EP0265347A1 - Procédé et dispositif pour le craquage catalytique en lit fluidisé d'une charge d'hydrocarbures - Google Patents

Procédé et dispositif pour le craquage catalytique en lit fluidisé d'une charge d'hydrocarbures Download PDF

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Publication number
EP0265347A1
EP0265347A1 EP87402393A EP87402393A EP0265347A1 EP 0265347 A1 EP0265347 A1 EP 0265347A1 EP 87402393 A EP87402393 A EP 87402393A EP 87402393 A EP87402393 A EP 87402393A EP 0265347 A1 EP0265347 A1 EP 0265347A1
Authority
EP
European Patent Office
Prior art keywords
charge
catalyst
temperature
cracked
column
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.)
Withdrawn
Application number
EP87402393A
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German (de)
English (en)
French (fr)
Inventor
Jean Bernard Sigaud
Michel Demar
Jean-Louis Mauleon
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.)
Compagnie Francaise de Raffinage SA
Total Marketing Services SA
Original Assignee
Compagnie Francaise de Raffinage SA
Compagnie de Raffinage et de Distribution Total France SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Compagnie Francaise de Raffinage SA, Compagnie de Raffinage et de Distribution Total France SA filed Critical Compagnie Francaise de Raffinage SA
Publication of EP0265347A1 publication Critical patent/EP0265347A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/28—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material
    • C10G9/32—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid material according to the "fluidised-bed" technique
    • 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
    • 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
    • C10G11/187—Controlling or regulating

