EP0208609B1 - Process and apparatus for the catalytic cracking of hydrocarbons, with control of the reaction temperature - Google Patents

Process and apparatus for the catalytic cracking of hydrocarbons, with control of the reaction temperature Download PDF

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Publication number
EP0208609B1
EP0208609B1 EP86401464A EP86401464A EP0208609B1 EP 0208609 B1 EP0208609 B1 EP 0208609B1 EP 86401464 A EP86401464 A EP 86401464A EP 86401464 A EP86401464 A EP 86401464A EP 0208609 B1 EP0208609 B1 EP 0208609B1
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European Patent Office
Prior art keywords
catalyst
charge
temperature
injection
auxiliary fluid
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German (de)
French (fr)
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EP0208609A1 (en
EP0208609B2 (en
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Jean-Louis Mauleon
François Ville
Jean-Bernard Sigaud
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TotalEnergies Marketing Services SA
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Total Raffinage Distribution SA
Compagnie de Raffinage et de Distribution Total France SA
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C10G11/187—Controlling or regulating
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S208/00—Mineral oils: processes and products
    • Y10S208/01—Automatic control

Definitions

  • the present invention relates to catalytic cracking of hydrocarbon charges in a fluidized bed. It relates more particularly to a process and a device for such a catalytic cracking, with a regulation of the reaction temperature by quenching of the reaction products.
  • the catalyst of the FCC process and the feedstock to be treated are brought into contact at the base of a reactor made up of a column known as a "load lift", which techniques often designate by the English term “riser”. .
  • a load lift which techniques often designate by the English term “riser”.
  • At the top of the column is an enclosure concentric with the elevator.
  • a ballistic separation system to recover the catalyst entrained with the vapors.
  • Cyclonic systems are generally used.
  • the charge is discharged at the top of said enclosure, while the catalyst particles deactivated by coke deposition are collected at the base of the enclosure and meet there a stripping fluid such as water vapor, injected at the base from said enclosure, before being evacuated to a regenerator, in order to restore their activity by burning coke.
  • Combustion air is injected at the base of the regenerator, while at the top of the latter are provided cyclones making it possible to separate the combustion gas from the entrained particles of the regenerated catalyst.
  • This is evacuated to the bottom of the regenerator and recycled to the base of the elevator or "riser", where the charge is usually injected at a temperature between 80 ° C and 400 ° C and under a pressure ranging from 0 , 7 '10 5 3,5'105 relative Pascals.
  • the pair “charge preheating temperature / regenerated catalyst circulation” is therefore adjusted so as to determine the reaction temperature in any reaction zone, and in particular at the outlet of the riser.
  • the catalyst can be introduced with the feedstock at the top of an essentially descending or “dropper” reaction column, at the base of which the spent catalyst is recovered, stripped and sent to regeneration.
  • US-A-3,896,024 describes a process for catalytic cracking of a charge whose boiling point is between 650 and 720 ° F (343 and 382 ° C).
  • the charge is brought into contact with the catalyst in a rising flow column where the temperature of the mixture can reach at most 1000 ° F (538 ° C).
  • the charge is thermally cracked into fractions of lower boiling points.
  • a charge of preheated gas oil is injected into the column to lower the temperature of the reaction mixture between 800 and 900 ° F (426 and 482 ° C).
  • the mixture obtained is then catalytically cracked under milder conditions in the upper part of the column.
  • Petroleum charges characterized in that at least 10% of their weight has a boiling point above 500 ° C., have thus been able to be treated in the catalytic cracking units, by virtue of an increase in the temperature in the zone of injecting the catalyst and of the charge to be cracked (or “mixing zone”) and of a good spraying of the charge in this zone.
  • the heterogeneity of temperatures which results from such an injection, necessitated the development of reactors with short residence times, in order to avoid the occurrence of overcracking or of secondary reactions, such as polymerization reactions of cracked products, as well as to avoid the production of an excess of gases which are difficult to recover.
  • the temperature regulation carried out according to the invention therefore makes it possible to control the duration of the contact between the molecules to be catalytically cracked and the catalyst, and thus to avoid an excessive prolongation of the thermocracking generating coke and light gases, as well as the occurrence of side reactions linked to an unsuitable catalytic cracking temperature.
  • An object of the present invention is, therefore, in a process for catalytic cracking of a charge of hydrocarbons in a fluidized bed, to bring the charge and the catalyst into contact at a high temperature capable of preventing deposits of coke on the catalyst and optimally promote catalytic cracking of this charge.
  • Another object of the invention is to control the duration of contact of the catalyst and of the charge at this high temperature, so as to reduce the secondary reactions or to limit the thermocracking liable to occur.
  • the subject of the invention is therefore a process for catalytic cracking in a dilute fluidized bed and with a short contact time of a heavy hydrocarbon charge of which more than 10% by weight has a boiling point above 500 ° C., this process comprising a contacting phase, with ascending or descending flow, in a column, under cracking conditions, of said charge and of particles of a cracking catalyst, a phase of separation of the spent catalyst and of the charge cracked downstream of the injection zone of said charge with at least one stripping phase of the spent catalyst using a fluid, then a regeneration phase of said catalyst under conditions of combustion of the coke deposited on it , and finally a phase of recycling the regenerated catalyst to the supply of said column, this process being characterized in that injected into said column of regenerated catalyst under conditions such as the equilibrium temperature resulting from the melan ge of the vaporized charge and of the catalyst is at least greater than 500 ° C.
  • the injected fluid may be a liquid or a gas and, in particular, water, water vapor, or any hydrocarbon vaporizable under the injection conditions, in particular, coking or visbreaking gas oils. , catalytic thinners, heavy aromatic solvents, as well as certain deasphalting cuts extracted with heavy solvent.
  • this fluid will therefore have a selective quenching effect on the reaction mixture constituted by the charge and the grains of catalyst, and the injection rate of said fluid must be such that it makes it possible to regulate, under optimum conditions, the temperature of the catalytic cracking reaction, without harming the subsequent stripping of the spent catalyst and without causing condensation on the catalyst particles of the heaviest hydrocarbons present, which would result in an increased deposition of coke on the catalyst.
  • the conditions for injecting the fluid will be such that it causes an instantaneous lowering of the temperature of the reaction mixture of the order of 10 to 70 ° C., which, at constant final reaction temperature, therefore results in a substantially equivalent increase in the mixing temperature between the charge to be cracked and the regenerated catalyst grains.
  • the quenching carried out using the auxiliary fluid will take place less than a second after the injection of the cracked charge and , preferably, less than half a second after this.
  • the process according to the invention can be implemented both in a cracking column with ascending flow (riser, also called “riser”) and in a column with downward flow (“dropper”).
  • An important advantage of the process according to the invention is that it makes it possible to limit the catalyst regeneration temperature, due to a reduced deposition of coke, and makes it possible to convert heavy charges normally excluded in the catalytic cracking process into fluidized bed.
  • the conditions for injecting the charge and the catalyst will be such that the mixing temperature will be slightly higher than the vaporization temperature of the charge.
  • the conditions of injection of the auxiliary quenching fluid in particular, the flow rate, the temperature and the pressure, will have to be adjusted as a function of the characteristics of the charge and of the catalyst, as well as of the conditions of reaction of catalytic cracking and of profile of the desired temperature, that is to say in practice as a function of the mixing temperature and of the desired final reaction temperature.
  • a preferred embodiment of the process according to the invention therefore consists in regulating the injection of said auxiliary fluid into the cracking column so that the reaction temperature which results from this injection is maintained at a value predetermined and constant, but high enough that the effectiveness of the stripping is not substantially impaired.
  • the invention also relates to a catalytic cracking device for heavy loads of hydrocarbons of which more than 10% by weight have a boiling point above 500 ° C., comprising a cracking column with rising or falling flow, means for supplying said column under pressure with a hydrocarbon feedstock and particles of a regenerated cracking catalyst, a means for separating the products from the cracked feedstock and spent catalyst particles, at least one stripping means with at least one fluid from the spent catalyst particles, at least one unit for regenerating said catalyst by combustion of the coke deposited thereon, means for recycling the regenerated catalyst to said supply means and, downstream of the mixing zone in said column of the charge of hydrocarbons and particles of regenerated catalyst, at least one means for injecting an auxiliary fluid under flow, temperature and pressure conditions, such as the injection of this auxiliary fluid decreases the temperature of the reaction zone located immediately downstream independently of the mixing temperature, this device being characterized in that it comprises means for regulating the flow rate of said auxiliary fluid so that the temperature of the reaction zone downstream of the injection of the
  • this device will also include means for increasing the flow rate of the hot catalyst when the final reaction temperature tends to decrease compared to the set value.
  • the means for injecting an auxiliary fluid may advantageously be located in the reaction zone at a distance which may be between 0.1 and 0.8 times the length of said reaction zone and, preferably, between 0.1 and 0.5 times this length, downstream of the injection site of the load to be cracked.
  • This or these injection means will advantageously consist of an injection device of a type known per se, making it possible to distribute the fluid homogeneously over the entire section of the reaction zone.
  • the quantities necessary for regulating the mixing temperature will be injected using a spraying device making it possible, in a manner known per se, to spray this liquid in the form very fine mist over the entire section of the reaction zone so as to obtain as instantaneous heat transfer as possible.
  • a spraying device making it possible, in a manner known per se, to spray this liquid in the form very fine mist over the entire section of the reaction zone so as to obtain as instantaneous heat transfer as possible.
  • the flow required to achieve an identical temperature increase will be from 100 to 700 liters of hydrocarbon per cubic meter of charge treated.
  • the regenerated catalyst is injected via a pipe 1 at the base of an ascending flow column 2 or “riser”, as well as a carrier gas injected at 3.
  • the charge of hydrocarbons to be treated is itself even injected in 4 at the base of the column and the hydrocarbons and the particles of the catalyst are in contact in zone 2, immediately downstream of the injection of the feed.
  • the temperature of the catalyst + vaporized charge mixture is between approximately 500 and 650 ° C., depending on the nature of the charge and the desired conversion objectives.
  • an enclosure 6 for separating the cracked products and the spent catalyst particles.
  • injectors 7 of a stripping fluid generally steam, acting against the current of the separated catalyst particles.
  • the catalyst particles are removed at 8 to a second stripping device or to a regenerator, while the cracked products are removed at the upper part (not shown) of the enclosure 6.
  • an auxiliary fluid for quenching the cracked products is injected at 9 into part 5 of column 2, downstream of the contact zone between catalyst particles and vaporized charge.
  • This auxiliary fluid - water, water vapor, hydrocarbons, or other - is injected at a rate such that it lowers from 10 to 70 ° C, depending on the desired result, the temperature of the mixture, in order to optimize the reactions catalytic cracking of the charge.
  • the final temperature of the reaction zone thus cooled may be, for example, of the order of 500 ° C, but must be higher than the dew point of the heaviest hydrocarbons present.
  • a temperature probe 10 will be provided inside the enclosure 6 to measure the temperature there and to possibly control the valve 12 controlling the flow of the auxiliary fluid in the supply line 13 of the injection means. 9, so that the temperature in the enclosure 6 is maintained above a set temperature specific to the type of load treated.
  • the cracking column 20 is of the so-called “dropper” type, that is to say that the particles of regenerated catalyst 21 are injected into the upper part of the column 20 and fall there by gravity .
  • the charge to be cracked is also introduced into the upper part of the column at 22.
  • An enclosure 23 located at the base of the column 20 makes it possible to separate and evacuate the effluents, namely the products of cracking through the pipe 24, and the spent catalyst particles towards the base of this enclosure 23, in order to strike them, then convey them to the regeneration.
  • an auxiliary quenching fluid for the cracked products is injected at 26, downstream of the means 22 for injecting the charge. Its flow rate is such that, for a given mixing temperature, it lowers the final reaction temperature by approximately 10 to 70 ° C, to allow the catalytic cracking reactions to be carried out under optimal conditions.
  • a temperature probe 27, disposed before the pipe 24, makes it possible to control, by a valve 29 arranged on the supply pipe 30, the flow of auxiliary fluid of the injection means 26, in such a way that the temperature recorded in 27 is constantly equal to or higher than a set temperature, while the probe makes it possible to act on the injection temperature in the reaction zone and on the regulation of the injection flow rate in 26.
  • the cracking column 2 is again of the riser type and the reference numerals designating the elements of the unit are the same as for those of FIG. 1.
  • This figure presents a simplified and particularly advantageous mode of regulation. , according to the present invention.
  • the auxiliary fluid is injected at 9, or when the injection volume is increased, the final temperature of the catalytic reaction, measured at 10, will tend to decrease compared to the desired setpoint for the corresponding charge.
  • the valve 16, acting on the flow of hot regenerated catalyst will immediately ensure an increase in the mixing temperature which, taking into account the flow injected at 9, will make it possible to bring the final cracking temperature back to the set value.
  • the following two examples illustrate the advantages of the process according to the invention.
  • a commercial catalyst is used for cracking, comprising zeolites of high stability and a matrix capable of cracking - the heaviest hydrocarbon molecules under cracking conditions.
  • the table above shows the advantage resulting from raising the initial cracking temperature above 550 ° C and quenching the reaction products, using water, to bring the temperature down. of the mixture at 525 ° C.
  • the auxiliary fluid this time consists of a recycling of cracking effluents with a boiling point of between 340 ° C. and 460 ° C., carried out 0.2 seconds after injection of the charge into the mixing zone.
  • the operating conditions are as follows:
  • the heavy load considered could not have been treated without resorting to the means used in the present invention, insofar as, according to the prior art, at least 15% by weight of this load could not have been be vaporized, which would have led to a production of coke outside the limits compatible with the satisfaction of the thermal balance of the unit.
  • the mixing temperature was increased by approximately 40 ° C to ensure complete vaporization and the thermal shock conditions necessary for cracking the heaviest compounds present in this charge, after which the spraying of a hydrocarbon in the reaction medium makes it possible to reduce the final temperature to 510 ° C. and thus to ensure optimal conversion.
  • the process according to the invention therefore makes it possible to improve the performance of a cracking unit for a determined charge of hydrocarbons. It can advantageously be used to treat heavier and more contaminated loads with greater efficiency. In the same way, this process presents an exceptional attraction for the treatment of nitrogenous charges, or rich in polar compounds (resins, asphaltenes), where the strong presence of aromatic nitrogen is responsible for a spectacular fall of the conversion.
  • the conversion gain with the process according to the invention is of the order of 5.5% by volume. This is explained by the higher mixing temperature, which favorably displaces the adsorption balance of aromatic nitrogen, thereby reducing the neutralization of certain acid sites of the catalyst.

