FR2894975A1 - Hydrocarbon product obtained by a moving/fluidized bed catalytic cracking of a hydrocarbon charge using a catalytic composition comprising an amorphous catalytic component and a crystalline catalytic component - Google Patents

Hydrocarbon product obtained by a moving/fluidized bed catalytic cracking of a hydrocarbon charge using a catalytic composition comprising an amorphous catalytic component and a crystalline catalytic component Download PDF

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FR2894975A1
FR2894975A1 FR0610904A FR0610904A FR2894975A1 FR 2894975 A1 FR2894975 A1 FR 2894975A1 FR 0610904 A FR0610904 A FR 0610904A FR 0610904 A FR0610904 A FR 0610904A FR 2894975 A1 FR2894975 A1 FR 2894975A1
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Prior art keywords
catalytic
hydrocarbon product
product according
weight
catalytic component
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French (fr)
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Walter Vermeiren
Sebastien Decker
Marc Bories
Jean Pierre Dath
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Total Marketing Services SA
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Total France SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J35/19—
    • B01J35/60—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J35/647—
    • B01J35/651—

Abstract

Hydrocarbon product obtained by a moving or fluidized bed catalytic cracking (FCC) of a hydrocarbon charge having a boiling point >=350[deg]C, using a catalytic composition comprising an amorphous catalytic component (I) (50-99.5 wt.%) containing at least an amorphous mesoporous and/or macroporous metallic oxide such as silica, alumina or aluminosilicates and a crystalline catalytic component (II) (0.5-50 wt.%) containing a microporous crystalline aluminosilicate, where the composition is free from zeolite Y, as cracking catalyst in a cracking reaction zone.

Description

Produit hydrocarbons obtenu par un procede de craquage catalytique en litHydrocarbon product obtained by a process of catalytic cracking in bed

fluidise utilisant une composition catalytique particuliere La presente invention concerne un produit hydrocarbons obtenu par un procede de craquage catalytique en lit fluidise utilisant une composition catalytique particuliere, exempte de zeolithe Y. Les procedes de craquage catalytique en lit fluidise des coupes de distillation ayant une temperature d'ebullition superieure ou egale a 350 C sont bien connus de 1'homme du metier. Le catalyseur utilise est choisi de facon a convertir tout ou partie des coupes provenant des residus de distillation atmospherique en un maximum de produits commercialisables tels que notamment les GPL (en anglais LPG, pour liquefied petroleum gas ))) qui sont des hydrocarbures en C3 et C4, les essences ayant une temperature d'ebullition de 15 a 221 C et les gazoles de type LCO (pour light cycle oil ) dont la temperature d'ebullition est de 221 350 C. Un autre produit de cette conversion est le residu de craquage, ou slurry en anglais (appele slurry par extension de langage dans la suite, comme cela est courant pour 1'homme du metier), difficilement valorisable, dont la temperature d'ebullition est superieure ou egal.e a 350 C. Le choix du catalyseur va permettre d'influer sur la conversion, la repartition des produits (selectivite) ainsi que sur la qualite de ces derniers. Les catalyseurs connus utilises actuellement en craquage catalytique en lit fluidise (FCC) contiennent generalement une zeolithe de type Y plus ou moins echangees aux terres rares. Cette zeolithe ne pouvant pas etre utilisee telle quelle du fait de sa petite taille, elle est systematiquement diluee (a 1'aide d'un diluant) et agregee (a l'aide d'un liant), puis combinee a une matrice active ' constituee d'oxydes metalliques amorphes et/ ou cristallins, choisis parmi l'alumine, la silice et les aluminosilicates. On obtient ainsi un materiau catalytique presentant une bonne granulometrie, resistant a 1'attrition et suffisamment actif et selectif. I1 est egalement bien c:onnu de 1'homme du metier que l'incorporation, au catalyseur de FCC connu, de quelques pour cent en poids d'un deuxieme catalyseur contenant une zeolithe MFI (de type ZSM-5 par exemple) permet d'augmenter encore la production de GPL et  The present invention relates to a hydrocarbon product obtained by a fluidized catalytic cracking process using a specific catalytic composition, free from zeolite Y. The processes for catalytic cracking in a fluidized bed distillation cups having a temperature of 20 ° C. boiling above or equal to 350 C are well known to those skilled in the art. The catalyst used is chosen so as to convert all or part of the cuts from the atmospheric distillation residues into a maximum of marketable products such as LPG (in English LPG, for liquefied petroleum gas))) which are hydrocarbons C3 and C4, gasolines with a boiling temperature of 15 to 221 ° C and gasolines of the LCO (light cycle oil) type having a boiling point of 221,350 ° C. Another product of this conversion is the cracking residue. or slurry in English (called slurry by language extension in the following, as is common for those skilled in the art), difficult to exploit, whose boiling temperature is higher or equal to 350 C. The choice of catalyst will influence the conversion, the distribution of products (selectivity) as well as the quality of the latter. The known catalysts currently used in fluidized-bed catalytic cracking (FCC) generally contain a Y-type zeolite more or less exchanged with rare earths. Since this zeolite can not be used as such because of its small size, it is systematically diluted (with the aid of a diluent) and aggregated (with the aid of a binder) and then combined with an active matrix. composed of amorphous and / or crystalline metal oxides chosen from alumina, silica and aluminosilicates. This gives a catalytic material having a good particle size, resistant to attrition and sufficiently active and selective. It is also well known to one of ordinary skill in the art that the incorporation of a few percent by weight of a second catalyst containing an MFI zeolite (eg ZSM-5) into the known FCC catalyst allows for 'further increase the production of LPG and