Definitions

  • the present invention relates to catalytic cracking of hydrocarbon charges. It relates more particularly to improvements made to the methods and devices used for catalytic cracking in a fluidized bed of petroleum charges, in particular heavy charges.
  • the catalyst regenerated at a temperature generally above 600 ° C. and the charge to be treated are brought into continuous contact at the base of a vertical or inclined tubular reactor known as a "charge elevator", which technicians often designate. by the English term “riser”.
  • the charge 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 transport pneumatic ascending 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 1 to 4 seconds, the hydrocarbon vapors, at a temperature of the order of 475 to 550 ° C., are separated from the catalyst at the top of the reactor, and sent to the fractionation sections of various products.
  • the spent catalyst charged with 0.5 to 2.0% by weight of coke, is first stripped with steam, then discharged to a regenerator, where its activity is restored by combustion of the coke.
  • the heat of combustion of this coke which may contain from 5 to 10% by weight of hydrogen, 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 feed, 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.
  • charge preheating temperature / circulation of the regenerated catalyst is therefore adjusted so as to obtain the desired reaction temperature throughout the reaction zone and, in particular, at the outlet of the reactor.
  • the temperature levels required for the catalytic cracking reactions lead, in the injection zone, to an equilibrium temperature between catalyst and supposedly vaporized charge which can become below the dew point of this one.
  • the present invention aims to remedy this drawback by controlling the temperature of the mixture of catalyst and fresh vaporized charge, so that it is sufficient to minimize the production of coke due to the non-vaporization of the heaviest fractions, while by ensuring an optimal catalytic cracking temperature in the reaction zone.
  • This control and optimization of the temperature is carried out using a judicious use of various recycle cuts from the fractionation of the effluents. of the cracking reaction.
  • the subject of the invention is therefore a process for catalytic cracking of a hydrocarbon feed, this process comprising a phase of bringing into contact with ascending or descending flow in a column, under cracking conditions in a fluidized bed, of said charge and of the grains of a cracking catalyst, a phase of separation of the spent catalyst and of the cracked charge downstream of the reaction zone, at least one phase of stripping of the spent catalyst, a phase of regeneration of said catalyst in conditions for combustion of the coke deposited thereon and, finally, a phase of recycling the regenerated catalyst to the supply of said column, this process being characterized in that: the recycled catalyst is introduced in the diluted fluidized phase into said column in quantity and at a temperature such that the temperature of the mixture of this catalyst and of the finely sprayed charge is at least equal to the dew point of the charge to be cracked, - At least one section from the fractionation of the cracked charge is recycled to the liquid state by spraying, immediately, downstream of the mixing and vaporization zone of the charge to be cracked, preferably
  • the following cuts are usually distinguished: - the gasoline cup, the boiling range of which generally extends from the C5 cup to around 200-220 ° C; - the diesel cut, often called LCO, by reference to the English term “Light Cycle Oil”, whose boiling range generally extends from 160-220 ° C (start of cut) up to around 320-380 ° C ( end of cut), this cut and the previous one being those which are usually sought during catalytic cracking, the units generally operating either in diesel operation (maximum production of diesel), or in petrol operation (maximum production of petrol), depending on the case; - the heavy thinner cut, often called HCO, by reference to the English term “Heavy Cycle Oil", less well valued (low viscosity fuel base) and whose boiling range is generally between 300-380 and 460-500 ° C; - and, finally, a cut of distillation residue, which contains the heaviest and most difficult to crack products, and
  • the recycles injected by spraying at different intervals into the cracking or riser column have the effect of dividing it into several distinct thermal zones, characterized by different reaction conditions and adjustable independently of each other.
  • the area between the injection points of the fresh charge and the first recycle is notably characterized by: an average equilibrium temperature of the catalyst + feed mixture at least equal to the dew temperature thereof, in order to allow complete vaporization thereof, this high temperature being moreover favorable to the dislocation of the heaviest elements and the less solid, such as asphaltenes, in smaller compounds, then accessible to catalytic cracking; - A high catalyst to hydrocarbon ratio, favorable to a rapid and efficient heat transfer between the catalyst and the feed, in particular making it possible to minimize the undesirable thermal cracking reactions and to promote as much as possible the more selective catalytic cracking reactions; - a very short reaction time, less than 0.5 and preferably 0.3 seconds, in order to control the conversion at the desired level and avoid the development of side reactions detrimental to good selectivity.
  • the zone or zones situated further downstream, after the temperature has been lowered due to the endothermicity of the reaction itself and the quenching effect caused by the spraying of the recycle (s), are characterized by more conventional cracking conditions, which are suitable for a fully vaporized product after passing through the first zone.
  • a total contact time of between 0.5 and 5 seconds and, preferably, between 0.5 and 2 seconds and a final reaction temperature of between 475 and 510 ° C when running at maximum diesel, or 500 to 550 ° C in the case of maximum petrol operation.
  • the invention requires in particular, for maximum efficiency, a very rapid vaporization of the charge. This is why it is essential that the system for spraying and distributing the charge in the catalyst flow ensures both fine atomization of this charge and a homogeneous mixture with the catalyst.
  • Another object of the invention lies in further optimization of the so-called “maximum diesel” operations, whatever the type of loads treated.
  • the catalytic cracking process which is the subject of the present invention therefore makes it possible to minimize unnecessary coke formations, that is to say those which do not result from a conversion.
  • This process also makes it possible, by a judicious choice of the cracking conditions for the recycle cut (s) resulting from the fractionation of the cracked effluents, to maximize, as the case may be, the production of petrol or diesel, whatever the charges at cracking sent into the unit, while ensuring the thermal equilibrium of the unit by limiting the formation of coke to what is strictly necessary for its needs.
  • the subject of the invention is also a device for catalytic cracking of a hydrocarbon feedstock comprising a cracking column with upward or downward flow of catalyst grains, means for supplying said column under pressure by spraying with a feedstock.