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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)
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Description

La présente invention concerne le craquage catalytique de charges d'hydrocarbures en lit fluidisé. Elle a plus particulièrement pour objet un procédé et un dispositif pour un tel craquage catalytique, avec une régulation de la température réactionnelle par trempe des produits de la réaction.The present invention relates to catalytic cracking of hydrocarbon charges in a fluidized bed. It relates more particularly to a process and a device for such a catalytic cracking, with a regulation of the reaction temperature by quenching of the reaction products.

On sait que, dans les procédés dits de craquage catalytique (en anglais Fluid Catalytic Cracking, ou encore procédé FCC), la charge d'hydrocarbures est complètement vaporisée par mise en contact à haute température avec un catalyseur de craquage approprié maintenu en suspension. Après que l'on ait atteint par craquage la gamme de poids moléculaires désirée, avec un abaissement correspondant des points d'ébullition, le catalyseur est rapidement séparé des produits obtenus.It is known that, in the so-called catalytic cracking processes (in English Fluid Catalytic Cracking, or FCC process), the hydrocarbon charge is completely vaporized by contacting at high temperature with an appropriate cracking catalyst kept in suspension. After the desired molecular weight range has been reached by cracking, with a corresponding lowering of the boiling points, the catalyst is rapidly separated from the products obtained.

