping efficiency by extending the time contact with the stripping fluid, because during the stripping operation, the conditions are also favorable for coking reactions of heavy hydrocarbons, with production of hydrogen and methane in particular; the net result is then a reduction in the hydrogen in the residual coke remaining on the spent catalyst, in favor of the production of light gases.
  • the Applicant has established that the recovery of the hydrocarbon effluents from the cracking reaction can be considerably improved by practicing, between the two previously described zones, a mixture of the spent catalyst grains coming from the ballistic separation zone, with grains of regenerated or partially regenerated catalyst, having a temperature higher than that of the grains of spent catalyst.
  • EP-A-137998 teaches the use of a second stripping chamber in which the spent catalyst is mixed with the hot regenerated catalyst in order to vaporize the heavy hydrocarbons possibly present on the spent catalyst. The recovery of effluents is improved, but it is necessary to use two stripping chambers. Furthermore, according to EP-A-137998, the hot regenerated catalyst is injected at the bottom of the stripping zone of the spent catalyst.
  • the present invention aims to remedy this drawback and it therefore relates to a process for the catalytic cracking in the fluid state of a hydrocarbon charge, comprising a step of bringing the charge into contact with the upward or downward flow and grains of a cracking catalyst in a tubular reactor, a step of ballistic separation of the spent catalyst and the cracked charge, downstream of the end of said reactor, a step of stripping in dense fluid phase of the spent catalyst thus separated, using a fluid injected against the current of this catalyst, a step of regenerating said catalyst under conditions of combustion of the coke deposited on it, and a step of recycling the regenerated catalyst to the supply of said reactor, characterized in that, between said step of ballistic separation and said stripping step, grains of catalyst at least partially regenerated, having a temperature higher than that of spent catalyst, are dispersed substantially homogeneously, above the dense fluidized phase, along substantially the entire horizontal section of the diluted fluidized phase located above this dense fluidized phase.
  • the hot catalyst grains coming from the regeneration zone are advantageously mixed in quantity and at a temperature such that the local temperature of the mixture resulting from this dispersion undergoes an increase from 10 to 150 ° C. and, preferably, from 20 to 70 ° C.
  • This mixture or recycle of catalyst, hot and at least partially regenerated, is preferably itself previously stripped, to eliminate the presence of inert compounds due to entrainment of regeneration gas, so as to avoid an unnecessary overload of the gas compressor cracked.
  • the recycled catalyst can advantageously either be completely regenerated, in the same way as the catalyst supplying the reaction zone, or be only partially regenerated and, in this case, the recycled catalyst in accordance with the present invention may be taken from various points in the area of regeneration and, in particular, in the first regeneration chamber, if the unit has several successive chambers for regenerating the spent catalyst.
  • the recycling of catalyst grains is preferably carried out in the immediate vicinity of the surface of the dense fluidized bed of the stripping zone.
  • the invention also relates to a device for the catalytic cracking of a hydrocarbon feedstock, comprising a cracking column with ascending or descending flow, means for feeding the upstream end of said column with grains of regenerated catalyst, means for introducing into said column a hydrocarbon feedstock, a means of ballistic separation of the products of the cracked feedstock and of the spent catalyst grains, a stripping means in dense fluidized phase of spent catalyst, by at least one fluid, of the spent catalyst, at least one unit for regenerating said catalyst by combustion of the coke deposited thereon, and means for recycling the regenerated catalyst to the supply of said column,
  • this device being characterized in that it comprises, between said ballistic separation means and said stripping means, at least one means for the distribution, in a substantially homogeneous manner, of catalyst grains at m oins partially regenerated, having a temperature higher than that of the spent catalyst grains, above the dense fluidized phase, along substantially the entire horizontal section of the diluted fluidized phase, located above this dense fluidized phase.
  • This means of introducing and dispersing the hot regenerated catalyst will be arranged in such a way that the mixing with the spent catalyst will take place in the immediate vicinity of the surface of the dense fluidized bed of the stripping zone.
