EP0282371A1 - 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
EP0282371A1
EP0282371A1 EP88400305A EP88400305A EP0282371A1 EP 0282371 A1 EP0282371 A1 EP 0282371A1 EP 88400305 A EP88400305 A EP 88400305A EP 88400305 A EP88400305 A EP 88400305A EP 0282371 A1 EP0282371 A1 EP 0282371A1
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EP
European Patent Office
Prior art keywords
catalyst
grains
stripping
spent catalyst
spent
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.)
Granted
Application number
EP88400305A
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English (en)
French (fr)
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EP0282371B1 (de
Inventor
Jean-Louis Mauleon
Jean-Bernard Sigaud
Bernard Chapotel
Léonard Seglin
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.)
Total Marketing Services SA
Original Assignee
Total France SA
Compagnie de Raffinage et de Distribution Total France SA
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Application filed by Total France SA, Compagnie de Raffinage et de Distribution Total France SA filed Critical Total France SA
Priority to AT88400305T priority Critical patent/ATE67233T1/de
Publication of EP0282371A1 publication Critical patent/EP0282371A1/de
Application granted granted Critical
Publication of EP0282371B1 publication Critical patent/EP0282371B1/de
Anticipated expiration legal-status Critical
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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 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 ballistic separator arranged 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 quantity of coke deposited on the catalyst is therefore a fundamental variable of the reaction, since it contributes to the supply of heat necessary for the cracking of the hydrocarbons.
  • the quantity of coke which is deposited on the catalyst grains, during the reaction is greater than that which is necessary to ensure the thermal equilibrium of the unit: - this is particularly the case when the hydro charges cracking carbides are rich in heavy products such as asphaltenes or compounds with high metal content; - This is also what often occurs due to a poor quality of the separation of the effluents from the cracking reaction or the poor quality of the stripping of the catalyst grains coming from this reaction.
  • 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 equilibrium of the unit.
  • a device ba list of type known per se makes it possible to orient the catalyst grains downward, while that 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 of 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, for the benefit 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 zones described above, 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-137 998 teaches the use of a second stripping chamber in which the spent catalyst is mixed with the hot regenerated catalyst with a view to vaporizing the heavy hydrocarbons present on the spent catalyst. The recovery of effluents is improved, but it is necessary to use two stripping chambers.
  • the present invention aims to remedy this drawback and it therefore has for its object, in a process for the catalytic cracking in the fluid state of a hydrocarbon charge, comprising a step of bringing said upward or downward flow into contact.
  • charge and grains of a cracking catalyst in a tubular reactor a ballistic separation step of the spent catalyst and the cracked charge, downstream of said reactor, a step of stripping in dense fluid phase of the spent catalyst using a fluid injected against the current of this catalyst, a step of regeneration of said catalyst under conditions of combustion of the deposited coke thereon, and a step of recycling the regenerated catalyst to the supply of said reactor, the improvement consisting in that, between said step of ballistic separation and said stripping step, said spent catalyst is homogeneously mixed with grains of at least partially regenerated catalyst, having a temperature higher than that of the spent catalyst grains, which are distributed in a substantially homogeneous manner above the 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 regeneration zone and, in particular, from the first chamber regeneration, if the unit has several successive chambers for regenerating the spent catalyst.
  • the recycling of hot and at least partially regenerated catalyst grains will take place: either by gravity, when the regeneration section of the catalyst is in a position higher than that of said grain introduction zone and, in particular, when the unit operates in descending mode (dropper), - Either by pneumatic transport using a fluid, which will preferably be water vapor or a light hydrocarbon, alone or mixed.
  • 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 dispersion of hot catalyst from the regenerator will be carried out homogeneously, along the entire horizontal section of the enclosure, in the dilute fluidized phase located immediately above the upper surface of the dense fluidized bed in which is used for stripping the spent catalyst grains.
  • the invention also relates to a device for the catalytic cracking of a hydrocarbon feedstock comprising a cracking column with rising or falling flow, means for feeding the upstream end of said column with grains of regenerated catalyst, means for introducing a charge of hydrocarbons into said column under pressure, a means of ballistic separation of the products of the cracked charge and of spent catalyst grains, at least one means of stripping in dense fluidized phase of the spent catalyst, by at least one fluid, 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 means of separation ballistics and said means of stripping, at least one means for the distribution in a substantially homogeneous manner, above said dense fluidized phase of grains of catalyst at least partially regenerated, having a temperature higher than that of the grains of spent catalyst, which are thus homogeneously mixed with said spent catalyst.
  • 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 promotes immediate homogenization of the catalyst grains at the top of the bed.
  • the grains of hot and at least partially regenerated catalyst will be dispersed homogeneously along the entire horizontal section of the dilute 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.
  • the invention has numerous advantages over the known catalyst stripping systems usually used in catalytic cracking processes of hydrocarbon charges. Indeed : - whereas, in the usual stripping devices, the temperature of the spent catalyst suspension is generally not sufficient to appreciably shift the desorption equilibrium of the hydrocarbons remaining on the catalyst, especially if the cracking conditions are low severe, the increase in temperature which results from the recycling of hot catalyst at least partially regenerated leads to better desorption of heavy and / or viscous hydrocarbons both in the dense fluidized phase and in the diluted fluidized phase which overcomes it; this results in improved recovery of the cracked products and, consequently, in a lower catalyst regeneration temperature; the catalyst recycling avoids, during combustion in the regenerator, the appearance of hot spots, detrimental to the activity of the catalyst and linked to the particularly exothermic combustion of the hydrocarbon compounds remaining on the surface of the catalyst grains; the mixture of spent catalyst and at least partially regenerated catalyst makes it possible to increase the heat absorption capacity of the heat of combustion of the coke at the regenerator, which results in better temperature and combustion homogen
  • 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 ture 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 be 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)
EP88400305A 1987-02-11 1988-02-10 Verfahren und Vorrichtung für das katalytische Kracken von Kohlenwasserstoffeinsätzen Expired - Lifetime EP0282371B1 (de)