Dans la pratique, le catalyseur du procédé FCC et la charge à traiter sont mis en contact à la base d'un réacteur constitué d'une colonne dite «élévateur de charge», que les techniques désignent souvent par le terme anglais de «riser». Au sommet de la colonne est disposée un enceinte concentrique à l'élévateur. Dans la partie supérieure de cette enceinte et au-dessus de l'élévateur est logé un système de séparation balistique, pour récupérer le catalyseur entraîné avec les vapeurs. Des systèmes cycloniques sont généralement utilisés. La charge est évacuée au sommet de ladite enceinte, tandis que les particules de catalyseur désactivées par dépôt de coke sont rassemblées à la base de l'enceinte et y rencontrent un fluide de strippage tel que de la vapeur d'eau, injecté à la base de ladite enceinte, avant d'être évacuées vers un régénérateur, en vue de restaurer leur activité par brûlage du coke. De l'air de combustion est injecté à la base du régénérateur, tandis qu'à la partie supérieure de celui-ci sont prévus des cyclones permettant de séparer le gaz de combustion des particules entraînées du catalyseur régénéré. Celui-ci est évacué à la partie inférieure du régénérateur et recyclé vers la base de l'élévateur ou «riser», où la charge est habituellement injectée à une température comprise entre 80°C et 400°C et sous une pression allant de 0,7'105 à 3,5'105 Pascals relatifs.In practice, the catalyst of the FCC process and the feedstock to be treated are brought into contact at the base of a reactor made up of a column known as a "load lift", which techniques often designate by the English term "riser". . At the top of the column is an enclosure concentric with the elevator. In the upper part of this enclosure and above the elevator is housed a ballistic separation system, to recover the catalyst entrained with the vapors. Cyclonic systems are generally used. The charge is discharged at the top of said enclosure, while the catalyst particles deactivated by coke deposition are collected at the base of the enclosure and meet there a stripping fluid such as water vapor, injected at the base from said enclosure, before being evacuated to a regenerator, in order to restore their activity by burning coke. Combustion air is injected at the base of the regenerator, while at the top of the latter are provided cyclones making it possible to separate the combustion gas from the entrained particles of the regenerated catalyst. This is evacuated to the bottom of the regenerator and recycled to the base of the elevator or "riser", where the charge is usually injected at a temperature between 80 ° C and 400 ° C and under a pressure ranging from 0 , 7 '10 5 3,5'105 relative Pascals.

Le procédé FCC est naturellement mis en oeuvre de façon que l'unité de craquage soit en équilibre thermique, toute la chaleur nécessaire étant apportée par la combustion du coke déposé au cours de la réaction de craquage sur les grains du catalyseur. Autrement dit, l'alimentationen en catalyseur chaud régénéré et la température d'injection de la charge à craquer doivent être telles que l'unité puisse répondre aux diverses exigences thermiques de la section réactionnelle, à savoir, en particulier:

  • - la vaporisation de la charge,
  • - l'apport de chaleur exigé par les réactions impliquées, lesquelles, globalement, sont endothermiques,
  • - les pertes de chaleur de l'unité.
The FCC process is naturally implemented so 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 grains of the catalyst. In other words, the supply of regenerated hot catalyst and the injection temperature of the charge to be cracked must be such that the unit can meet the various thermal requirements of the reaction section, namely, in particular:
  • - vaporization of the charge,
  • - the heat input required by the reactions involved, which, overall, are endothermic,
  • - heat losses from the unit.

Le couple «température de préchauffage de la charge/circulation de catalyseur régénéré» est donc ajusté de façon à déterminer la température de réaction dans toute zone réactionnelle, et en particulier en sortie du riser.The pair “charge preheating temperature / regenerated catalyst circulation” is therefore adjusted so as to determine the reaction temperature in any reaction zone, and in particular at the outlet of the riser.

En variante, le catalyseur peut être introduit avec la charge au sommet d'une colonne de réaction essentiellement descendante ou «dropper», à la base de laquelle le catalyseur usé est récupéré, strippé et envoyé à la régénération.As a variant, the catalyst can be introduced with the feedstock at the top of an essentially descending or “dropper” reaction column, at the base of which the spent catalyst is recovered, stripped and sent to regeneration.

US-A-3 896 024 décrit un procédé de craquage catalytique d'une charge dont le point d'ébullition est compris entre 650 et 720°F (343 et 382°C). La charge est mise en contact avec le catalyseur dans une colonne à flux montant où la température du mélange peut atteindre au plus 1000°F (538°C). Dans cette zone de mélange, la charge est craquée thermiquement en fractions de points d'ébullition inférieurs. En aval de cette zone, une charge de gas-oil préchauffée est injectée dans la colonne pour abaisser la température du mélange réactionnel entre 800 et 900°F (426 et 482°C). Le mélange obtenu est ensuite craqué catalytiquement dans des conditions plus douces dans la partie supérieure de la colonne.US-A-3,896,024 describes a process for catalytic cracking of a charge whose boiling point is between 650 and 720 ° F (343 and 382 ° C). The charge is brought into contact with the catalyst in a rising flow column where the temperature of the mixture can reach at most 1000 ° F (538 ° C). In this mixing zone, the charge is thermally cracked into fractions of lower boiling points. Downstream of this zone, a charge of preheated gas oil is injected into the column to lower the temperature of the reaction mixture between 800 and 900 ° F (426 and 482 ° C). The mixture obtained is then catalytically cracked under milder conditions in the upper part of the column.

Les développements les plus récents en matière de craquage catalytique n'ont cependant permis de résoudre que partiellement le problème d'injection des charges pétrolières lourdes dans les unités de craquage catalytique.The most recent developments in catalytic cracking have, however, only partially resolved the problem of injecting heavy petroleum charges into catalytic cracking units.

On sait, en effet, que plus la charge pétrolière à craquage possède un point d'ébullition élevé, plus elle possède de composés à haut poids moléculaire et riches en métaux, qui sont des précurseurs de coke: ces composés, qui comprennent des asphaltènes, ont une nature cyclique ou polycyclique et présentent la particularité d'être difficiles à vaporiser dans les conditions usuelles d'injection, et par conséquent de former des dépôts de coke importants lorsqu'il sont mis en présence des grains de catalyseur, en vue de la réaction de craquage catalytique.It is known, in fact, that the higher the cracked petroleum charge has a higher boiling point, the more it has compounds with high molecular weight and rich in metals, which are precursors of coke: these compounds, which include asphaltenes, have a cyclic or polycyclic nature and have the particularity of being difficult to vaporize under the usual injection conditions, and consequently of forming significant coke deposits when they are brought into contact with the catalyst grains, with a view to the catalytic cracking reaction.

Une première solution a donc été proposée (brevet US 4 427 537), selon laquelle des charges pétrolières lourdes, possédant en particulier des quantités importantes d'aspaltènes, pouvaient être craquées en améliorant leur pulvérisation dans la zone d'injection du catalyseur, de façon à créer, lors du contact avec les grains de catalyseur, un choc thermique suffisant pour permettre un thermocraquage des molécules à poids moléculaire élevé. La scission thermique de ces molécules en molécules plus petites permet à ces dernières d'être ensuite recraquées catalytiquement en phase gazeuse, lors de leur mise en présence des grains de catalyseur.A first solution has therefore been proposed (US Pat. No. 4,427,537), according to which heavy petroleum charges, in particular having significant quantities of aspaltenes, could be cracked by improving their spraying in the zone of injection of the catalyst, so to create, upon contact with the catalyst grains, a sufficient thermal shock to allow thermocracking of the molecules with high molecular weight. The thermal cleavage of these molecules into smaller molecules allows the latter to be catalytically recreated in the gas phase, when they are placed in the presence of the catalyst grains.

Des charges pétrolières, caractérisées en ce qu'au moins 10% de leur poids possède un point d'ébullition supérieur à 500°C, ont ainsi pu être traitées dans les unités de craquage catalytique, grâce à une augmentation de la température dans la zone d'injection du catalyseur et de charge à craquer (ou «zone de mélange») et à une bonne pulvérisation de la charge dans cette zone. Cependant, l'hétérogénéité des températures, qui résulte d'une telle injection, a nécessité la mise au point de réacteurs à courts temps de séjour, afin d'éviter l'occurence d'un sur- craquage ou de réactions secondaires, telles que des réactions de polymérisation des produits craqués, ainsi que pour éviter la production d'un excès de gaz difficiles à valoriser.Petroleum charges, characterized in that at least 10% of their weight has a boiling point above 500 ° C., have thus been able to be treated in the catalytic cracking units, by virtue of an increase in the temperature in the zone of injecting the catalyst and of the charge to be cracked (or “mixing zone”) and of a good spraying of the charge in this zone. However, the heterogeneity of temperatures, which results from such an injection, necessitated the development of reactors with short residence times, in order to avoid the occurrence of overcracking or of secondary reactions, such as polymerization reactions of cracked products, as well as to avoid the production of an excess of gases which are difficult to recover.

