EP0663434A1 - Fluid catalytic cracking process for hydrocarbon feed, particularly a high basic nitrogen content feed - Google Patents

Fluid catalytic cracking process for hydrocarbon feed, particularly a high basic nitrogen content feed Download PDF

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Publication number
EP0663434A1
EP0663434A1 EP94403062A EP94403062A EP0663434A1 EP 0663434 A1 EP0663434 A1 EP 0663434A1 EP 94403062 A EP94403062 A EP 94403062A EP 94403062 A EP94403062 A EP 94403062A EP 0663434 A1 EP0663434 A1 EP 0663434A1
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Prior art keywords
catalyst
reaction zone
charge
zone
cracking
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German (de)
French (fr)
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EP0663434B1 (en
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Michel Bourgogne
Thierry Patureaux
Nathalie Boisdron
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Total Marketing Services SA
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Total Raffinage Distribution 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
    • 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
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • the present invention relates to a catalytic cracking process in a fluidized bed of a hydrocarbon feedstock, in particular a feedstock with a high content of basic nitrogen compounds.
  • the cracking of the charge is carried out at a temperature of the order of 500 ° C., at a pressure close to atmospheric pressure, in the absence of hydrogen.
  • the catalyst becomes covered with coke and heavy hydrocarbons, and its regeneration is carried out continuously, outside the cracking reactor.
  • the heat resulting from the combustion of coke and of the traces of hydrocarbons remaining in the presence of air or oxygen serves to bring the catalyst particles to the desired temperature, which are recycled to the reactor.
  • the catalysts can be of various types and reference may be made on this point, for example, to EP-A-0 206 871.
  • upstream reactors also known as risers or, in English, "risers”
  • risers also known as risers or, in English, "risers”
  • basic nitrogen compounds present in the feed, mention will in particular be made of pyridine, quinoline, acridine, phenanthridine, hydroxyquinoline, hydroxypyridine and their alkylated derivatives. With such charges, the drop in conversion rate can reach up to 15 points compared to a normal charge. It is known, in fact, that basic nitrogen fixes itself on the active sites of the catalyst, which are acid sites, and thus alters the catalytic properties of the catalyst.
  • the object of the invention is also to eliminate or limit, in such a process, the wall effects of the reactor and the retro-movements of the catalyst particles.
  • the process according to the invention has the advantage of being suitable for cracking under good conditions of nitrogenous charges, on the one hand, because the low acidity of the catalyst, which reduces its activity, is compensated for by the increase in the reaction temperature, made possible by the use of a downflow reactor and by the resulting reduction in reaction time, and, on the other hand, because the increase of the reaction temperature makes it possible to shift towards adsorption the adsorption-desorption balance of the basic molecules on the acid sites of the catalyst.
  • the flow rate of catalyst used can advantageously be increased, which will increase the number of active sites.
  • the ratio of the mass of catalyst present in the reactor to the mass of hydrocarbons may, in particular, advantageously be greater than 5 and, preferably between 7 and 15.
  • the new catalyst used may, for example, comprise a limited amount of alumina (s), not exceeding 30% by weight, at least one zeolite, in an amount representing from 15 to 40% by weight, the complement to 100% may consist of kaolin, a basic or weakly acid clay, such as sepiolite and vermiculite, a silica-based binder and optionally a metal trap such as for example a metal oxide.
  • alumina s
  • zeolite in an amount representing from 15 to 40% by weight
  • the complement to 100% may consist of kaolin, a basic or weakly acid clay, such as sepiolite and vermiculite, a silica-based binder and optionally a metal trap such as for example a metal oxide.
  • the device shown comprises a tubular reactor 1 with downward flow, or “downer”, supplied at its upper part, from an enclosure 2, which is concentric with it, in particles of regenerated catalyst.
  • This charge is sprayed into fine droplets by injectors in the upper part of the reactor 1, towards the bottom of the latter, to mix with the catalyst particles, in contact with which the cracking reaction occurs. As will be seen below, these particles were brought to a temperature suitable for cracking by the regeneration operation of the spent catalyst.
  • the catalyst particles and the charge to be treated therefore flow from top to bottom, co-current, in reactor 1.
  • the spent catalyst particles are discharged into a stripping chamber 6, provided at its base with a diffuser 7, supplied with steam by a line 8.
  • the stripped catalyst particles are evacuated by gravity from the enclosure 6, through an inclined conduit 22, to an ascending column 12, in which they are conveyed upwards, to a regenerator 13, using a carrier gas. , disseminated at 14 at the base of column 12, starting from line 15.
  • the column 12 opens into the regenerator 13 below a ballistic separator 16, which ensures the separation of the catalyst particles and the carrier gas.
  • the catalyst particles are then regenerated, in a manner known per se, in the regenerator, by combustion of the coke which has deposited on their surface and of the remaining hydrocarbons, using a stream of air or oxygen. brought by line 17 to diffuser 18.
  • the regenerated catalyst particles are removed by gravity through the pipe 19 in the direction of the enclosure 2, without thermal losses.
  • the gases coming from the combustion are evacuated towards cyclones 23, which separate the fines, recycled by the conduit 20 towards the regenerator, and the gases, evacuated by the line 21.
  • Type of load processed A low nitrogen
  • B very nitrogenous
  • - density 17.7 18.5 - sulfur
  • % by weight 2.42
  • 0.9 - hydrogen % by weight
  • ppm 11.6 11.95 -
  • Conradson carbon % by weight
  • ppm basic nitrogen
  • ppm 350 1015 - PT 50% TBP (° C) 470 475 - vanadium (ppm) 1.5 1.0 - nickel (ppm) 1.1 1.9
  • the catalyst used is that described according to the invention.
  • Test 1 2 3 Catalyst injection temperature (° C) 750 748 733 Charge injection temperature (° C) 233 250 250 Reactor outlet temperature (° C) 520 530 540 C / O report 4.9 5.4 7.8