l'indice d'octane des essences de craquage catalytique. En raison de la faible proportion de ce deuxieme catalyseur, qui ne depasse generalement pas 15 % en poids de la composition catalytique totale, it est communement admis de le nommer additif . La teneur en zeolithe ZSM-5 de cet additif est generalement comprise entre 10 et 40 % en poids, le reste etant constitus de maniere connue d'une matrice dite active ' composee soit d'alurnine amorphe ou cristallisee sous differentes formes cristallines soit d'aluminosilicate, d'un liant et d'un diluant.  the octane number of catalytic cracking gasolines. Because of the small proportion of this second catalyst, which generally does not exceed 15% by weight of the total catalytic composition, it is commonly accepted to name it additive. The ZSM-5 zeolite content of this additive is generally between 10 and 40% by weight, the remainder being known in the known manner of a so-called active matrix composed of either amorphous or crystalline alumina in different crystalline forms or of aluminosilicate, a binder and a thinner.

On peut citer a ce sujet le brevet US 6 566 293 au nom de Akzo Nobel NV, qui divulgue l'utilisation d'une zeolithe de type MFI activee grace a un compose phosphors dans une composition catalytique a base de zeolithe Y, dans le but d'augmenter le rendement en olefines legeres d'un procede de craquage catalytique.  On this subject, mention can be made of U.S. Patent No. 6,566,293 to Akzo Nobel NV, which discloses the use of an MFI type zeolite activated by means of a phosphorus compound in a zeolite Y catalytic composition for the purpose. to increase the yield of light olefins of a catalytic cracking process.