En poursuivant ses travaux sur le craquage catalytique des charges pétrolières lourdes, la Demanderesse a mis en évidence le fait que cette première solution ne résolvait que partiellement le problème du craquage des charges lourdes particulièrement difficiles à valoriser, par exemple celles dont 10% du poids possède un point d'ébullition supérieur à 550°C, car la chaleur nécessaire au thermocraquage des molécules lourdes devenait tellement importante que la vitesse de réaction, liée à la température de mélange dans la zone d'injection de la charge à craquer, nécessitait un temps de séjour limité à quelques secondes seulement, d'où un contrôle très difficile des conditions de la réaction avec les moyens actuels.Continuing its work on cataly cracking tick of heavy petroleum charges, the Applicant has highlighted the fact that this first solution only partially solved the problem of cracking heavy charges which are particularly difficult to recover, for example those of which 10% by weight has a boiling point greater than 550 ° C, because the heat necessary for the thermocracking of heavy molecules became so important that the reaction rate, linked to the mixing temperature in the injection area of the charge to be cracked, required a residence time limited to only a few seconds , hence a very difficult control of the reaction conditions with current means.

Il a cependant été établi par la Demanderesse que le craquage des charges lourdes peut être effectué de façon simple et efficace en assurant une régulation appropriée de la température dans la zone réactionnelle, grâce à laquelle:

  • - un choc thermique maximum est effectué à l'injection pendant une durée très courte mais suffisante pour permettre la conversion thermique des molécules à poids moléculaire élevé et notamment des asphaltènes présents dans la charge, et une meilleure vaporisation des molécules destinées à être craqués catalytiquement, puis,
  • - la température de la réaction catalytique souhaitée et maintenue et reste indépendante de celle qui résulte de l'injection du catalyseur et de la charge craquer, par introduction, en aval de la zone d'injection de la charge, d'un fluide auxiliaire, dans des conditions telles de débit, de température et de pression, que l'introduction de ce fluide permette à la réaction de craquage catalytique de s'effectuer dans des conditions plus douces et indépendantes de la température de mélange.
It has however been established by the Applicant that the cracking of heavy loads can be carried out in a simple and effective manner by ensuring appropriate regulation of the temperature in the reaction zone, by means of which:
  • a maximum thermal shock is carried out on injection for a very short time, but sufficient to allow the thermal conversion of the molecules with high molecular weight and in particular of the asphaltenes present in the feed, and better vaporization of the molecules intended to be catalytically cracked, then,
  • the temperature of the desired and maintained catalytic reaction and remains independent of that which results from the injection of the catalyst and of the cracked charge, by introduction, downstream of the charge injection zone, of an auxiliary fluid, under such flow, temperature and pressure conditions, that the introduction of this fluid allows the catalytic cracking reaction to take place under milder conditions independent of the mixing temperature.

Cette régulation présente un double avantage:

  • - d'une part, l'augmentation substantielle de la température de mélange dans la zone d'injection de la charge lourde sur le catalyseur permet une meilleure vaporisation de celle-ci et un craquage thermique instantané des composés les plus lourds, ce qui- diminue la formation de coke sur les grains de catalyseurs, liée en particulier au fait que les composés à haut point d'ébullition, ou à caractère basique (composés aromatiques azotés, hydrocarbures aromatiques condensés etc.), ont tendance à s'adsorber et à neutraliser certains sites acides de catalyseur;
  • - d'autres part, si le thermocraquage des molécules les plus lourdes est réalisé de façon quasi-instantanée à haute température, les composés plus légers, en provenance soit de la charge elle-même, soit de la réaction de thermocraquage, doivent être craqués catalytiquement, par contact avec les sites actifs de grains de catalyseur, au cours d'une réaction plus lente, dont l'optimum de température n'est pas nécessairement celui qui résulte des conditions précédemment évoquées.
This regulation has a double advantage:
  • on the one hand, the substantial increase in the mixing temperature in the injection zone of the heavy load on the catalyst allows better vaporization of the latter and instantaneous thermal cracking of the heaviest compounds, which decreases the formation of coke on the grains of catalysts, linked in particular to the fact that the compounds with high boiling point, or of basic character (aromatic nitrogen compounds, condensed aromatic hydrocarbons etc.), tend to adsorb and neutralize certain acid catalyst sites;
  • - on the other hand, if the heavier cracking of the heaviest molecules is carried out almost instantaneously at high temperature, the lighter compounds, coming either from the filler itself, or from the thermocracking reaction, must be cracked catalytically, by contact with the active sites of catalyst grains, during a slower reaction, the optimum temperature of which is not necessarily that which results from the conditions mentioned above.

La régulation de la température conduite selon l'invention permet donc de contrôler la durée du contact entre les molécules à craquer catalytiquement et le catalyseur, et d'éviter ainsi une prolongation excessive du thermocraquage générateur de coke et du gaz légers, ainsi que l'occurence de réactions secondaires liées à une température de craquage catalytique inadaptée.The temperature regulation carried out according to the invention therefore makes it possible to control the duration of the contact between the molecules to be catalytically cracked and the catalyst, and thus to avoid an excessive prolongation of the thermocracking generating coke and light gases, as well as the occurrence of side reactions linked to an unsuitable catalytic cracking temperature.

Un but de la présente invention est, par conséquent, dans un procédé de craquage catalytique d'une charge d'hydrocarbures en lit fluidisé, de mettre en contact la charge et le catalyseur à une température élevée apte à prévenir les dépôts de coke sur le catalyseur et à favoriser de façon optimum le craquage catalytique de cette charge.An object of the present invention is, therefore, in a process for catalytic cracking of a charge of hydrocarbons in a fluidized bed, to bring the charge and the catalyst into contact at a high temperature capable of preventing deposits of coke on the catalyst and optimally promote catalytic cracking of this charge.

Un autre but de l'invention est de contrôler la durée de contact du catalyseur et de la charge à cette température élevée, de façon à diminuer les réactions secondaires ou à limiter le thermocraquage susceptible de se produire.Another object of the invention is to control the duration of contact of the catalyst and of the charge at this high temperature, so as to reduce the secondary reactions or to limit the thermocracking liable to occur.

L'invention a par conséquent pour objet un procédé de craquage catalytique en lit fluidisé dilué et à court temps de contact d'une charge d'hydrocarbures lourde dont plus de 10% en poids possèdent un point d'ébullition supérieur à 500°C, ce procédé comprenant une phase de mise en contact, à flux ascendant ou descendant, dans une colonne, dans des conditions de craquage, de ladite charge et de particules d'un catalyseur de craquage, une phase de séparation du catalyseur usé et de la charge craquée en aval de la zone d'injection de ladite charge avec au moins une phase de strippage du catalyseur usé à l'aide d'un fluide, puis une phase de régénération dudit catalyseur dans des conditions de combustion du coke déposé sur celui-ci, et enfin une phase de recyclage du catalyseur régénéré à l'alimentation de ladite colonne, ce procédé étant caractérisé en ce que l'on injecte dans ladite colonne du catalyseur régénéré dans des conditions telles que la température d'équilibre résultant du mélange de la charge vaporisée et du catalyseur soit au moins supérieure à 500°C et au moins supérieure de 40 à 100°C à la température finale de réaction en fin de colonne, et en ce que l'on injecte enaval de cette zone de mélange, mais en amont de la phase de séparation, un fluide auxiliaire dans des conditions telles que l'injection de ce fluide auxiliaire permette à la réaction de craquage catalytique de s'effectuer dans des conditions plus douces et indépendantes par rapport à ladite température de mélange, la température finale de réaction étant toutefois supérieure au point de rosée des hydrocarbures présents les plus lourds.The subject of the invention is therefore a process for catalytic cracking in a dilute fluidized bed and with a short contact time of a heavy hydrocarbon charge of which more than 10% by weight has a boiling point above 500 ° C., this process comprising a contacting phase, with ascending or descending flow, in a column, under cracking conditions, of said charge and of particles of a cracking catalyst, a phase of separation of the spent catalyst and of the charge cracked downstream of the injection zone of said charge with at least one stripping phase of the spent catalyst using a fluid, then a regeneration phase of said catalyst under conditions of combustion of the coke deposited on it , and finally a phase of recycling the regenerated catalyst to the supply of said column, this process being characterized in that injected into said column of regenerated catalyst under conditions such as the equilibrium temperature resulting from the melan ge of the vaporized charge and of the catalyst is at least greater than 500 ° C. and at least 40 to 100 ° C. greater than the final reaction temperature at the end of the column, and in that one injects downstream of this zone of mixing, but upstream of the separation phase, an auxiliary fluid under conditions such that the injection of this auxiliary fluid allows the catalytic cracking reaction to take place under milder and independent conditions with respect to said temperature mixing, the final reaction temperature however being higher than the dew point of the heaviest hydrocarbons present.