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

A fluid catalytic cracking (FCC) process for the cracking of a hydrocarbon charge, partic. one contg. a high basic N content in a tubular reaction zone comprises: - a supply of catalyst particles (at least in part regenerated) to the upper part of the reaction zone; - introduction and dispersion of the charge to be treated in the upper part of the reactor (beneath the entry pt. of the catalyst); - co-current circulation in mutual contact in the reaction zone of the catalyst and charge to be treated; - sepn. at the lower part of the reaction zone, of the deactivated catalyst from the reaction prods.; - stripping of the deactivated catalyst; - regeneration of at least part of the stripped catalyst in a regeneration zone; - recycling of the regenerated catalyst to the upper reaction zone, and - transfer of the cracked prods. to a sepn. zone. The process has the following characteristics: the catalyst circulates from top to bottom co-currently with the charge in the tubular zone; a catalyst is used which in equilibrium state (150 degrees C and 5 mbars) adsorbs less than 250 mu moles (pref. < 50 mu moles)/g of pyridine and retains after heating at 350 degrees C in a vacuum, no more than 20% (pref. 10%) of the amt. absorbed.

Description

La présente invention concerne un procédé de craquage catalytique en lit fluidisé d'une charge d'hydrocarbures, notamment d'une charge à forte teneur en composés azotés basiques.The present invention relates to a catalytic cracking process in a fluidized bed of a hydrocarbon feedstock, in particular a feedstock with a high content of basic nitrogen compounds.

On sait que, dans l'industrie pétrolière, le craquage catalytique des charges hydrocarbonées a progressivement remplacé, depuis plus de cinquante ans, le craquage thermique. Les lits fixes de catalyseur initialement utilisés ont été rapidement remplacés par des lits mobiles et, notamment, par des lits fluidisés, pour conduire aux procédés maintenant connus sous l'appellation de craquage catalytique en lit fluidisé (en anglais, Fluid Catalytic Cracking, ou encore procédé FCC).We know that, in the petroleum industry, catalytic cracking of hydrocarbon feedstocks has gradually replaced thermal cracking for more than fifty years. The fixed catalyst beds initially used were quickly replaced by mobile beds and, in particular, by fluidized beds, to lead to the processes now known under the name of catalytic cracking in a fluidized bed (in English, Fluid Catalytic Cracking, or FCC process).

Dans ces procédés, le craquage de la charge est réalisé à une température de l'ordre de 500°C, à une pression voisine de la pression atmosphérique, en l'absence d'hydrogène. Au cours du craquage, le catalyseur se recouvre de coke et d'hydrocarbures lourds, et l'on procède à sa régénération en continu, à l'extérieur du réacteur de craquage. La chaleur résultant de la combustion du coke et des traces d'hydrocarbures restantes en présence d'air ou d'oxygène sert à amener à la température désirée les particules de catalyseur, qui sont recyclées au réacteur.In these methods, the cracking of the charge is carried out at a temperature of the order of 500 ° C., at a pressure close to atmospheric pressure, in the absence of hydrogen. During the cracking, the catalyst becomes covered with coke and heavy hydrocarbons, and its regeneration is carried out continuously, outside the cracking reactor. The heat resulting from the combustion of coke and of the traces of hydrocarbons remaining in the presence of air or oxygen serves to bring the catalyst particles to the desired temperature, which are recycled to the reactor.

Les catalyseurs peuvent être de types variés et l'on pourra se référer sur ce point, par exemple, à EP-A-0 206 871.The catalysts can be of various types and reference may be made on this point, for example, to EP-A-0 206 871.

Ces procédés FCC conduisent à des essences pour automobiles de qualité bien supérieure à celles obtenues par craquage thermique, et avec des rendements beaucoup plus élevés.These FCC processes lead to gasoline for automobiles of much higher quality than that obtained by thermal cracking, and with much higher yields.

Ces procédés sont habituellement mis en oeuvre avec un flux ascendant de particules de catalyseur, mais il en résulte un certain nombre d'inconvénients, dûs au fait que les gaz présents ont tendance à s'élever, alors que les particules de catalyseur, du fait de leur masse, résistent au mouvement ascendant. Il en résulte que le rapport C/0 du débit C de catalyseur au débit O de charge à traiter est généralement compris entre 3 et 7, dans les réacteurs actuels, et habituellement voisin de 5.These processes are usually carried out with an upward flow of catalyst particles, but this results in a number of drawbacks, due to the fact that the gases present tend to rise, while the Catalyst particles, due to their mass, resist upward movement. As a result, the ratio C / 0 of the flow rate C of catalyst to the flow rate O of feedstock to be treated is generally between 3 and 7, in current reactors, and usually close to 5.

Plus précisément, dans un réacteur à flux ascendant, les particules de catalyseur ont tendance à redescendre et ce sont la charge à craquer, vaporisée, et le gaz d'entraînement (en anglais, "lift gas") qui soutiennent et entraînent le lit de catalyseur. Il n'est donc pas possible d'accroître librement le débit C du catalyseur, sans risquer de freiner abusivement la montée des particules de catalyseur. Bien évidemment, un tel problème ne se pose pas avec un réacteur à flux descendant.More specifically, in an upward flow reactor, the catalyst particles tend to descend and it is the cracked charge, vaporized, and the drive gas (in English, "lift gas") which support and drive the bed of catalyst. It is therefore not possible to freely increase the flow rate C of the catalyst, without risking unduly braking the rise of the catalyst particles. Obviously, such a problem does not arise with a downflow reactor.