On peut en outre citer le brevet US 5 846 402 au nom de Indian Oil, qui divulgue un procede de craquage catalytique a haut rendement en GPL et en olefines legeres utilisant une composition catalytique contenant, outre une zeolithe Y et un additif de craquage de fond, une zeolithe dont les pores presentent un diametre de tres petite taille (5 a 6 A, avec 1 A = 10-10 m). Le petit diametre des pores des zeolithes decrites dans ces documents implique que le diametre cinetique des composes concernes par la reaction de craquage doit are inferieur a ces valeurs pour pouvoir penetrer dans les pores de la zeolithe ou sont situes les sites actifs. De meme, le diametre cinetique des produits issus de la reaction de craquage doit etre inferieur au diametre des pores pour que les produits de craquage puissent quitter 1'interieur de la zeolithe a l'issue de la reaction. Dans les procedes de craquage catalytique des coupes lourdes, it se pose donc le probleme des molecules de grande taille, c'est-a-dire celles ayant une temperature d'ebullition superieure ou egale a 350 C, qui n'arrivent pas a penetrer dans les tres petits pores des zeolithes et sont ainsi exclues de la reaction de craquage. Pour amsliorer le craquage de ces molecules lourdes, it est connu d'augmenter la teneur en matrice active des catalyseurs FCC, de favoriser la presence d'un reseau mesoporeux dans cette matrice et/ou d'ajuster 1'acidite de celleci. En utilisant ainsi un materiau dont les pores presentent un diametre  In addition, US Pat. No. 5,846,402 to Indian Oil, which discloses a catalytic cracking process with a high yield of LPG and of light olefins, using a catalytic composition containing, in addition to a zeolite Y and a bottom cracking additive. , a zeolite whose pores have a diameter of very small size (5 to 6 A, with 1 A = 10-10 m). The small pore diameter of the zeolites described in these documents implies that the kinetic diameter of the compounds concerned by the cracking reaction must be below these values in order to be able to penetrate into the pores of the zeolite where the active sites are located. Likewise, the kinetic diameter of the products resulting from the cracking reaction must be smaller than the diameter of the pores so that the cracking products can leave the interior of the zeolite at the end of the reaction. In the processes of catalytic cracking of heavy cuts, there is therefore the problem of large molecules, that is to say those having a boiling point greater than or equal to 350 ° C., which can not penetrate in the very small pores of the zeolites and are thus excluded from the cracking reaction. To improve the cracking of these heavy molecules, it is known to increase the active matrix content of the FCC catalysts, to promote the presence of a mesoporous network in this matrix and / or to adjust the acidity thereof. By using a material whose pores have a diameter

de 20 a 500 A, plus large que le diametre des pores de la zeolithe MFI, on parvient a favoriser la diffusion des grosses molecules dans la matrice active ou elles subissent un premier craquage qui s'accompagne de la formation de fragments plus petits.  from 20 to 500 A, wider than the pore diameter of the MFI zeolite, it is possible to promote the diffusion of the large molecules in the active matrix or they undergo a first cracking which is accompanied by the formation of smaller fragments.