Le fluide injecté pourra être un liquide ou un gaz et, en particulier, de l'eau,de la vapeur d'eau, ou tout hydrocarbure vaporisable dans les conditions d'injection, en particulier, les gas-oil de cokéfaction ou de viscoréduction, des diluants catalytiques, des solvants lourds aromatiques, ainsi que certaines coupes de désasphaltage extraites au solvant lourd.The injected fluid may be a liquid or a gas and, in particular, water, water vapor, or any hydrocarbon vaporizable under the injection conditions, in particular, coking or visbreaking gas oils. , catalytic thinners, heavy aromatic solvents, as well as certain deasphalting cuts extracted with heavy solvent.

L'injection de ce fluide aura donc un effet de trempe sélective sur le mélange réactionnel constitué par la charge et les grains de catalyseur, et le débit d'injection dudit fluide devra être tel qu'il permette de réguler, dans des conditions optimum, la température de la réaction de craquage catalytique, sans nuire pour autant au strippage subséquent du catalyseur usé et sans entraîner de condensation sur les particules de catalyseur des hydrocarbures présents les plus lourds, ce qui se traduirait par un dépôt accru de coke sur le catalyseur. Dans la pratique, les conditions d'injection du fluide seront telles qu'elle provoque un abaissement instantané de la température du mélange réactionnel de l'ordre de 10 à 70°C, ce qui, à température finale de réaction constante, se traduit donc par une augmentation sensiblement équivalente de la température de mélange entre la charge à craquer et les grains de catalyseur régénéré.The injection of this fluid will therefore have a selective quenching effect on the reaction mixture constituted by the charge and the grains of catalyst, and the injection rate of said fluid must be such that it makes it possible to regulate, under optimum conditions, the temperature of the catalytic cracking reaction, without harming the subsequent stripping of the spent catalyst and without causing condensation on the catalyst particles of the heaviest hydrocarbons present, which would result in an increased deposition of coke on the catalyst. In practice, the conditions for injecting the fluid will be such that it causes an instantaneous lowering of the temperature of the reaction mixture of the order of 10 to 70 ° C., which, at constant final reaction temperature, therefore results in a substantially equivalent increase in the mixing temperature between the charge to be cracked and the regenerated catalyst grains.

Dans la pratique, la vaporisation de la charge et la réaction initiale de craquage des composés les plus lourds étant pratiquement instantanée, la trempe opérée à l'aide du fluide auxiliaire aura lieu moins d'une seconde après l'injection de la charge craquée et, de préférence, moins d'une demi-seconde après celle-ci.In practice, the vaporization of the charge and the initial cracking reaction of the heaviest compounds being practically instantaneous, the quenching carried out using the auxiliary fluid will take place less than a second after the injection of the cracked charge and , preferably, less than half a second after this.

Ainsi qu'on l'exposera ci-après plus en détail, le procédé conforme à l'invention peut être mis en oeuvre aussi bien dans une colonne de craquage à flux ascendant (élévateur, dit encore «riser») que dans une colonne à flux descendant («dropper»).As will be explained below in more detail, the process according to the invention can be implemented both in a cracking column with ascending flow (riser, also called "riser") and in a column with downward flow ("dropper").

Un avantage important du procédé selon l'invention est qu'il permet de limiter la température de régénération du catalyseur, du fait d'un dépôt réduit de coke, et rend possible la conversion de charges lourdes normalement excluses dans le procédé de craquage catalytique en lit fluidisé.An important advantage of the process according to the invention is that it makes it possible to limit the catalyst regeneration temperature, due to a reduced deposition of coke, and makes it possible to convert heavy charges normally excluded in the catalytic cracking process into fluidized bed.

Il est ainsi possible de maintenir, à l'entrée de la zone réactionnelle, le débit de recyclage du cataly-C seur et le rapport - entre la masse (C) du catalyseur 0 et celle (O) de la charge à craquer aux valeurs désirées pour assurer une vaporisation rapide et homogène de la charge se rapprochant des conditions de «flash», et d'obtenir une conversion optimum des produits de la charge, par craquage catalytique, en produits désirés possédant en particulier un meilleur indice d'octane.It is thus possible to maintain, at the entrance to the reaction zone, the rate of recycling of the catalyst-C sor and the ratio - between the mass (C) of catalyst 0 and that (O) of the charge to be cracked at values desired to ensure rapid and homogeneous vaporization of the charge approaching the "flash" conditions, and to obtain optimum conversion of the products of the charge, by catalytic cracking, into desired products having in particular a better octane number.

A cet effet, les conditions d'injection de la charge et du catalyseur seront telles que la température de mélange sera légèrement supérieure à la température de vaporisation de la charge.To this end, the conditions for injecting the charge and the catalyst will be such that the mixing temperature will be slightly higher than the vaporization temperature of the charge.

Naturellement, les conditions d'injection du fluide auxiliaire de trempe, en particulier, le débit, la température et la pression, devront être ajustées en fonction des caractéristiques de la charge et du catalyseur, ainsi que des conditions de réaction de craquage catalytique et du profil de la température souhaités, c'est-à-dire en pratique en fonction de la température de mélange et de la température finale de réaction souhaitée.Naturally, the conditions of injection of the auxiliary quenching fluid, in particular, the flow rate, the temperature and the pressure, will have to be adjusted as a function of the characteristics of the charge and of the catalyst, as well as of the conditions of reaction of catalytic cracking and of profile of the desired temperature, that is to say in practice as a function of the mixing temperature and of the desired final reaction temperature.

Une forme de mise en oeuvre préférée du procédé selon l'invention consiste donc en ce que l'on régule l'injection dudit fluide auxiliaire dans la colonne de craquage de façon telle que la température réactionnelle qui résulte de cette injection soit maintenue à une valeur prédéterminée et constante, mais suffisamment élevée pour que l'efficacité du strippage ne soit pas substantiellement altérée.A preferred embodiment of the process according to the invention therefore consists in regulating the injection of said auxiliary fluid into the cracking column so that the reaction temperature which results from this injection is maintained at a value predetermined and constant, but high enough that the effectiveness of the stripping is not substantially impaired.

L'invention a également pour objet un dispositif de craquage catalytique de charges lourdes d'hydrocarbures dont plus de 10% en poids possèdent un point d'ébullition supérieur à 500°C, comprenant une colonne de craquage à flux ascendant ou descendant, des moyens pour alimenter sous pression ladite colonne avec une charge d'hydrocarbures et des particules d'un catalyseur de craquage régénéré, un moyen de séparation des produits de la charge craquée et des particules de catalyseur usé, au moins un moyen de strippage par au moins un fluide des particules de catalyseur usé, au moins une unité de régénération dudit catalyseur par combustion du coke déposé sur celui-ci, des moyens de recyclage du catalyseur régénéré auxdits moyens d'alimentation et, en aval de la zone de mélange dans ladite colonne de la charge d'hydrocarbures et des particules de catalyseur régénéré, au moins un moyen d'injection d'un fluide auxiliaire dans des conditions de débit, de température et de pression, telles que l'injection de ce fluide auxiliaire diminue la température de la zone réactionnelle située immédiatemment en aval de façon indépendante de la température de mélange, ce dispositif étant caractérisé en ce qu'il comporte des moyens pour réguler le débit dudit fluide auxiliaire de façon telle que la température de la zone réactionnelle en aval de l'injection du fluide auxiliaire soit maintenue à une valeur de consigne qui est propre à la nature de la charge à craquer, au type de catalyseur et à son mode de régénération.The invention also relates to a catalytic cracking device for heavy loads of hydrocarbons of which more than 10% by weight have a boiling point above 500 ° C., comprising a cracking column with rising or falling flow, means for supplying said column under pressure with a hydrocarbon feedstock and particles of a regenerated cracking catalyst, a means for separating the products from the cracked feedstock and spent catalyst particles, at least one stripping means with at least one fluid from the spent catalyst particles, at least one unit for regenerating said catalyst by combustion of the coke deposited thereon, means for recycling the regenerated catalyst to said supply means and, downstream of the mixing zone in said column of the charge of hydrocarbons and particles of regenerated catalyst, at least one means for injecting an auxiliary fluid under flow, temperature and pressure conditions, such as the injection of this auxiliary fluid decreases the temperature of the reaction zone located immediately downstream independently of the mixing temperature, this device being characterized in that it comprises means for regulating the flow rate of said auxiliary fluid so that the temperature of the reaction zone downstream of the injection of the auxiliary fluid is maintained at a set value which is specific to the nature of the charge to be cracked, to the type of catalyst and to its mode of regeneration.