Ces limitations des réacteurs à flux ascendant (dits encore élévateurs ou, en anglais, "risers") de la technique antérieure, sont particulièrement manifestes dans le cas du craquage de charges à forte teneur en azote basique. Parmi les composés azotés basiques présents dans la charge, on mentionnera notamment la pyridine, la quinoléine, l'acridine, la phénanthridine, l'hydroxyquinoléine, l'hydroxypyridine et leurs dérivés alkylés. Avec de telles charges, la chute du taux de conversion peut atteindre jusqu'à 15 points par rapport à une charge normale. Il est connu, en effet, que l'azote basique se fixe sur les sites actifs du catalyseur, qui sont des sites acides, et altère ainsi les propriétés catalytiques du catalyseur.These limitations of upstream reactors (also known as risers or, in English, "risers") of the prior art, are particularly evident in the case of cracking feedstocks with a high content of basic nitrogen. Among the basic nitrogen compounds present in the feed, mention will in particular be made of pyridine, quinoline, acridine, phenanthridine, hydroxyquinoline, hydroxypyridine and their alkylated derivatives. With such charges, the drop in conversion rate can reach up to 15 points compared to a normal charge. It is known, in fact, that basic nitrogen fixes itself on the active sites of the catalyst, which are acid sites, and thus alters the catalytic properties of the catalyst.

De plus, dans les réacteurs à flux ascendant se produit une accumulation de particules au voisinage des parois du réacteur, avec pour conséquence un surcraquage des hydrocarbures à ce niveau, se traduisant par la formation de coke et d'hydrogène, au lieu des produits à haut indice d'octane recherchés, tandis qu'au centre du réacteur, où moins de particules sont présentes, on obtient une conversion insuffisante de la charge.In addition, in upflow reactors, an accumulation of particles occurs in the vicinity of the reactor walls, with the result that the hydrocarbons are overcracked at this level, resulting in the formation of coke and hydrogen, instead of the products to be high octane number sought, while in the center of the reactor, where fewer particles are present, an insufficient conversion of the charge is obtained.

Par ailleurs, si, globalement, les grains de catalyseur s'élèvent dans le réacteur, certains d'entre eux peuvent localement redescendre. Ce phénomène, connu sous l'appellation anglaise de "back-mixing" (rétro-mélange), se traduit lui aussi par une chute locale de la conversion, puisque les grains qui redescendent sont partiellement désactivés et ont moins d'effet sur la charge que les grains qui s'élèvent. Ce phénomène est d'autant plus gênant que le rapport C/0 précédemment mentionné est plus faible.Furthermore, if, overall, the grains of catalyst rise in the reactor, some of they can go down locally. This phenomenon, known under the English name of "back-mixing", also results in a local drop in conversion, since the grains which descend are partially deactivated and have less effect on the load. than the grains that rise. This phenomenon is all the more troublesome the lower the C / 0 ratio mentioned above.

Pour remédier à ces inconvénients, qui rendent très difficile et peu économique le craquage catalytique des charges à forte teneur en azote basique, il a été proposé de procéder à un hydrotraitement des charges, qui a pour effet de réduire leur teneur en azote basique, mais qui nécessite des pressions et des températures élevées, et qui est par conséquent coûteux.To overcome these drawbacks, which make catalytic cracking of feedstocks with a high basic nitrogen content very costly, it has been proposed to hydrotreat the fillers, which has the effect of reducing their basic nitrogen content, but which requires high pressures and temperatures, and which is therefore expensive.

Il a également été proposé d'utiliser des absorbants solides ou des solvants non miscibles avec la charge, pour en éliminer les composés basiques, mais un tel processus est long et coûteux.It has also been proposed to use solid absorbents or solvents immiscible with the filler, to remove the basic compounds therefrom, but such a process is long and costly.

Il en est de même des traitements de la charge avec des additifs acides pour neutraliser les composés à azote basique, et l'on a donc recours, de préférence, à des catalyseurs de craquage, utilisables dans les procédés FCC, qui sont résistants à l'azote basique (voir Nitrogen Resistance of FCC Catalysts, de J.Scherzer et D.P. McArthur, communication présentée au "Katalistiks 7th Annual Cat Cracking Symposium", Venise, Italie, 12-13 Mai 1986).The same is true of the treatments of the feed with acid additives to neutralize the basic nitrogen compounds, and therefore recourse is preferably had to cracking catalysts, usable in FCC processes, which are resistant to 'basic nitrogen (see Nitrogen Resistance of FCC Catalysts, by J. Scherzer and DP McArthur, paper presented at "Katalistiks 7th Annual Cat Cracking Symposium", Venice, Italy, 12-13 May 1986).

C'est à ce type de procédé FCC à flux descendant, utilisant un catalyseur de craquage résistant aux composés azotés basiques, que s'intéresse la présente invention et elle vise à permettre le craquage dans de bonnes conditions de charges hydrocarbonées contenant plus de 350 p.p.m. en poids d'azote basique, la teneur en azote basique pouvant atteindre 1300 p.p.m. en poids, voire davantage.It is this type of FCC downflow process, using a cracking catalyst resistant to basic nitrogen compounds, that the present invention is interested in and it aims to allow cracking under good conditions of hydrocarbon feeds containing more than 350 ppm. by weight of basic nitrogen, the basic nitrogen content possibly reaching 1300 ppm by weight, or even more.

L'invention a également pour but de supprimer ou de limiter, dans un tel procédé, les effets de paroi du réacteur et les rétro-mouvements des particules de catalyseur.The object of the invention is also to eliminate or limit, in such a process, the wall effects of the reactor and the retro-movements of the catalyst particles.