  • hydrocarbons a means for separating the products from the cracked charge and the spent catalyst grains, at least one means for stripping by at least one fluid of the spent catalyst grains, at least one unit for regenerating said catalyst by combustion at high temperature of the coke deposited thereon, and means for recycling the regenerated catalyst to said supply means
  • this device being characterized in that it comprises a means for fractionating the reaction effluents and a means for recycling to said column, in the sprayed state, at least one section of liquid coming from this separation at at least one point placed immediately downstream of the zone for mixing the fresh charge and the regenerated catalyst.
  • the device for recycling by spraying into the cracking column one or more distillation cuts for cracking effluents makes it possible to optimize the cracking conditions with a view to the desired result (maximum yield of gasoline or diesel).
  • the injection rates of the recycled section (s) will be controlled by the temperature measured immediately downstream of the injection area.
  • the device will include at least one means for regulating the feed rate of the column in one or more recycled cups so that the temperature of the reaction zone, downstream of the injection zone, is maintained at a set value adapted to the nature of the load to be cracked, the petrol or diesel operation sought, the type of catalyst used and its mode of regeneration.
  • Each recycled section will preferably be injected homogeneously over the entire section of the reaction zone using one or more spraying devices, so as to ensure instant heat transfer.
  • the injection of the charge to be cracked and that of the recycle (s) resulting from the fractionation are carried out using high-performance sprayers, such as impaction sprayers or venturi-type nozzles, so as to give the liquid droplets with the smallest possible diameter, generally less than 100 microns and preferably less than 50 microns; this fine spray allows the droplets formed to be transformed into hydrocarbon vapors almost instantaneously when they are brought into contact with the flow of catalyst grains at high temperature.
  • the device will include means for regulating the feed rate of the column in recycled section so that the final reaction temperature is kept equal to a set value adapted to the load to be cracked, to the cracking conditions. and the type of operation sought (petrol operation: final temperature 500-530 ° C, or diesel operation: final temperature 480-510 ° C).
  • the temperature of the vaporized charge + catalyst mixture can thus be maintained above the dew point of the charge, while adapting the cracking temperature to the desired selectivity for the cracking effluents.
  • the temperature resulting from the catalyst + vaporized charge mixture is measured using a temperature probe 6, which controls the valve 7 for the arrival of the hot and regenerated catalyst, so as to maintain the temperature measured in 6 at an equal value. or higher than that of the dew point of the load to be cracked.
  • an enclosure 8 for separating the cracked products and the spent catalyst particles.
  • a diffuser 9 for stripping fluid, generally water vapor, acting against the current of the separated catalyst particles.
  • the catalyst particles recovered at the bottom of the enclosure 8 are evacuated at 10 to a second stripping device or to a regenerator, while the cracked products are evacuated at the top of the enclosure 8 to a fractionation column.
  • a fractionation column of a type known per se, not shown in this figure and making it possible to separate petrol, diesel, heavy thinner or catalytic slurry cuts.
  • These cuts can, in accordance with the process according to the present invention, be recycled and pulverized in column 5, downstream of the injectors 4 of the charge to be cracked, using the injector (s) 11 and 12, and optionally using other injectors not shown in this figure.
  • the mixing temperature in the zone immediately downstream of the charge injectors 4 is brought back to the reaction temperature catalytic desirable by spraying into 11 of a section containing mainly diluent in the liquid state, which arrives via line 13.
  • the temperature in the column which results from this spraying will generally be about 10 to 30 ° C higher than that measured at the end of the reaction by the probe 14, placed here in the enclosure 8, at the outlet of the cracking effluents.
  • a section of catalytic slurry arriving via line 17 is sprayed at 12 in column 5, downstream of the injection of the light diluent.
  • the probe 14 controls the valves 15 and 16 arranged on the lines 13 and 17 for supplying the column 5 with sections coming from the fractionation zone, with a view to adjusting the flow rate so that the temperature of the cracking zone located downstream of their injection is maintained at the desirable value, while maintaining at 14 a value equal to or greater than that of the set point.
  • fraction or fractions of recycled sections will advantageously be sections of heavy diluent at 11, and sections of light diluent or catalytic slurry at 12, depending on the nature of the charge (heavy or light) and according to the type of market sought (petrol or diesel).
  • a heavy feedstock which is here a direct atmospheric distillation residue (RAT) having the following characteristics, is sent to a catalytic cracking unit, comprising a cracking column and a catalyst regeneration system of a type known per se.
  • RAT direct atmospheric distillation residue
  • a commercial catalyst is used for cracking, comprising ultra-stabilized zeolites and a matrix capable of cracking the heaviest hydrocarbon molecules under cracking conditions.
  • this charge can be completely vaporized and the production of coke associated with the non-vaporized fraction in the previous case is avoided.
  • the report is significantly higher, the regeneration temperature lower, and the temperature of the charge significantly higher, resulting in a lower viscosity and a better quality of atomization, which, in turn, contributes to further reduce the tendency to produce coke.
  • the first recycle is, as in Example 1, consisting of HCO whose boiling range is between 340 and 460 ° C, also carried out 0.2 seconds after injection into the mixing zone.
  • a second recycle is made up this time of a catalytic slurry recycle, the boiling point of which is greater than 460 ° C.
  • the operating conditions are as follows:
  • the temperature which results from the vaporization of the charge to be cracked in the presence of the stream of hot and regenerated catalyst is substantially higher than the dew point of the charge.
  • the quenching effect due to the spraying of the heavy diluent (HCO) then of the residue (catalytic slurry), is here relatively moderate, which is linked to the fact that with this type of crackable filler, the process according to the present invention, unlike the usual cracking process, allows to go to the complete exhaustion of the least valuable product, namely the residue, the latter additionally providing the additional coke necessary for the thermal equilibrium of the unit , taking into account the high injection temperature of the regenerated catalyst.
  • HCO heavy diluent