Une fawn connue de favoriser cette diffusion consiste a ajouter aux compositions catalytiques FCC connues a base de zeolithe Y et de zeolithe MFI, un composant particulier appele additif de craquage de fond (abrege BCA, de 1'anglais Bottom Cracking Additive ). Ces additifs de structure amorphe (parfois partiellement cristalline) sont composes de diluant, de liant, d'oxydes metalliques tels que 1'alumine, la silice ou les aluminosilicates. Parfois, certains fournisseurs incorporent en outre dans ces additifs une zeolithe de type Y, echangee aux terres rares, ce qui leur confere une structure partiellement cristalline. La demande internationale WO 97/ 12011 deposee par la societe Intercat decrit ainsi un procede de fabrication d'un catalyseur de craquage de fond et un procede de craquage catalytique en lit fluidise dans lequel le craquage des molecules a haut poids moleculaire s'effectue grace a un catalyseur classique de FCC (contenant des zeolithes de type Y et de type MFI) auquel on a ajoute 1 a 15 % en poids d'un additif de craquage de fond de type aluminosilicate. Cet additif possede une surface specifique comprise entre 150 et 175 m2/g et presente une teneur en silice comprise entre 0,5 et 50 % en poids. Le procede decrit permet d'obtenir un bon rendement en essences et un rendement faible en fuels lourds et en coke. La concentration de 1'additif de craquage de fond dans l'inventaire des catalyseurs d'une unite FCC excede rarement 15 % en poids. Dans 1'etat de la technique, le role essentiel de la zeolithe Y pour orienter les procedes de craquage catalytique vers la production de GPL est donc largement connu, et les additifs de craquage de fond, servant principalement a ameliorer le craquage des molecules lourdes, ne sont utilises qu'en de faibles quantites, generalement inferieures A. 15 %. La demarche logique de 1'homme du metier souhaitant ameliorer la production de GPL consisterait donc a augmenter le plus possible la concentration de la zeolithe Y dans le support catalytique et A. utiliser simultanement un additif de craquage de fond. Le cout relativement eleve de la zeolithe Y s'oppose toutefois a une telle augmentation.  A known way to promote this diffusion is to add to the known FCC catalytic compositions based on zeolite Y and MFI zeolite, a particular component called bottom cracking additive (abbreviation BCA, English Bottom Cracking Additive). These amorphous (sometimes partially crystalline) additives are composed of diluent, binder, metal oxides such as alumina, silica or aluminosilicates. Sometimes, some suppliers also incorporate in these additives a zeolite Y type, exchanged with rare earths, which gives them a partially crystalline structure. The international application WO 97/12011 filed by the company Intercat thus describes a process for producing a bottom cracking catalyst and a process for fluidized catalytic cracking in which the cracking of high molecular weight molecules is carried out by means of a conventional FCC catalyst (containing Y type and MFI type zeolites) to which 1 to 15% by weight of an aluminosilicate bottom cracking additive was added. This additive has a specific surface of between 150 and 175 m 2 / g and has a silica content of between 0.5 and 50% by weight. The method described makes it possible to obtain a good yield in gasolines and a low yield in heavy fuels and in coke. The concentration of the bottom cracking additive in the catalyst inventory of an FCC unit rarely exceeds 15% by weight. In the state of the art, the essential role of zeolite Y in directing catalytic cracking processes to the production of LPG is therefore widely known, and the bottom cracking additives are mainly used to improve the cracking of heavy molecules. are only used in small quantities, generally below 15%. The logical approach of the person skilled in the art wishing to improve the production of LPG would therefore be to increase as much as possible the concentration of zeolite Y in the catalytic support and A. simultaneously use a bottom cracking additive. The relatively high cost of the Y zeolite, however, opposes such an increase.

La Demanderesse, dans le cadre de ses recherches visant a mettre au point de nouvelles compositions catalytiques utilisees dans des procedes de craquage catalytique connus en lit mouvant ou en lit fluidise circulant sur des coupes hydrocarbonees lourdes (i.e. distillant generalement a une temperature superieure ou egale a 350 C), a decouvert de facon tout a fait inattendue qu'il etait possible de maximiser la production de produits valorisables non pas en augmentant la concentration de zeolithe Y dans les compositions catalytiques FCC, mais au contraire, en se passant totalement de zeolithe Y en tant que catalyseur FCC et en augmentant considerablement la proportion de materiaux de type additif de craquage de fond. Ces derniers materiaux sont utilises dans les compositions catalytiques utilises selon la presente invention en tant que composant catalytique majoritaire et non plus comme simple additif ajoute en faible quantite (en general moins de 15 % en poids). La Demanderesse a constate que la combinaison de ces mesures permettait d'augmenter la production de gazoles de type LCO et de GPL, en particulier d'olefines legeres en C3 et C4, et d'ameliorer la qualite des gazoles tout en conservant les conditions operatoires utilisees classiquement en FCC, c'est-a-dire generalement une temperature reactionnelle de 495 a 580 C et un rapport debit catalyseur/debit huile (note ratio cat/oil ) de 3 a 10 exprime par rapport au debit total de charge (coupes a temperature d'sbullition superieure ou egale a 350 C et recycles).  The Applicant, in the context of his research to develop new catalytic compositions used in catalytic cracking processes known as moving bed or fluidized bed circulating on heavy hydrocarbon cuts (ie distilling generally at a temperature greater than or equal to 350 C), discovered quite unexpectedly that it was possible to maximize the production of valuable products not by increasing the concentration of zeolite Y in the FCC catalytic compositions, but on the contrary, completely bypassing Y zeolite. as an FCC catalyst and significantly increasing the proportion of bottom crack additive type materials. These latter materials are used in the catalyst compositions used according to the present invention as a major catalytic component and no longer as a simple additive added in a small amount (usually less than 15% by weight). The Applicant has found that the combination of these measures makes it possible to increase the production of gas oils of the LCO and LPG type, in particular of light olefins in C3 and C4, and to improve the quality of the gas oils while maintaining the operating conditions. conventionally used in FCC, that is to say generally a reaction temperature of 495 to 580 C and a ratio of catalyst / oil flow rate (note ratio cat / oil) of 3 to 10 expressed with respect to the total flow of charge (cuts at boiling temperature greater than or equal to 350 C and recycles).