La Demanderesse a établi qu'un tel résultat avantageux peut être obtenu en utilisant conjointement :

  • un réacteur, dans lequel la charge à traiter et le lit fluidisé du catalyseur se déplacent, de façon connue en soi, à co-courant et de haut en bas dans le réacteur ;
  • des particules d'un catalyseur qui, à l'état d'équilibre, adsorbe à 150°C, sous une pression de 5mbars, une quantité de pyridine inférieure à 250 micromoles/g et, de préférence, inférieure à 50 micromoles/g, et dont la rétention de pyridine, après chauffage à 350°C sous vide, n'excède pas 20%.
The Applicant has established that such an advantageous result can be obtained by using jointly:
  • a reactor, in which the charge to be treated and the fluidized bed of the catalyst move, in a manner known per se, cocurrently and up and down in the reactor;
  • particles of a catalyst which, at steady state, adsorbs at 150 ° C, under a pressure of 5 mbar, an amount of pyridine less than 250 micromoles / g and, preferably, less than 50 micromoles / g, and whose retention of pyridine, after heating to 350 ° C. under vacuum, does not exceed 20%.

L'invention a, par conséquent, pour objet un procédé de craquage catalytique en lit fluidisé d'une charge d'hydrocarbures, notamment d'une charge à forte teneur en composes azotés basiques, dans une zone réactionnelle tubulaire, ce procédé comprenant :

  • une étape d'alimentation en particules de catalyseur, au moins en partie régénéré, de la partie supérieure de la zone réactionnelle ;
  • une étape d'introduction et de pulvérisation de la charge à traiter dans la partie supérieure de la zone réactionnelle, au-dessous de la zone d'alimentation en catalyseur ;
  • une étape de circulation en contact mutuel, dans la zone réactionnelle, du catalyseur et de la charge à traiter, dans des conditions propres à permettre le craquage de la charge ;
  • une étape de séparation, à la partie inférieure de la zone réactionnelle, du catalyseur désactivé et des produits de la réaction de craquage ;
  • une étape de strippage du catalyseur désactivé ;
  • une étape de régénération d'une partie au moins du catalyseur désactivé strippé, dans une zone de régénération ;
  • une étape de recyclage du catalyseur régénéré à la partie supérieure de la zone réactionnelle ;
  • et une étape de transfert des produits de craquage de la charge hydrocarbonée vers une zone de séparation de ces produits ;
   ce procédé étant caractérisé en ce que la charge et le catalyseur circulent de haut en bas et à co-courant dans la zone tubulaire et en ce que l'on utilise un catalyseur, qui, à l'état d'équilibre , à 150 °C, sous une pression de 5 mbars, adsorbe une quantité de pyridine inférieure à 250 micromoles/g et, de préférence, inférieure à 50 micromoles/g, et dont la rétention de pyridine, après chauffage à 350°C sous vide, n'excède pas 20 % et, de préférence, 10 %, de la quantité adsorbée à 150°C.The invention therefore relates to a process for catalytic cracking in a fluidized bed of a hydrocarbon feedstock, in particular a feedstock with a high content of basic nitrogen compounds, in a tubular reaction zone, this process comprising:
  • a step of feeding catalyst particles, at least partly regenerated, to the upper part of the reaction zone;
  • a step of introducing and spraying the feed to be treated into the upper part of the reaction zone, below the catalyst supply zone;
  • a step of circulation in mutual contact, in the reaction zone, of the catalyst and of the feed to be treated, under conditions suitable for allowing cracking of the feed;
  • a step of separation, at the bottom of the reaction zone, of the deactivated catalyst and the products of the cracking reaction;
  • a step of stripping the deactivated catalyst;
  • a step of regenerating at least part of the stripped deactivated catalyst, in a regeneration zone;
  • a step of recycling the regenerated catalyst at the top of the reaction zone;
  • and a step of transferring the cracked products from the hydrocarbon charge to a zone for separating these products;
this process being characterized in that the charge and the catalyst circulate from top to bottom and co-current in the tubular zone and in that a catalyst is used, which, at steady state, at 150 ° C, under a pressure of 5 mbar, adsorbs a quantity of pyridine less than 250 micromoles / g and, preferably, less than 50 micromoles / g, and whose retention of pyridine, after heating to 350 ° C. under vacuum, n ' not exceed 20% and preferably 10% of the amount adsorbed at 150 ° C.

Comme on le verra ci-après, le procédé conforme à l'invention présente l'avantage de se prêter au craquage dans de bonnes conditions de charges azotées, d'une part, parce que la faible acidité du catalyseur, qui réduit son activité, est compensée par l'augmentation de la température de réaction, rendue possible par l'utilisation d'un réacteur à flux descendant et par l'abaissement du temps de réaction qui en résulte, et, d'autre part, parce que l'augmentation de la température de réaction permet de déplacer vers la désorption l'équilibre adsorption-désorption des molécules basiques sur les sites acides du catalyseur.As will be seen below, the process according to the invention has the advantage of being suitable for cracking under good conditions of nitrogenous charges, on the one hand, because the low acidity of the catalyst, which reduces its activity, is compensated for by the increase in the reaction temperature, made possible by the use of a downflow reactor and by the resulting reduction in reaction time, and, on the other hand, because the increase of the reaction temperature makes it possible to shift towards adsorption the adsorption-desorption balance of the basic molecules on the acid sites of the catalyst.

En effet, dans un réacteur à flux descendant (dit encore "downer" ou "dropper"), la vitesse de déplacement des particules de catalyseur s'accroît de haut en bas dans le réacteur, à mesure que la réaction de craquage progresse, et, à la sortie de la zone réactionnelle, elle est pratiquement égale à celle des gaz et de l'ordre de 25 m/s, et donc beaucoup plus importante que selon un mode à flux ascendant.In fact, in a downflow reactor (also called "downer" or "dropper"), the speed of displacement of the catalyst particles increases from top to bottom in the reactor, as the cracking reaction progresses, and , at the outlet of the reaction zone, it is practically equal to that of the gases and of the order of 25 m / s, and therefore much greater than in an upward flow mode.