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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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP87402393A 1986-10-24 1987-10-23 Procédé et dispositif pour le craquage catalytique en lit fluidisé d'une charge d'hydrocarbures Withdrawn EP0265347A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8614830 1986-10-24
FR8614830A FR2605643B1 (fr) 1986-10-24 1986-10-24 Procede et dispositif pour le craquage catalytique en lit fluidise d'une charge d'hydrocarbures

Publications (1)

Publication Number Publication Date
EP0265347A1 true EP0265347A1 (fr) 1988-04-27

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Application Number Title Priority Date Filing Date
EP87402393A Withdrawn EP0265347A1 (fr) 1986-10-24 1987-10-23 Procédé et dispositif pour le craquage catalytique en lit fluidisé d'une charge d'hydrocarbures

Country Status (5)

Country Link
EP (1) EP0265347A1 (ko)
JP (1) JPS63183991A (ko)
KR (1) KR880005240A (ko)
FR (1) FR2605643B1 (ko)
ZA (1) ZA877955B (ko)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2953851A1 (fr) * 2009-12-14 2011-06-17 Total Raffinage Marketing Procede de craquage catalytique avec maximisation des bases gazoles

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060231459A1 (en) * 2005-03-28 2006-10-19 Swan George A Iii FCC process combining molecular separation with staged conversion
FR2894848B1 (fr) * 2005-12-21 2008-02-22 Inst Francais Du Petrole Dispositif de redistribution du catalyseur dans les risers de fcc
KR101921696B1 (ko) 2016-09-22 2018-11-23 한국기계연구원 촉매 재생기, 유동 촉매 크랙킹 반응 시스템 및 촉매 재생 방법

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3193494A (en) * 1962-07-24 1965-07-06 Sinclair Research Inc Progressive flow cracking of contaminated hydrocarbon feedstocks
US3692667A (en) * 1969-11-12 1972-09-19 Gulf Research Development Co Catalytic cracking plant and method
US3896024A (en) * 1974-04-02 1975-07-22 Mobil Oil Corp Process for producing light fuel oil
FR2298595A1 (fr) * 1975-01-24 1976-08-20 Mobil Oil Production d'essence a l'aide de catalyseurs du type faujasite " y "
EP0074501A2 (en) * 1981-08-27 1983-03-23 Ashland Oil, Inc. Process and catalyst for the conversion of oils that contain carbon precursors and heavy metals
US4422925A (en) * 1981-12-28 1983-12-27 Texaco Inc. Catalytic cracking
EP0208609A1 (fr) * 1985-07-10 1987-01-14 Total Raffinage Distribution S.A. Procédé et dispositif pour le craquage catalytique de charges d'hydrocarbures, avec contrôle de la température de réaction

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3193494A (en) * 1962-07-24 1965-07-06 Sinclair Research Inc Progressive flow cracking of contaminated hydrocarbon feedstocks
US3692667A (en) * 1969-11-12 1972-09-19 Gulf Research Development Co Catalytic cracking plant and method
US3896024A (en) * 1974-04-02 1975-07-22 Mobil Oil Corp Process for producing light fuel oil
FR2298595A1 (fr) * 1975-01-24 1976-08-20 Mobil Oil Production d'essence a l'aide de catalyseurs du type faujasite " y "
EP0074501A2 (en) * 1981-08-27 1983-03-23 Ashland Oil, Inc. Process and catalyst for the conversion of oils that contain carbon precursors and heavy metals
US4422925A (en) * 1981-12-28 1983-12-27 Texaco Inc. Catalytic cracking
EP0208609A1 (fr) * 1985-07-10 1987-01-14 Total Raffinage Distribution S.A. Procédé et dispositif pour le craquage catalytique de charges d'hydrocarbures, avec contrôle de la température de réaction

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2953851A1 (fr) * 2009-12-14 2011-06-17 Total Raffinage Marketing Procede de craquage catalytique avec maximisation des bases gazoles
EP2336273A1 (fr) * 2009-12-14 2011-06-22 Total Raffinage Marketing Procédé de craquage catalytique avec maximisation des bases gazoles
US8764971B2 (en) 2009-12-14 2014-07-01 Total Raffinage Marketing Method for catalytic cracking with maximization of diesel base stocks
RU2554867C2 (ru) * 2009-12-14 2015-06-27 Тоталь Рафинаж Маркетинг Способ каталитического крекинга с максимизацией базовых компонентов дизельного топлива

Also Published As

Publication number Publication date
KR880005240A (ko) 1988-06-28
JPS63183991A (ja) 1988-07-29
FR2605643B1 (fr) 1989-08-18
ZA877955B (en) 1988-04-26
FR2605643A1 (fr) 1988-04-29

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