De préférence, ce dispositif comprendra également des moyens accroître le débit du catalyseur chaud lorsque la température finale de réaction tend à décroître par rapport à la valeur de consigne.Preferably, this device will also include means for increasing the flow rate of the hot catalyst when the final reaction temperature tends to decrease compared to the set value.

Le moyen d'injection d'un fluide auxiliaire pourra être avantageusement situé dans la zone réactionnelle à une distance qui pourra être comprise entre 0,1 et 0,8 fois la longueur de ladite zone réactionnelle et, de préférence, entre 0,1 et 0,5 fois cette longueur, en aval de la zone d'injection de la charge à craquer.The means for injecting an auxiliary fluid may advantageously be located in the reaction zone at a distance which may be between 0.1 and 0.8 times the length of said reaction zone and, preferably, between 0.1 and 0.5 times this length, downstream of the injection site of the load to be cracked.

Ce ou ces moyens d'injection seront avantageusement constitués par un dispositif d'injection de type connu en soi, permettant de répartir le fluide de façon homogène sur toute la section de la zone réactionnelle.This or these injection means will advantageously consist of an injection device of a type known per se, making it possible to distribute the fluid homogeneously over the entire section of the reaction zone.

En particulier, lorsque le fluide régulateur sera constitué par un liquide, les quantités nécessaires à la régulation de la température de mélange seront injectées à l'aide d'un dispositif de pulvérisation permettant, de façon connue en soi, de pulvériser ce liquide sous forme d'un brouillard très fin sur toute la section de la zone réactionnelle de façon à obtenir un transfert de chaleur aussi instantané que possible. Ainsi, dans une unité industrielle de type classique, une injection de 20 à 150 litres d'eau liquide par mètre cube de charge traitée permettra d'abaisser la température de la zone de mélange située en amont d'environ 10 à 70°C.In particular, when the regulating fluid consists of a liquid, the quantities necessary for regulating the mixing temperature will be injected using a spraying device making it possible, in a manner known per se, to spray this liquid in the form very fine mist over the entire section of the reaction zone so as to obtain as instantaneous heat transfer as possible. Thus, in an industrial unit of the conventional type, an injection of 20 to 150 liters of liquid water per cubic meter of charge treated will make it possible to lower the temperature of the mixing zone located upstream from approximately 10 to 70 ° C.

En outre, lorsque le fluide injecté sera un hydrocarbure, tel que par exemple un diluant catalytique, le débit nécassaire pour réaliser une augmentation identique de température sera de 100 à 700 litres d'hydrocarbure par mètre cube de charge traitée.In addition, when the injected fluid will be a hydrocarbon, such as for example a catalytic diluent, the flow required to achieve an identical temperature increase will be from 100 to 700 liters of hydrocarbon per cubic meter of charge treated.

L'invention va être décrite ci-après plus en détail, en référence aux dessins schématiques annexés, sur lesquels:

  • la figure 1 illustre l'application du procédé selon l'invention à un ensemble de craquage catalytique en lit fluidisé à colonne ascendante ou «riser»;
  • la figure 2 illustre l'application de l'invention à un ensemble de craquage à colonne à flux descendant ou «dropper»;
  • la figure 3 illustre une variante de la figure 1, avec un autre mode de régulation du procédé.
The invention will be described below in more detail, with reference to the accompanying schematic drawings, in which:
  • FIG. 1 illustrates the application of the method according to the invention to a set of catalytic cracking in a fluidized bed with an ascending column or “riser”;
  • FIG. 2 illustrates the application of the invention to a cracking assembly with a downflow column or “dropper”;
  • FIG. 3 illustrates a variant of FIG. 1, with another method of regulating the process.

Sur la figure 1, le catalyseur régénéré est injecté par une conduite 1 à la base d'une colonne à flux ascendant 2 ou «élévateur», ainsi qu'un gaz vecteur injecté en 3. La charge d'hydrocarbures à traiter est elle-même injectée en 4 à la base de la colonne et les hydrocarbures et les particules du catalyseur sont en contact dans la zone 2, immédiatement en aval de l'injection de la charge. La température du mélange catalyseur + charge vaporisée est comprise entre environ 500 et 650°C, suivant la nature de la charge et les objectifs de conversion désirée.In FIG. 1, the regenerated catalyst is injected via a pipe 1 at the base of an ascending flow column 2 or “riser”, as well as a carrier gas injected at 3. The charge of hydrocarbons to be treated is itself even injected in 4 at the base of the column and the hydrocarbons and the particles of the catalyst are in contact in zone 2, immediately downstream of the injection of the feed. The temperature of the catalyst + vaporized charge mixture is between approximately 500 and 650 ° C., depending on the nature of the charge and the desired conversion objectives.

A la partie supérieure de la colonne 1 est prévue une enceinte 6 de séparation des produits craqués et des particules de catalyseur usé. A la base de cette enceinte 6 sont disposés des injecteurs 7 d'un fluide de strippage, généralement de la vapeur d'eau, agissant à contre-courant des particules de catalyseur séparées. A la base de l'enceinte 6, les particules de catalyseur sont évacuées en 8 vers un second dispositif de strippage ou vers un régénérateur, tandis que les produits craqués sont évacués à la partie supérieure (non représentée) de l'enceinte 6.At the upper part of the column 1 is provided an enclosure 6 for separating the cracked products and the spent catalyst particles. At the base of this enclosure 6 are arranged injectors 7 of a stripping fluid, generally steam, acting against the current of the separated catalyst particles. At the base of the enclosure 6, the catalyst particles are removed at 8 to a second stripping device or to a regenerator, while the cracked products are removed at the upper part (not shown) of the enclosure 6.

Conformément à l'invention, un fluide auxiliaire de trempe des produits de craquage est injecté en 9 dans la partie 5 de la colonne 2, en aval de la zone de contact entre particules de catalyseur et charge vaporisée. Ce fluide auxiliaire - eau, vapeur d'eau, hydrocarbures, ou autre - est injecté avec un débit tel qu'il abaisse de 10 à 70°C, suivant le résultat désiré, la température du mélange, en vue d'optimiser les réactions de craquage catalytique de la charge. La température finale de la zone réactionnelle ainsi refroidie pourra être, par exemple, de l'ordre de 500°C, mais devra être supérieur au point de rosée des hydrocarbures présents les plus lourds.In accordance with the invention, an auxiliary fluid for quenching the cracked products is injected at 9 into part 5 of column 2, downstream of the contact zone between catalyst particles and vaporized charge. This auxiliary fluid - water, water vapor, hydrocarbons, or other - is injected at a rate such that it lowers from 10 to 70 ° C, depending on the desired result, the temperature of the mixture, in order to optimize the reactions catalytic cracking of the charge. The final temperature of the reaction zone thus cooled may be, for example, of the order of 500 ° C, but must be higher than the dew point of the heaviest hydrocarbons present.

A cet effet, une sonde de température 10 sera prévue à l'intérieur de l'enceinte 6 pour y mesurer la température et pour éventuellement contrôler la vanne 12 commandant le débit du fluide auxiliaire dans la ligne d'alimentation 13 du moyen d'injection 9, de façon telle que la température dans l'enceinte 6 soit maintenue supérieure à une température de consigne propre au type de charge traitée. Une autre sonde de température 14, disposée dans la colonne 2 en amont du moyen d'injection 9 du fluide auxiliaire, c'est-à-dire dans la zone de mise en contact de la charge avec les particules de catalyseur, commande, d'une part, la vanne 16, permettant ainsi d'agir sur le débit d'injection du catalyseur régénéré dans la colonne et donc sur la température dans la zone de mise en contact et, d'autre part, la vanne 12 pour réguler le débit du fluide auxiliaire dans la ligne d'alimentation 13 du moyen d'injection 9.For this purpose, a temperature probe 10 will be provided inside the enclosure 6 to measure the temperature there and to possibly control the valve 12 controlling the flow of the auxiliary fluid in the supply line 13 of the injection means. 9, so that the temperature in the enclosure 6 is maintained above a set temperature specific to the type of load treated. Another temperature probe 14, arranged in the column 2 upstream of the means 9 for injecting the auxiliary fluid, that is to say in the zone for bringing the charge into contact with the particles of catalyst, control, d on the one hand, the valve 16, thus making it possible to act on the injection rate of the regenerated catalyst in the column and therefore on the temperature in the contacting zone and, on the other hand, the valve 12 to regulate the flow rate of the auxiliary fluid in the supply line 13 of the injection means 9.