Le débit de catalyseur utilisé pourra avantageusement être accru, ce qui augmentera le nombre des sites actifs. Le rapport de la masse de catalyseur présente dans le réacteur à la masse d'hydrocarbures pourra, en particulier, être avantageusement supérieur à 5 et, de préférence, compris entre 7 et 15.The flow rate of catalyst used can advantageously be increased, which will increase the number of active sites. The ratio of the mass of catalyst present in the reactor to the mass of hydrocarbons may, in particular, advantageously be greater than 5 and, preferably between 7 and 15.

Le catalyseur neuf utilisé pourra, par exemple, comprendre une quantité limitée d'alumine(s), ne dépassant pas 30 % en poids, au moins une zéolithe, en une quantité représentant de 15 à 40 % en poids, le complément à 100 % pouvant être constitué de kaolin, d'une argile basique ou faiblement acide, telle que la sépiolite et la vermiculite, d'un liant à base de silice et éventuellement d'un piège à métaux tel que par exemple un oxyde métallique.The new catalyst used may, for example, comprise a limited amount of alumina (s), not exceeding 30% by weight, at least one zeolite, in an amount representing from 15 to 40% by weight, the complement to 100% may consist of kaolin, a basic or weakly acid clay, such as sepiolite and vermiculite, a silica-based binder and optionally a metal trap such as for example a metal oxide.

Une forme de mise en oeuvre de l'invention va être décrite ci-après, en référence à la figure unique du dessin annexé, qui est un schéma de l'appareillage utilisé.An embodiment of the invention will be described below, with reference to the single figure of the accompanying drawing, which is a diagram of the apparatus used.

Le dispositif représenté comprend un réacteur tubulaire 1 à flux descendant, ou "downer", alimenté à sa partie supérieure, à partir d'une enceinte 2, qui lui est concentrique, en particules de catalyseur régénéré. Une vanne 3, destinée à réguler le rapport de la masse de catalyseur à la masse de charge à traiter dans le réacteur, est interposée entre le réacteur 1 et l'enceinte 2. Au-dessus de cette vanne débouche une ligne 4, équipée d'une vanne 5, d'alimentation du réacteur 1 en la charge d'hydrocarbures à traiter, préchauffée de façon connue en soi. Cette charge est pulvérisée en fines gouttelettes par des injecteurs dans la partie supérieure du réacteur 1, en direction du fond de celui-ci, pour venir se mélanger aux particules de catalyseur, au contact desquelles se produit la réaction de craquage. Comme on le verra ci-après, ces particules ont été portées à une température appropriée au craquage par l'opération de régénération du catalyseur usé. Les particules de catalyseur et la charge à traiter s'écoulent donc de haut en bas, à co-courant, dans le réacteur 1.The device shown comprises a tubular reactor 1 with downward flow, or "downer", supplied at its upper part, from an enclosure 2, which is concentric with it, in particles of regenerated catalyst. A valve 3, intended to regulate the ratio of the mass of catalyst to the mass of feedstock to be treated in the reactor, is interposed between the reactor 1 and the enclosure 2. Above this valve opens a line 4, equipped with 'A valve 5, supplying the reactor 1 with the hydrocarbon charge to be treated, preheated in a manner known per se. This charge is sprayed into fine droplets by injectors in the upper part of the reactor 1, towards the bottom of the latter, to mix with the catalyst particles, in contact with which the cracking reaction occurs. As will be seen below, these particles were brought to a temperature suitable for cracking by the regeneration operation of the spent catalyst. The catalyst particles and the charge to be treated therefore flow from top to bottom, co-current, in reactor 1.

A la base de celui-ci, les particules de catalyseur usé se déversent dans une enceinte de strippage 6, munie à sa base d'un diffuseur 7, alimenté en vapeur d'eau par une ligne 8.At the base of the latter, the spent catalyst particles are discharged into a stripping chamber 6, provided at its base with a diffuser 7, supplied with steam by a line 8.

Egalement à la base du réacteur 1, au-dessus de l'enceinte 6, débouche une ligne 9, par laquelle les produits du craquage et les hydrocarbures provenant du strippage sont évacués vers une colonne de séparation 10. Avant de parvenir à cette colonne 10, les gaz évacués par la ligne 9 peuvent éventuellement être trempés par un hydrocarbure ou de la vapeur d'eau, introduit par la ligne 11 dans la ligne 9.Also at the base of the reactor 1, above the enclosure 6, there is a line 9, through which the cracked products and the hydrocarbons coming from the stripping are evacuated to a separation column 10. Before reaching this column 10 , the gases evacuated by line 9 can optionally be quenched by a hydrocarbon or steam, introduced by line 11 into line 9.

Les particules de catalyseur strippé sont évacuées par gravité de l'enceinte 6, par un conduit incliné 22, vers une colonne ascendante 12, dans laquelle ils sont acheminés vers le haut, vers un régénérateur 13, à l'aide d'un gaz vecteur, diffusé en 14 à la base de la colonne 12, à partir de la ligne 15.The stripped catalyst particles are evacuated by gravity from the enclosure 6, through an inclined conduit 22, to an ascending column 12, in which they are conveyed upwards, to a regenerator 13, using a carrier gas. , disseminated at 14 at the base of column 12, starting from line 15.

La colonne 12 débouche dans le régénérateur 13 au-dessous d'un séparateur balistique 16, qui assure la séparation des particules de catalyseur et du gaz vecteur. Les particules de catalyseur sont alors régénérées, de façon connue en soi, dans le régénérateur, par combustion du coke qui s'est déposé à leur surface et des hydrocarbures restants, à l'aide d'un courant d'air ou d'oxygène amené par la ligne 17 au diffuseur 18.The column 12 opens into the regenerator 13 below a ballistic separator 16, which ensures the separation of the catalyst particles and the carrier gas. The catalyst particles are then regenerated, in a manner known per se, in the regenerator, by combustion of the coke which has deposited on their surface and of the remaining hydrocarbons, using a stream of air or oxygen. brought by line 17 to diffuser 18.