  • the introduction of the hot and at least partially regenerated catalyst may be carried out, in a simple manner and in a manner known per se, by pouring said catalyst immediately above the surface of the dense bed.
  • This type of stripping enclosure in fact promotes immediate homogenization of the catalyst grains at the top of the bed.
  • the grains of hot and at least partially regenerated catalyst will therefore be dispersed homogeneously along the entire horizontal section of the diluted fluidized phase, located immediately above the surface of the dense fluidized bed of the zone of stripping, so that the hydrocarbons vaporized during this dispersion are immediately displaced by the rising water vapor. It goes without saying that such a vaporization of the hydrocarbons remaining on the surface of the catalyst grains will be all the better as the ballistic device situated above the outlet of the reaction zone will itself ensure good homogeneous dispersion of the grains of catalyst along the entire section of the enclosure.
  • FIG. 1 we can see the upper part of an upward cracking column 1, opening into an enclosure 2 which is concentric with it, opposite a ballistic separator 3 promoting disengagement, homogeneous dispersion along the entire section. of enclosure 2 and the fall by gravity of the spent catalyst grains.
  • the cracked products pass through a cyclone 4, where they are separated from the last particles of catalyst, and they are then evacuated by a line 5 to a fractionation zone.
  • the spent catalyst particles collect by gravity at the base of the enclosure 2, where a stripping fluid such as water vapor is introduced against the current by the diffuser 6 while forming a dense fluidized bed of catalyst.
  • the stripped catalyst is then evacuated via line 9 at the base of enclosure 2, to the regeneration device, not shown.
  • a fraction of the catalyst originating from the regeneration zone, and the temperature of which is greater than that of the spent catalyst grains, is introduced via line 10 into the diluted fluidized bed and is dispersed in a substantially homogeneous manner.
  • the inclined pipe 10 is extended at its downstream end by a part 11 curved upwards, which ensures by gravity the homogeneous distribution of the catalyst along the entire horizontal section of the enclosure 2, immediately above the surface 8 of the dense fluidized bed 7.
  • the temperature at the outlet of column 1 and in the upper part of enclosure 2 will, for example, be between 480 and 550 ° C., so that by injecting a sufficient quantity of regenerated catalyst at a temperature comprised between 650 and 850 ° C, it will be possible to raise the temperature of the catalyst in dense fluidized phase between 550 and 650 ° C.
  • the curved part 11 extending the pipe 10 may comprise two branches separated by an interval oriented towards the column 1, so as to project two jets of catalyst of on either side of this column.
  • FIGS. 2 and 3 which represent alternative embodiments of the invention in the case of a rising cracking column, or "riser"
  • the members already described with reference to FIG. 1 are designated by the same reference figures.
  • the recycled catalyst is no longer distributed by gravity in enclosure 2, but is conveyed by a carrier fluid such as water vapor, a light hydrocarbon or a mixture of the two .
  • the catalyst supply pipe 14 is an ascending pipe opening laterally into the enclosure 2 and extending at its upper part by a curved part 15, which forms a deflector for the catalyst particles, so as to allow a homogeneous dispersion in the diluted fluidized phase located immediately above the surface 8 of the stripping bed 7.
  • the recycled catalyst is again conveyed to the enclosure 2 by a carrier fluid circulating in an ascending pipe 14, but this pipe opens out at the center of the enclosure in an annular distributor 16, surrounding the column 1, which distributes the catalyst through lateral openings 17.
  • the invention also applies to devices with a falling cracking column or "dropper", as shown in FIG. 4.
  • the column 18 opens into the enclosure 19 directly above a deflector 20, which distributes the spent catalyst in the enclosure, while ensuring the release of the hydrocarbons: as before, the hydrocarbon vapors pass in a cyclone 21 and are discharged via line 22, while the catalyst grains collect at the bottom of the enclosure. They are kept there in a dense fluidized bed 23 and stripped by steam injected at 24, before being evacuated via line 25 to the regenerator.
  • the recycle catalyst is introduced into the enclosure 19 by an inclined pipe 26, which opens directly above a distributor 27, here disposed in the center of the enclosure 19, below the deflector 20.
  • the invention therefore uses simple means, making it possible to appreciably improve the separation of the cracked products and the spent catalyst, as well as the quality of the stripping.