La presente invention a par consequent pour objet un produit hydrocarbons obtenu par une procede de craquage en lit mouvant ou fluidise (FCC), d'au moins une charge hydrocarbonee ayant une temperature d'ebullition superieure ou egale a 350 C, utilisant, en tant que seul catalyseur de craquage dans une zone reactionnelle de craquage, la composition catalytique constituee : - de 50% a 99,5% en poids, rapportes A. la somme de (1) et (2), d'au moins un composant catalytique amorphe (1) contenant au moins un oxyde metallique amorphe mssoporeux et/ou macroporeux choisi parmi la silice, 1'alumine et les aluminosilicates, et - de 0,5% a 50% en poids, rapportes A. la somme de (1) et (2), d'au moins un composant catalytique cristallin (2) contenant au moins un aluminosilicate cristallin microporeux,  The subject of the present invention is therefore a hydrocarbon product obtained by a moving bed or fluidized bed (FCC) cracking process, of at least one hydrocarbon feed having a boiling point greater than or equal to 350 ° C., using, as a that only cracking catalyst in a cracking reaction zone, the catalytic composition constitutes: from 50% to 99.5% by weight, referred to A. the sum of (1) and (2), of at least one catalytic component amorphous material (1) containing at least one amorphous and / or macroporous amorphous metal oxide selected from silica, alumina and aluminosilicates, and - from 0.5% to 50% by weight, based on the sum of (1) and (2) at least one crystalline catalyst component (2) containing at least one microporous crystalline aluminosilicate,

et exempte de zeolithe Y. On considere dans la presente invention, la composition catalytique en tant que catalyseur frais c'est-a-dire telle qu'elle est obtenue a l'issue de sa preparation.  and free from zeolite Y. In the present invention, the catalyst composition is considered as a fresh catalyst, that is to say as it is obtained at the end of its preparation.

Les adjectifs mecoporeux ' et macroporeux utilises pour decrire le composant catalytique amorphe (1) designent des materiaux ayant un diametre moyen de pores compris respectivement de 20 a 500 A (2 a 50 nm) et superieur a 500 A (50 nm). L'adjectif microporeux decrivant le composant catalytique cristallin (2) designe un materiau ayant un diametre moyen de pores inferieur a 20 A, de preference inferieur a 7,5 A (0,75 nm). De maniere preferee, la composition catalytique utilisee selon la presente invention est constituee de 50% a 95% en poids, rapportes a la somme de (1) et (2), d'au moins un composant catalytique amorphe (1) contenant au moins un oxyde metallique amorphe mecoporeux et/ou macroporeux choisi parmi la silice, 1'alumine et les aluminosilicates, et de 5 % a 50 % en poids, rapportes a la somme de (1) et (2), d'au moins un composant catalytique cristallin (2) contenant au moins un aluminosilicate cristallin microporeux, et elle est exempte de zeolithe Y.  The mecoporous and macroporous adjectives used to describe the amorphous catalytic component (1) designate materials having an average pore diameter of 20 to 500 A (2 to 50 nm) and greater than 500 A (50 nm), respectively. The microporous adjective describing the crystalline catalyst component (2) denotes a material having an average pore diameter of less than 20 Å, preferably less than 7.5 Å (0.75 Å). Preferably, the catalytic composition used according to the present invention is comprised of 50% to 95% by weight, based on the sum of (1) and (2), of at least one amorphous catalyst component (1) containing at least a moporous and / or macroporous amorphous metal oxide selected from silica, alumina and aluminosilicates, and from 5% to 50% by weight, based on the sum of (1) and (2), of at least one component crystalline catalyst (2) containing at least one microporous crystalline aluminosilicate, and is free of zeolite Y.