Les particules de catalyseur régénéré sont évacuées par gravité par le conduit 19 en direction de l'enceinte 2, sans pertes thermiques.The regenerated catalyst particles are removed by gravity through the pipe 19 in the direction of the enclosure 2, without thermal losses.

A la partie supérieure du régénérateur 13, les gaz provenant de la combustion sont évacués vers des cyclones 23, qui séparent les fines , recyclées par le conduit 20 vers le régénérateur, et les gaz, évacués par la ligne 21.At the upper part of the regenerator 13, the gases coming from the combustion are evacuated towards cyclones 23, which separate the fines, recycled by the conduit 20 towards the regenerator, and the gases, evacuated by the line 21.

De nombreuses variantes d'un tel dispositif peuvent naturellement être conçues par l'homme de l'art pour la mise en oeuvre du procédé de l'invention.Many variants of such a device can naturally be designed by a person skilled in the art for implementing the method of the invention.

Les exemples qui suivent, qui n'ont pas de caractère limitatif, illustrent cette mise en oeuvre.The examples which follow, which are not limiting, illustrate this implementation.

Exemple 1Example 1

Trois essais de craquage catalytique ont été réalisés à partir de deux charges d'hydrocarbures décrites ci-après. Nature de la charge traitée A (faiblement azotée) B (très azotée) - densité (°API) 17,7 18,5 - soufre (% en poids) 2,42 0,9 - hydrogène(% en poids) 11,6 11,95 - carbone Conradson (% en poids) 1,92 1,08 - azote basique(ppm) 350 1015 - PT 50% TBP (°C) 470 475 - vanadium (ppm) 1,5 1,0 - nickel (ppm) 1,1 1,9 Three catalytic cracking tests were carried out using two hydrocarbon charges described below. Type of load processed A (low nitrogen) B (very nitrogenous) - density (° API) 17.7 18.5 - sulfur (% by weight) 2.42 0.9 - hydrogen (% by weight) 11.6 11.95 - Conradson carbon (% by weight) 1.92 1.08 - basic nitrogen (ppm) 350 1015 - PT 50% TBP (° C) 470 475 - vanadium (ppm) 1.5 1.0 - nickel (ppm) 1.1 1.9

Au cours de ces trois essais, la charge A a été craquée selon le procédé de craquage traditionnel en mode ascendant (Essai 1). La charge B a été traitée à la fois selon le procédé de craquage traditionnel (Essai 2) et selon le procédé selon l'invention (Essai 3). Le catalyseur de craquage dans les essais 1 et 2 est le même et classique. C'est un catalyseur acide tel que l'on peut s'en procurer chez les fabricants GRACE DANISON, AKZO, ENGELHARD, choisi dans la famille des produits désignés par les appellations commerciales SPECTRA, RESOC, OCTACAT, RESIDCAT, ORION, XP (GRACE), ADVANCE, OCTAVISION, VISION (AKZO) PRECISION, DIMENSION (ENGELHARD), qui ont en commun d'avoir une capacité d'adsorption de pyridine à l'état d'équilibre supérieure à 250 micromoles/g à 150°C, sous une pression de 5 mbars. Dans l'essai 3, le catalyseur utilisé est celui décrit selon l'invention.
Les conditions opératoires ont été les suivantes : Essai 1 2 3 Température d'injection du catalyseur (°C) 750 748 733 Température d'injection de la charge (°C) 233 250 250 Température de sortie du réacteur (°C) 520 530 540 Rapport C/O 4,9 5,4 7,8 During these three tests, the load A was cracked according to the traditional cracking method in ascending mode (Test 1). Load B was treated both according to the traditional cracking method (Test 2) and according to the method according to the invention (Test 3). The cracking catalyst in tests 1 and 2 is the same and conventional. It is an acid catalyst such as can be obtained from the manufacturers GRACE DANISON, AKZO, ENGELHARD, chosen from the family of products designated by the trade names SPECTRA, RESOC, OCTACAT, RESIDCAT, ORION, XP (GRACE ), ADVANCE, OCTAVISION, VISION (AKZO) PRECISION, DIMENSION (ENGELHARD), which have in common an equilibrium pyridine adsorption capacity greater than 250 micromoles / g at 150 ° C, under a pressure of 5 mbar. In test 3, the catalyst used is that described according to the invention.
The operating conditions were as follows: Test 1 2 3 Catalyst injection temperature (° C) 750 748 733 Charge injection temperature (° C) 233 250 250 Reactor outlet temperature (° C) 520 530 540 C / O report 4.9 5.4 7.8