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

Claims (9)

1. Verfahren für das katalytische Craken in fluidem Zustand eines Kohlenwasserstoffeinstatzes, umfassend einen Schritt eines Kontaktierens in aufsteigender oder absteigender Strömungsrichtung des Einsatzes und der Partikel eines Katalysators zum Cracken in einem rohrförmigen Reaktor, einen Schritt einer ballistischen Trennung des gebrauchten Katalysators von dem gecrackten Einsatz nach dem Ende des Reaktors, einen Schritt eines Strippens in dichter, fluidisierter Phase der derart getrennten, gebrauchten Katalysators mit Hilfe eines im Gegenstrom zum Katalysator eingespritzten Fluids, einen Schritt einer Regeneration des Katalysators unter Bedingungen einer Verbrennung von auf diesem abgelagertem Koks und einen Schritt einer Recyclierung des regenerierten Katalysators zur Speisung des Reaktors, dadurch gekennzeichnet, daß swischen dem Schritt der ballistischen Trennung und dem Schritt des Strippens in im wesentlichen homogener Weise Partikel des zumindest teilweise regeneriertien Katalysators mit einer die Temperatur des gebrauchten Katalysators übersteigender Temperatur oberhalb der dichten fluidisierten Phase verteilt werden, wobei sich im wesentlichen der gesamte horizontale Querschnitt der verdünnten fluidisierten Phase oberhalb der dichten fluidisierten Phase befindet.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Mischung des Katalysators in einer Menge und bei einer Temperatur erfolgt, sodaß daraus eine Erhöhung der lokalen Temperatur zwischen 10 und 150°C, vorzugsweise zwischen 20 und 70°C, resultiert.
3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß der zumindest teilweise regenerierte Katalysator in unmittelbarer Nähe der Oberfläche des dichten, fluidisierten Bettes des Strippzone verteilt wird.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der zumindest teilweise regenerierte Katalysator aus der Regenerationszone nach der Abtrennung wenigstens eines Teiles der Verbrennungsgase stammt.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Abtrennung wenigstens eines Teiles der Verbrennungsgase durch ein Strippen mit Hilfe eines Fluids, wie beispielsweise Wasserdampf, einem Inertgas oder einer Mischung dieser, durchgeführt wird.
6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß der zumindest teilweise regenerierte katalysator während der Regeneration des Katalysators, insbesondere nach seinem Durchtritt durch die erste Verbrennungskammer, wenn der Regenerator mehrere umfaßt, abgezogen wird.
7. Vorrichtung für das katalytische Craken eines Kohlenwasserstoffeinsatzes, umfassend eine Crakkolonne (1, 18) mit aufsteigender oder absteigender Strömungsrichtung, Mittel zur Zufuhr von Partikeln eines regerierten Katalysators am vorderen Ende der Kolonne, Mittel zum Einführen eines Kohlenwasserstoffeinsatzes in die Kolonne, Mittel zur ballistischenTrennung (3, 27) der Produkte des gecrackten Einsatzes sowie der Partikel des gebrauchten katalysators, Mittel zum Strippen (6, 24) der Partikel des gebrauchten Katalysators in dichter, fluidisierter Phase des gebrauchten Katalysators mit wenigstens einem Fluid, wenigstens eine Regenerationseinheit für den Katalysator durch Verbrennung von auf diesem abgelagertem Koks und Mittel zur Recyclierung des regenerierten Katalysators zur Zufuhr in die Kolonne, dadurch gekenzeichnet, daß sie zwischen den Mitteln zur ballistischen Trennung (4, 21) und den Mitteln zum Strippen (6, 24) wenigstens ein Mittel (10, 11; 14, 15; 14, 16; 26, 27) zum Verteilen von Partikeln des zumindest teilweise regenerierten Katalysators in im wesentlichen homogener Weise mit einer die Temperatur der Partikel des gebrauchten Katalysators übersteigender Temperatur oberhalb der dichten, fluidisierten Phase umfaßt, wobei sich im wesentlichen der gesamte horizontale Querschnitt der verdünnten, fludisierten Phase oberhalb der dichten, fluidisierten Phase befindet.
8. Vorrichtung nach Anspruch 7, dadurch gekennzeichnet, daß sie Mittel (10, 11; 14, 15; 14, 16; 26, 27) für eine homogene Verteilung des zumindest teilweise regenerierten Katalysators oberhalb der Oberfläche (8) des fluidisierten Bettes (7, 23) des gebrauchten Katalysators während des Strippens umfaßt.
9. Vorrichtung nach einem der Ansprüche 7 oder 8, dadurch gekennzeichnet, daß sie vor den Mitteln (10, 11; 14, 15; 14, 16; 26, 27) zur Zuführung und Mischung des zumindest teilweise regenerierten Katalysators Mittel für ein Strippen umfaßt, welche geeignet sind, vom teilweise regenerierten Katalysator die Verbrennungsgase aus der Regenerationseinheit zu entfernen.
EP88400305A 1987-02-11 1988-02-10 Verfahren und Vorrichtung für das katalytische Kracken von Kohlenwasserstoffeinsätzen Expired - Lifetime EP0282371B1 (de)