Dans un premier mode de realisation, les composants catalytiques (1) et (2) sont presents dans la composition catalytique de la presente invention, en melange que l'on peut qualifier d'intime. La composition catalytique comporte alors, et de preference consiste en, au moins une matiere particulaire. Dans ce cas, chaque particule de ladite matiere particulaire, dite particule composite, comprend, du composant catalytique (1) et du composant catalytique (2), dans une proportion variable ou semblable d'une particule a une autre particule. Le plus souvent, dans ce cas, le composant catalytique cristallin (2) est incorpore dans une matrice formee par le composant catalytique amorphe (1) lors de la fabrication de ce dernier. Dans un second mode de realisation, les composants catalytiques (1) et (2) sont presents dans la composition catalytique, en melange que l'on peut qualifier de physique. La composition catalytique comprend alors au moins une matiere particulaire comprenant, de preference consistant en, deux types differents de particules. En effet, la matiere particulaire comporte des particules contenant, de preference  In a first embodiment, the catalyst components (1) and (2) are present in the catalytic composition of the present invention, in a mixture that can be described as intimate. The catalytic composition then comprises, and preferably consists of, at least one particulate material. In this case, each particle of said particulate matter, referred to as the composite particle, comprises catalytic component (1) and catalytic component (2) in a variable or similar proportion of one particle to another particle. Most often, in this case, the crystalline catalyst component (2) is incorporated in a matrix formed by the amorphous catalytic component (1) during the manufacture of the latter. In a second embodiment, the catalytic components (1) and (2) are present in the catalytic composition, in a mixture that can be described as physical. The catalytic composition then comprises at least one particulate material comprising, preferably consisting of two different types of particles. Indeed, the particulate matter comprises particles preferably containing