Les résultats rassemblés ci-après montrent l'effet nocif de l' azote basique sur la conversion (Essai 2 comparé à Essai 1) et que le dispositif selon l'invention permet, à partir d'une charge fortement azotée (contenant 1015 ppm poids d'azote basique), d'obtenir une meilleure conversion de la charge en gaz de pétrole liquéfié, c'est-à-dire la coupe (C3 + C4) plus essence plus diluant léger, ainsi qu'une appréciable réduction du dépôt de coke sur le catalyseur ("delta coke"), avec par conséquent, une meilleure stabilité du catalyseur et une diminution en appoint de catalyseur frais (Essai 3 comparé à 2). Essai 1 2 3 Gaz secs (% en poids) 4,1 4,0 4,0 Coupe C3 + C4 (% en poids) 13,4 10,0 12,1 Essence (% en poids) 41,4 38,1 41,2 Diluant léger (% en poids) 18,9 19,1 18,7 Diluant lourd (% en poids) 17,3 23,7 17,4 Coke (% en poids) 4,9 5,1 6,6 Conversion 220°C (% en poids) 63,8 57,2 63,9 Conversion 350°C (% en poids) (C3+C4+Essence+diluant léger) 73,7 67,2 72,0 Delta coke (% en poids) 1,00 0,94 0,84 The results collected below show the harmful effect of basic nitrogen on the conversion (Test 2 compared to Test 1) and that the device according to the invention makes it possible, from a highly nitrogenous feed (containing 1015 ppm by weight basic nitrogen), to obtain a better conversion of the charge into liquefied petroleum gas, that is to say the cut (C3 + C4) plus more light thinner gasoline, as well as an appreciable reduction in the deposit of coke on the catalyst ("delta coke"), with consequently, a better stability of the catalyst and a decrease in addition of fresh catalyst (Test 3 compared to 2). Test 1 2 3 Dry gases (% by weight) 4.1 4.0 4.0 Section C3 + C4 (% by weight) 13.4 10.0 12.1 Essence (% by weight) 41.4 38.1 41.2 Light thinner (% by weight) 18.9 19.1 18.7 Heavy thinner (% by weight) 17.3 23.7 17.4 Coke (% by weight) 4.9 5.1 6.6 220 ° C conversion (% by weight) 63.8 57.2 63.9 Conversion 350 ° C (% by weight) (C3 + C4 + Petrol + light thinner) 73.7 67.2 72.0 Delta coke (% by weight) 1.00 0.94 0.84

Exemple 2Example 2

Trois essais de craquage catalytique ont été réalisés sur la charge azotée B décrite précédemment et selon le procédé "Downer" tel que décrit sur la figure en annexe. Au cours de ces essais, les caractéristiques du catalyseur selon l'invention ont été les suivantes : Essai 1 2 3 Catalyseur A B C Quantité de pyridine adsorbée à 150°C (mole/g) 550 200 45 Rétention de pyridine après chauffage à 350°C sous vide (%) 40 20 10 Les conditions opératoires ont été les suivantes : Température d'injection du catalyseur (°C) 737 733 720 Température d'injection de la charge (°C) 250 250 250 Température sortie réacteur (°C) 530 540 550 Rapport C/O 6,2 7,8 11,5 Three catalytic cracking tests were carried out on the nitrogenous feed B described above and according to the "Downer" process as described in the attached figure. During these tests, the characteristics of the catalyst according to the invention were as follows: Test 1 2 3 Catalyst AT B VS Amount of pyridine adsorbed at 150 ° C (mole / g) 550 200 45 Retention of pyridine after heating at 350 ° C under vacuum (%) 40 20 10 The operating conditions were as follows: Catalyst injection temperature (° C) 737 733 720 Charge injection temperature (° C) 250 250 250 Reactor outlet temperature (° C) 530 540 550 C / O report 6.2 7.8 11.5

Les résultats rassemblés ci-après montrent tout l'intérêt de diminuer l'acidité du catalyseur de craquage pour maximiser la conversion de la charge azotée en opérant conformément à l'invention. Essai 4 5 6 Gaz secs (% en poids) 3,8 4,0 4,2 Coupe C3 + C4 (% en poids) 10,8 12,1 14,3 Essence (% en poids) 39,1 41,2 43,8 Diluant léger (% en poids) 20,7 18,7 17,4 Diluant lourd (% en poids) 20,0 17,4 11,8 Coke (% en poids) 5,6 6,6 8,5 Conversion 220°C (% en poids) 59,3 63,9 70,8 Conversion 350°C (C3+C4+essence+diluant léger) 70,6 72,0 75,5 Delta coke (% en poids) 0,90 0,84 0,74 The results collected below show the advantage of reducing the acidity of the cracking catalyst to maximize the conversion of the nitrogenous charge by operating in accordance with the invention. Test 4 5 6 Dry gases (% by weight) 3.8 4.0 4.2 Section C3 + C4 (% by weight) 10.8 12.1 14.3 Essence (% by weight) 39.1 41.2 43.8 Light thinner (% by weight) 20.7 18.7 17.4 Heavy thinner (% by weight) 20.0 17.4 11.8 Coke (% by weight) 5.6 6.6 8.5 220 ° C conversion (% by weight) 59.3 63.9 70.8 350 ° C conversion (C3 + C4 + petrol + light thinner) 70.6 72.0 75.5 Delta coke (% by weight) 0.90 0.84 0.74

Claims (5)