Priority Applications (1)

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

Publications (2)

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

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EP88400305A Expired - Lifetime EP0282371B1 (de) 1987-02-11 1988-02-10 Verfahren und Vorrichtung für das katalytische Kracken von Kohlenwasserstoffeinsätzen

Country Status (7)

Country Link
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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0536054A1 (de) * 1991-10-04 1993-04-07 Total Raffinage Distribution S.A. Verbesserungen an Vorrichtungen für das katalytische Wirbelschichtkracken von Kohlenwasserstoffeinsätzen
WO2004056943A1 (en) * 2002-12-20 2004-07-08 Polimeri Europa S.P.A. Process and reactor for the production of olefins by the steam cracking reaction of liquid hydrocarbon feeds in the presence of a catalyst

Families Citing this family (10)

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US5376261A (en) * 1990-04-27 1994-12-27 Mobil Oil Corporation Process and apparatus for non-mechanical flow control of catalyst around a catalyst regenerator
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
US5259855A (en) * 1991-09-09 1993-11-09 Stone & Webster Engineering Corp. Apparatus for separating fluidized cracking catalysts from hydrocarbon vapor
DE69201703T2 (de) * 1991-09-09 1995-11-09 Stone & Webster Eng Corp Verfahren und Apparat zur Trennung von fluidisierten Krack- katalysatoren aus Kohlenwasserstoffdampf.
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

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US3886060A (en) * 1973-04-30 1975-05-27 Mobil Oil Corp Method for catalytic cracking of residual oils
EP0137988A2 (de) * 1983-08-31 1985-04-24 Texas Instruments Incorporated Infrarot-Bildwandler
EP0234924A2 (de) * 1986-02-24 1987-09-02 Engelhard Corporation Verfahren zur Behandlung von Kohlenwasserstoffen

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US3886060A (en) * 1973-04-30 1975-05-27 Mobil Oil Corp Method for catalytic cracking of residual oils
EP0137988A2 (de) * 1983-08-31 1985-04-24 Texas Instruments Incorporated Infrarot-Bildwandler
EP0234924A2 (de) * 1986-02-24 1987-09-02 Engelhard Corporation Verfahren zur Behandlung von Kohlenwasserstoffen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0536054A1 (de) * 1991-10-04 1993-04-07 Total Raffinage Distribution S.A. Verbesserungen an Vorrichtungen für das katalytische Wirbelschichtkracken von Kohlenwasserstoffeinsätzen
FR2682119A1 (fr) * 1991-10-04 1993-04-09 Total Raffinage Distribution Perfectionnements aux dispositifs de craquage catalytique a l'etat fluide de charges d'hydrocarbures.
US5430222A (en) * 1991-10-04 1995-07-04 Total Raffinage Distribution S.A. Apparatus for the catalytic cracking in the fluid state of hydrocarbon feedstocks
WO2004056943A1 (en) * 2002-12-20 2004-07-08 Polimeri Europa S.P.A. Process and reactor for the production of olefins by the steam cracking reaction of liquid hydrocarbon feeds in the presence of a catalyst

Also Published As

Publication number Publication date
FR2610638B1 (fr) 1990-04-13
US4875993A (en) 1989-10-24
JPS6433187A (en) 1989-02-03
ZA88968B (en) 1988-08-10
DE3864705D1 (de) 1991-10-17
FR2610638A1 (fr) 1988-08-12
JP2559790B2 (ja) 1996-12-04
EP0282371B1 (de) 1991-09-11
ATE67233T1 (de) 1991-09-15

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