Dans le cas de la figure 2, la colonne 20 de craquage est du type dit «dropper», c'est-à-dire que les particules de catalyseur régénéré 21 sont injectées à la partie supérieure de la colonne 20 et y tombent par gravité. La charge à craquer est également introduite à la partie supérieure de la colonne en 22. Une enceinte 23 située à la base de la colonne 20 permet de séparer et d'évacuer les effluents, à savoir les produits du craquage par la conduite 24, et les particules de catalyseur usé vers la base de cette enceinte 23, pour les stripper, puis les acheminer vers la régénération.In the case of FIG. 2, the cracking column 20 is of the so-called “dropper” type, that is to say that the particles of regenerated catalyst 21 are injected into the upper part of the column 20 and fall there by gravity . The charge to be cracked is also introduced into the upper part of the column at 22. An enclosure 23 located at the base of the column 20 makes it possible to separate and evacuate the effluents, namely the products of cracking through the pipe 24, and the spent catalyst particles towards the base of this enclosure 23, in order to strike them, then convey them to the regeneration.

Conformément à l'invention, un fluide auxiliaire de trempe des produits de craquage est injecté en 26, en aval des moyens d'injection 22 de la charge. Son débit est tel, pour une température de mélange donnée, qu'il abaisse la température finale de réaction d'environ 10 à 70°C, pour permettre aux réactions de craquage catalytique de s'effectuer dans des conditions optimales.In accordance with the invention, an auxiliary quenching fluid for the cracked products is injected at 26, downstream of the means 22 for injecting the charge. Its flow rate is such that, for a given mixing temperature, it lowers the final reaction temperature by approximately 10 to 70 ° C, to allow the catalytic cracking reactions to be carried out under optimal conditions.

Comme dans le cas précédent, une sonde de température 27, disposée avant la conduite 24, permet de commander, par une vanne 29 disposée sur la canalisation 30 d'alimentation, le débit de fluide auxiliaire du moyen d'injection 26, de façon telle que la température relevée en 27 soit constamment égale ou supérieure à une température de consigne, tandis que la sonde permet d'agir sur la température d'injection dans la zone réactionnelle et sur la régulationdu débit d'injection en 26.As in the previous case, a temperature probe 27, disposed before the pipe 24, makes it possible to control, by a valve 29 arranged on the supply pipe 30, the flow of auxiliary fluid of the injection means 26, in such a way that the temperature recorded in 27 is constantly equal to or higher than a set temperature, while the probe makes it possible to act on the injection temperature in the reaction zone and on the regulation of the injection flow rate in 26.

Sur la figure 3, la colonne 2 de craquage est à nouveau de type riser et les chiffres de référence désignant les éléments de l'unité sont les mêmes que pour ceux de la figure 1. Cette figure présente un mode de régulation simplifié et particulièrement avantageux, conforme à la présente invention. Dès que le fluide auxiliaire est injecté en 9, ou que l'on augmente le volume d'injection, la température finale de la réaction catalytique, mesurée en 10, aura tendance à décroître par rapport à la valeur de consigne souhaitée pour la charge correspondante. La vanne 16, agissant sur le débit de catalyseur chaud régénéré, assurera aussitôt une augmentation de la température de mélange qui, compte tenu du débit injecté en 9, permettra de faire remonter la température finale de craquage à la valeur de consigne. Les deux exemples suivants illustrent les avantages du procédé conforme à l'invention.In FIG. 3, the cracking column 2 is again of the riser type and the reference numerals designating the elements of the unit are the same as for those of FIG. 1. This figure presents a simplified and particularly advantageous mode of regulation. , according to the present invention. As soon as the auxiliary fluid is injected at 9, or when the injection volume is increased, the final temperature of the catalytic reaction, measured at 10, will tend to decrease compared to the desired setpoint for the corresponding charge. . The valve 16, acting on the flow of hot regenerated catalyst, will immediately ensure an increase in the mixing temperature which, taking into account the flow injected at 9, will make it possible to bring the final cracking temperature back to the set value. The following two examples illustrate the advantages of the process according to the invention.

Exemple 1Example 1

On craque dans un dispositif pilote de craquage, comprenant un élévateur à temps de séjour court et un système de régénération de catalyseur à deux étages, comme décrit dans la demande de brevet français n° 2 574 422, une charge résiduelle hydrodé- sulfurée ayant les caractéristiques suivantes:

Figure imgb0001
In a pilot cracking device, comprising a short residence time elevator and a two-stage catalyst regeneration system, as described in French patent application No. 2,574,422, a residual hydrodesulfurized charge having the following features:
Figure imgb0001

On utilise, pour le craquage, un catalyseur commercial, comprenant des zéolithes de grande stabilité et une matrice propre à craquer-les molécules d'hydrocarbures les plus lourdes dans des conditions de craquage.A commercial catalyst is used for cracking, comprising zeolites of high stability and a matrix capable of cracking - the heaviest hydrocarbon molecules under cracking conditions.

Deux essais ont été effectués avec la même charge, l'un dans des conditions usuelles de craquage, l'autre avec injection à mi-hauteur de l'élévateur d'un fluide de trempe constituée par de l'eau liquide.Two tests were carried out with the same load, one under usual cracking conditions, the other with injection halfway up the elevator of a quenching fluid consisting of liquid water.

Les conditions des deux essais ont été les suivantes:

Figure imgb0002
The conditions of the two tests were as follows:
Figure imgb0002

Le tableau ci-dessus montre l'avantage résultant d'une élévation de la température initiale de craquage à plus de 550°C et d'une trempe des produits de la réaction, à l'aide de l'eau, pour ramener la température du mélange à 525°C.The table above shows the advantage resulting from raising the initial cracking temperature above 550 ° C and quenching the reaction products, using water, to bring the temperature down. of the mixture at 525 ° C.

Pour une température finale de craquage identique (525°C) et du fait de la température d'injection (595°C au lieu de 578°C), la teneur en hydrogène du coke est plus faible dans le cas du procédé selon l'invention et le L coke est légèrement inférieur, ce qui montre que les fractions lourdes ont été efficacement craquées et ne restent pas adsorbées sur le catalyseur usé.For an identical final cracking temperature (525 ° C) and due to the injection temperature (595 ° C instead of 578 ° C), the hydrogen content of the coke is lower in the case of the process according to invention and the L coke is slightly lower, which shows that the heavy fractions have been effectively cracked and do not remain adsorbed on the spent catalyst.

On voit ici qu'avec une température plus basse pour le catalyseur usé et avec un L coke et une teneur en hydrogène plus faibles, il est possible d'abaisser la température finale de régénération du catalyseur d'environ 53°C. Ceci peut être mis à profit pour augmenter soit le rapport C/0 (cas de cet exemple), soit la température de la charge, ce qui améliore de façon notable la vaporisation de la charge.It is seen here that with a lower temperature for the spent catalyst and with a lower L coke and a lower hydrogen content, it is possible to lower the final catalyst regeneration temperature by approximately 53 ° C. This can be used to increase either the C / 0 ratio (case of this example) or the temperature of the charge, which significantly improves the vaporization of the charge.

Les effets bénéfiques obtenus par le procédé conforme à l'invention sont résumés ci-après:The beneficial effects obtained by the process according to the invention are summarized below:

On retiendra, essentiellement, une conversion améliorée, une meilleure sélectivité en essence et en distillat, et une production plus faible de gaz secs traduisant une réduction du craquage thermique, et de l'effet du nickel. Par ailleurs, le caractère plus oléfini- que et moins aromatique des produits se traduit par un meilleur indice d'octane et un meilleur indice de cétane. Eifin, une meilleure stabilite de catalyseur, due à une température de régénération moins élevée, permet d'en réduire le taux de renouvellement pour maintenir l'activité désirée.We will retain, essentially, an improved conversion, a better selectivity in gasoline and in distillate, and a lower production of dry gases translating a reduction of thermal cracking, and of the effect of nickel. Furthermore, the more olefinic and less aromatic nature of the products results in a better octane number and a better cetane number. Eifin, better catalyst stability, due to a lower regeneration temperature, makes it possible to reduce the renewal rate to maintain the desired activity.