Procédé de craquage catalytique en lit fluidisé d'une charge d'hydrocarbures, notamment d'une charge à forte teneur en composés azotés basiques, dans une zone réactionnelle tubulaire, ce procédé comprenant une étape d'alimentation en particules de catalyseur, au moins en partie régénéré, de la partie supérieure de la zone réactionnelle,une étape d'introduction et de pulvérisation de la charge à traiter dans la partie supérieure de la zone réactionnelle, au-dessous de la zone d'alimentation en catalyseur, une étape de circulation à co-courant et en contact mutuel, dans la zone réactionnelle, du catalyseur et de la charge à traiter, dans des conditions propres à permettre le craquage de la charge, une étape de séparation, à la partie inférieure de la zone réactionnelle, du catalyseur désactivé et des produits de la réaction de craquage, une étape de strippage du catalyseur désactivé, une étape de régénération d'une partie au moins du catalyseur désactivé strippé, dans une zone de régénération, une étape de recyclage du catalyseur régénéré à la partie supérieure de la zone réactionnelle, et une étape de transfert des produits de craquage de la charge hydrocarbonée vers une zone de séparation de ces produits,
   ce procédé étant caractérisé en ce que la charge et le catalyseur circulent de haut en bas et à co-courant dans la zone tubulaire et en ce que l'on utilise un catalyseur qui, à l'état d'équilibre , à 150 °C, sous une pression de 5 mbars, adsorbe une quantité de pyridine inférieure à 250 micromoles/g et, de préférence, inférieure à 50 micromoles/g, et dont la rétention de pyridine, après chauffage à 350°C sous vide, n'excède pas 20 %, et de préférence 10 %, de la quantité adsorbée à 150°C.Process for catalytic cracking in a fluidized bed of a hydrocarbon feedstock, in particular a feedstock with a high content of basic nitrogenous compounds, in a tubular reaction zone, this process comprising a step of supplying catalyst particles, at least in regenerated part, from the upper part of the reaction zone, a step of introducing and spraying the charge to be treated into the upper part of the reaction zone, below the catalyst supply zone, a circulation step cocurrently and in mutual contact, in the reaction zone, of the catalyst and of the charge to be treated, under conditions suitable for cracking the charge, a step of separation, at the bottom of the reaction zone, of the deactivated catalyst and products of the cracking reaction, a step of stripping the deactivated catalyst, a step of regenerating at least part of the catalyst d disables stripped, in a regeneration zone, a catalyst recycle step regenerated the upper part of the reaction zone, and a step of transfer of the hydrocarbon feedstock cracking products to a separation zone of these products,
this process being characterized in that the charge and the catalyst circulate from top to bottom and co-current in the tubular zone and in that a catalyst is used which, in the equilibrium state, at 150 ° C. , under a pressure of 5 mbar, adsorbs a quantity of pyridine less than 250 micromoles / g and, preferably, less than 50 micromoles / g, and whose retention of pyridine, after heating at 350 ° C. under vacuum, does not exceed not 20%, and preferably 10%, of the amount adsorbed at 150 ° C. Procédé selon la revendication 1, caractérisé en ce que le rapport de la masse du catalyseur à la masse de la charge d'hydrocarbures est supérieur à 5 et, de préférence, compris entre 7 et 15.Process according to claim 1, characterized in that the ratio of the mass of the catalyst to the mass of the hydrocarbon charge is greater than 5 and preferably between 7 and 15. Procédé selon l'une des revendications 1 et 2, caractérisé en ce que, à la sortie de la zone réactionnelle, la vitesse de déplacement des particules de catalyseur est sensiblement égale à celle des gaz.Method according to one of claims 1 and 2, characterized in that, at the exit from the reaction zone, the speed of movement of the catalyst particles is substantially equal to that of the gases. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que, à la sortie de la zone réactionnelle, la vitesse de déplacement des particules de catalyseur est de l'ordre de 25 m/s.Method according to one of claims 1 to 3, characterized in that, at the exit from the reaction zone, the speed of movement of the catalyst particles is of the order of 25 m / s. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que le catalyseur comprend, en % en poids, au plus 30 % d'alumine, entre 15 et 40 % d'au moins une zéolithe, le complément à 100 % étant constitué au moins partiellement d'un diluant choisi dans le groupe constitué par le kaolin, les argiles basiques ou faiblement acides, telles que la sépiolite et la vermiculite, d'un liant à base de silice, et éventuellement d'un piège à métaux.Process according to one of Claims 1 to 4, characterized in that the catalyst comprises, in% by weight, at most 30% of alumina, between 15 and 40% of at least one zeolite, the complement to 100% being consisting at least partially of a diluent chosen from the group consisting of kaolin, basic or weakly acidic clays, such as sepiolite and vermiculite, a silica-based binder, and optionally a metal trap.
EP94403062A 1994-01-18 1994-12-30 Fluid catalytic cracking process for hydrocarbon feed, particularly a high basic nitrogen content feed Expired - Lifetime EP0663434B1 (en)

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FR9400472A FR2715163B1 (en) 1994-01-18 1994-01-18 Process for catalytic cracking in a fluidized bed of a hydrocarbon feed, in particular a feed with a high content of basic nitrogen compounds.

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FR2753453A1 (en) * 1996-09-18 1998-03-20 Total Raffinage Distribution PROCESS AND DEVICE FOR CATALYTIC CRACKING IN A FLUIDIZED BED OF A HYDROCARBON CHARGE, IMPLEMENTING AN IMPROVED CONTACT ZONE
FR2753454A1 (en) * 1996-09-18 1998-03-20 Inst Francais Du Petrole METHOD AND DEVICE FOR DOWNLINKING CATALYTIC CRACKING USING THE INJECTION OF A LOAD UNDER AN ADEQUATE ANGLE ON A CONDITIONED CATALYST
WO1998012280A1 (en) * 1996-09-18 1998-03-26 Institut Français Du Petrole Method and device for descending catalytic cracking by injecting feedstock at an adequate angle on a conditioned catalyst
WO1998012279A1 (en) * 1996-09-18 1998-03-26 Total Raffinage Distribution S.A. Method and device for fluid catalytic cracking of hydrocarbon feedstock
US5997726A (en) * 1996-09-18 1999-12-07 Total Raffinage Distribution S.A. Method for fluid catalytic cracking of hydrocarbon feedstock
EP3575384A1 (en) 2018-05-28 2019-12-04 Total Research & Technology Feluy Biphasic solvent catalytic process for the production of mono-oxygenated molecules from a bio-feedstock comprising carbohydrates and use of said mono-oxygenated molecules in a fluid catalytic cracking process

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GR3026682T3 (en) 1998-07-31
ATE165111T1 (en) 1998-05-15
FR2715163A1 (en) 1995-07-21
CN1111274A (en) 1995-11-08
DE69409623D1 (en) 1998-05-20
DE69409623T2 (en) 1998-08-27
US5660716A (en) 1997-08-26
ES2116557T3 (en) 1998-07-16
ZA95399B (en) 1995-09-26
CN1050625C (en) 2000-03-22
JPH0834980A (en) 1996-02-06
FR2715163B1 (en) 1996-04-05
CA2140418A1 (en) 1995-07-19
EP0663434B1 (en) 1998-04-15

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