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Application Number Priority Date Filing Date Title
AT88400305T ATE67233T1 (de) 1987-02-11 1988-02-10 Verfahren und vorrichtung fuer das katalytische kracken von kohlenwasserstoffeinsaetzen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8701690A FR2610638B1 (fr) 1987-02-11 1987-02-11 Perfectionnements aux procedes et dispositifs pour le craquage catalytique de charges d'hydrocarbures
FR8701690 1987-02-11

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EP0282371A1 EP0282371A1 (de) 1988-09-14
EP0282371B1 true EP0282371B1 (de) 1991-09-11

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US (1) US4875993A (de)
EP (1) EP0282371B1 (de)
JP (1) JP2559790B2 (de)
AT (1) ATE67233T1 (de)
DE (1) DE3864705D1 (de)
FR (1) FR2610638B1 (de)
ZA (1) ZA88968B (de)

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US5215720A (en) * 1990-05-18 1993-06-01 Uop Conversion of side by side FCC unit
US5013425A (en) * 1990-05-18 1991-05-07 Uop Conversion of side by side FCC unit
EP0532071B1 (de) * 1991-09-09 1995-03-15 Stone & Webster Engineering Corporation Verfahren und Apparat zur Trennung von fluidisierten Krack- katalysatoren aus Kohlenwasserstoffdampf
US5259855A (en) * 1991-09-09 1993-11-09 Stone & Webster Engineering Corp. Apparatus for separating fluidized cracking catalysts from hydrocarbon vapor
FR2682119B1 (fr) * 1991-10-04 1994-09-30 Total Raffinage Distribution Perfectionnements aux dispositifs de craquage catalytique a l'etat fluide de charges d'hydrocarbures.
US5393415A (en) * 1991-12-06 1995-02-28 Uop FCC process with enclosed vented riser
US5393414A (en) * 1991-12-06 1995-02-28 Uop FCC process with enclosed vented riser
FR2757785B1 (fr) * 1996-12-31 1999-11-26 Total Raffinage Distribution Dispositif pour le traitement de particules solides en lit fluidise, et son utilisation
US6063263A (en) * 1998-04-24 2000-05-16 Uop Llc Process for feed contacting with immediate catalyst separation
US6846405B2 (en) * 2001-08-31 2005-01-25 Exxonmobil Chemical Patents Inc. Circulating fluid bed reactor system
ITMI20022710A1 (it) * 2002-12-20 2004-06-21 Enitecnologie Spa Procedimento e reattore per la produzione di olefine leggere mediante reazione di steam cracking di cariche idrocarburiche liquide in presenza di catalizzatore

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ATE67233T1 (de) 1991-09-15
DE3864705D1 (de) 1991-10-17
JPS6433187A (en) 1989-02-03
US4875993A (en) 1989-10-24
JP2559790B2 (ja) 1996-12-04
ZA88968B (en) 1988-08-10
FR2610638A1 (fr) 1988-08-12
EP0282371A1 (de) 1988-09-14
FR2610638B1 (fr) 1990-04-13

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