Exemple 2Example 2

Le même dispositif et le même catalyseur de craquage que dans l'exemple précédent sont utilisés avec une charge dont les catactéristiques sont les suivantes:

Figure imgb0003
The same device and the same cracking catalyst as in the previous example are used with a filler whose characteristics are as follows:
Figure imgb0003

Le fluide auxiliaire est constitué cette fois d'un recycle des effluents de craquage de point d'ébullition compris entre 340°C et 460°C, pratiqué 0,2 secondes après injection de la charge dans la zone de mélange.The auxiliary fluid this time consists of a recycling of cracking effluents with a boiling point of between 340 ° C. and 460 ° C., carried out 0.2 seconds after injection of the charge into the mixing zone.

Les conditions opératoires sont les suivantes:

Figure imgb0004
The operating conditions are as follows:
Figure imgb0004

Dans cet exemple, la charge lourde considérée n'aurait pu être traitée sans recourir aux moyens mis en oeuvre dans la présente invention, dans la mesure où, selon l'art antérieur, au moins 15% en poids de cette charge n'auraient pu être vaporisés, ce qui aurait conduit à une production de coke hors des limites compatibles avec la satisfaction du bilan thermique de l'unité. La température de mélange a été augmentée d'environ 40°C pour assurer la vaporisation complète et les conditions de choc thermique nécessaires au craquage des composés les plus lourds présents dans cette charge, après quoi la pulverisation d'un hydrocarbure dans le milieu réactionnel permet de ramener la température finale à 510°C et d'assurer ainsi une conversion optimale.In this example, the heavy load considered could not have been treated without resorting to the means used in the present invention, insofar as, according to the prior art, at least 15% by weight of this load could not have been be vaporized, which would have led to a production of coke outside the limits compatible with the satisfaction of the thermal balance of the unit. The mixing temperature was increased by approximately 40 ° C to ensure complete vaporization and the thermal shock conditions necessary for cracking the heaviest compounds present in this charge, after which the spraying of a hydrocarbon in the reaction medium makes it possible to reduce the final temperature to 510 ° C. and thus to ensure optimal conversion.

Le procédé conforme à l'invention permet donc d'améliorer les performances d'une unité de craquage pour une charge déterminée d'hydrocarbures. Il peut être utilisé avantageusement pour traiter avec une plus grande efficacité des charges plus lourdes et plus contaminées. De même, ce procédé présente un attrait exceptionnel pour le traitement de charges azotées, ou riches en composés polaires (résines, asphaltènes), où la forte présence d'azote aromatique est responsable d'une chute spectaculaire de la conversion. Sur un résidu Nigerian KOLE, par exemple, le gain de conversion avec le procédé conforme à l'invention est de l'ordre de 5,5% en volume. Ceci s'explique parla plus haute température de mélange, qui déplace favorablement l'équilibre d'adsorption de l'azote aromatique, en réduisant ainsi la neutralisation de certains sites acides du catalyseur.The process according to the invention therefore makes it possible to improve the performance of a cracking unit for a determined charge of hydrocarbons. It can advantageously be used to treat heavier and more contaminated loads with greater efficiency. In the same way, this process presents an exceptional attraction for the treatment of nitrogenous charges, or rich in polar compounds (resins, asphaltenes), where the strong presence of aromatic nitrogen is responsible for a spectacular fall of the conversion. On a Nigerian KOLE residue, for example, the conversion gain with the process according to the invention is of the order of 5.5% by volume. This is explained by the higher mixing temperature, which favorably displaces the adsorption balance of aromatic nitrogen, thereby reducing the neutralization of certain acid sites of the catalyst.

Claims (11)

1. A process for the catalytic cracking of a heavy charge of hydrocarbons, of which more than 10% by weight has a boiling point above 500°C, said process comprising a stage for bringing said charge and particles of a cracking catalyst into contact in a dilute fluidised bed and with a short contact time in ascending or descending flow in a column under cracking conditions, a stage for separating spent catalyst and the cracked charge downstream of the injection zone of said charge, at least one stage for stripping the spent catalyst, then a stage for regenerating said catalyst under combustion conditions of the coke deposited thereon, and, finally, a stage for recycling the regenerated catalyst to the feed of said column, this process being characterised in that regenerated catalyst is injected into said column under conditions such that the equilibrium temperature resulting from the mixing of the vaporised charge and the catalyst is at least higher than 500°C and at least 40 to 100°C higher than the final reaction temperature at the end of the column, and in that an auxiliary fluid is injected downstream of this mixing zone but upstream of the separating stage under conditions such that the injection of this auxiliary fluid enables the catalytic cracking reaction to be carried out under conditions which are more gentle and independent in relation to said mixing temperature, however, the final reaction temperature being higher than the dew point of the heaviest hydrocarbons present.
2. A process according to claim 1, characterised in that the auxiliary fluid is injected homogeneously over the entire section of the reaction zone by means of one or more spraying devices.
3. A process according to either of claims 1 and 2, characterised in that the injection conditions of said auxiliary fluid are such that the mixing temperature of the vaporised charge and the catalyst particles is lowered by about 10 to 70°C in relation to the temperature arising from bringing the catalyst and the charge into contact.
4. A process according to any of claims 1 to 3, characterised in that the means for injecting auxiliary fluid enabling the temperature to be controlled is situated at such a distance that the reduction in temperature resulting therefrom will take place less than one second after the injection of the charge and, preferably, less than one half second after this injection.
5. A process according to any of claims 1 to 4, characterised in that said auxiliary fluid is water or water vapour.
6. A process according to claim 5, characterised in that the water is injected in a quantity of between 20 and 150 litres per m3 of charge injected into the reaction zone.
7. A process according to any of claims 1 to 4, characterised in that the auxiliary fluid is a hydrocarbon which is vaporisable under the injection conditions and, in particular, a gas-oil, a catalytic diluent, a heavy aromatic solvent or a deasphalting fraction extracted from the heavy solvent.
8. A process according to claim 7, characterised in that the hydrocarbon is injected in a quantity of between 100 and 700 litres per cubic metre of treated charge.
9. A process according to any of claims 1 to 8, characterised in that the mixing temperature resulting from the injection of the catalyst and the charge to be cracked is between 500 and 650°C.
10. An apparatus for the catalytic cracking of heavy hydrocarbon charges, of which more than 10% by weight have a boiling point above 500°C, comprising an ascending (2) or descending (20) flow cracking column, means (4, 22; 1, 26) for feeding said column under pressure with a hydrocarbon charge and particles of a regenerated cracking catalyst, a means for separating products of the cracked charge and particles of spent catalyst, at least one means (7) for stripping with at least one fluid the particles of spent catalyst, at least one unit for regenerating said catalyst by combustion of the coke deposited thereon, means for recycling the regenerated catalyst to said feed means and, downstream of the mixing zone in said column of the hydrocarbon charge and the particles of regenerated catalyst, at least one means (9, 26) for injecting an auxiliary fluid under such conditions of flow, temperature and pressure that the injection of this auxiliary fluid reduces the temperature of the reaction zone situated immediately downstream independently of the mixing temperature, said apparatus being characterised in that it comprises means (10, 11, 12; 27, 28, 29) for controlling the flow of said auxiliary fluid in such a way that the temperature of the reaction zone downstream of the injection of the auxiliary fluid is maintained at a rated value which is appropriate to the nature of the charge to be cracked, of the type of catalyst used and its method of regeneration.
11. An apparatus according to claim 10, characterised in that it comprises means (15, 16) for increasing the flow of hot catalyst when the final reaction temperature tends to decrease in relation to the rated value.
EP86401464A 1985-07-10 1986-07-02 Process and apparatus for the catalytic cracking of hydrocarbons, with control of the reaction temperature Expired - Lifetime EP0208609B2 (en)

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EP0208609A1 (en) 1987-01-14
FR2584732B1 (en) 1988-08-19
FR2584732A1 (en) 1987-01-16
EP0208609B2 (en) 1995-08-16
AR240172A1 (en) 1990-02-28
CN86104812A (en) 1987-01-07
DE3663953D1 (en) 1989-07-20

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