consistant en, le composant cristallin microporeux (2) et des particules contenant, de preference consistant en, le composant amorphe (1). Bien entendu, rien ne s'oppose a ce qu'une composition catalytique utilisee selon l'invention contienne les deux matieres particulaires des deux modes de realisation precedents, c'est-a-dire des trois particules a la fois, a savoir des particules composites contenant (1) et (2), des particules contenant (1) et des particules contenant (2). Les composants (1) et (2) formant la composition catalytique utilisee selon l'invention contiennent generalement, outre au moins un oxyde metallique amorphe mesoporeux et/ou macroporeux et au moins un aluminosilicate cristallin microporeux, au moins un diluant et/ou liant, connu de 1'homme du metier de la catalyse, n'ayant sensiblement aucune activite catalytique en FCC et utilises communement dans les compositions catalytiques de craquage. Un diluant et/ou liant est par exemple du kaolin ou de la pseudo-boehmite. La teneur du composant catalytique amorphe (1) en oxyde metallique amorphe mesoporeux et/ou macroporeux est par consequent generalement inferieure a 100 % et en particulier de 5 % a 75 % en poids, le complement etant forme par au moins un liant et/ou diluant n'ayant sensiblement aucune activite catalytique. Lorsque ledit metal est 1'aluminium, la teneur du composant catalytique amorphe (1) en oxyde d'aluminium est generalement de 10 % a 90 % en poids, et lorsque ledit metal est le silicium, la teneur du composant catalytique amorphe (1) en oxyde de silicium est generalement de 0 % (exclu) a 30 % en poids. De preference, 1'oxyde metallique amorphe du composant catalytique (1) contient de 10 % en poids a 90 % en poids d'oxyde d'aluminium, et contient de 0 % en poids a 30 % en poids d'oxyde de silicium. Dans un mode de realisation particulier de la composition utilisee selon l'invention, 1'oxyde amorphe mesoporeux/macroporeux contient en outre un ou plusieurs elements metalliques M, choisis de preference parmi le magnesium, le calcium, le zinc, le bore, le titane, le zirconium et le phosphore. L'oxyde metallique amorphe du composant catalytique (1) presente de preference une surface specifique (mesuree selon la methode BET - pour Brunauer Emmet et Teller -) de 50 a 700 m2/g et, en general, 75 % de ses pores ont un diametre superieur a 2 nm.  consisting of the microporous crystalline component (2) and particles containing, preferably consisting of, the amorphous component (1). Of course, there is nothing to prevent a catalytic composition used according to the invention from containing the two particulates of the two preceding embodiments, that is to say of the three particles at the same time, namely particles composites containing (1) and (2), particles containing (1) and particles containing (2). The components (1) and (2) forming the catalytic composition used according to the invention generally contain, in addition to at least one mesoporous and / or macroporous amorphous metal oxide and at least one microporous crystalline aluminosilicate, at least one diluent and / or binder, known to those skilled in the art of catalysis, having substantially no catalytic activity in FCC and commonly used in catalytic cracking compositions. A diluent and / or binder is, for example, kaolin or pseudo-boehmite. The content of the amorphous catalytic component (1) in amorphous metal oxide mesoporous and / or macroporous is therefore generally less than 100% and in particular from 5% to 75% by weight, the complement being formed by at least one binder and / or diluent having substantially no catalytic activity. When said metal is aluminum, the content of the amorphous catalytic component (1) in aluminum oxide is generally from 10% to 90% by weight, and when said metal is silicon, the content of the amorphous catalytic component (1) Silicon oxide is generally from 0% (excluded) to 30% by weight. Preferably, the amorphous metal oxide of the catalyst component (1) contains from 10% by weight to 90% by weight of aluminum oxide, and contains from 0% by weight to 30% by weight of silicon oxide. In a particular embodiment of the composition used according to the invention, the amorphous mesoporous / macroporous oxide additionally contains one or more metal elements M, preferably chosen from magnesium, calcium, zinc, boron and titanium. , zirconium and phosphorus. The amorphous metal oxide of the catalyst component (1) preferably has a specific surface area (measured according to the BET method for Brunauer Emmet and Teller) of 50 to 700 m 2 / g and, in general, 75% of its pores have a diameter greater than 2 nm.

On peut citer a titre d'exemples de materiaux utilisables en tant que composant catalytique amorphe (1) le produit BCA commercialise par la societe Intercat, le BCMT 100 de la societe Albermarl et le produit Converter commercialise par la societe Engelhard. Selon l'invention, le composant catalytique cristallin (2) contient generalement moins de 100 %, et de preference de 5 % a 75 % en poids d'au moins un aluminosilicate cristallin microporeux, le complement etant forme par au moins un liant et/ou diluant n'ayant sensiblement aucune activite catalytique. L'aluminosilicate cristallin microporeux est de preference une zeolithe presentant generalement au moins une ouverture a dix ponts a oxygene. Cela la distingue de la. zeolithe Y dont l'ouverture est a 12 ponts a oxygene. L'aluminosilicate cristallin microporeux est de preference une zeolithe presentant generalement un rapport Si/Al superieur a 10. Cela la distingue de la zeolithe Y dont le rapport Si/Al est compris entre 2,5 et 10. De facon plus preferee, 1'aluminosilicate cristallin microporeux est de preference une zeolithe presentant au moins une ouverture a dix ponts a oxygene et ayant un rapport Si/Al superieur a 10. Cela la distingue de la zeolithe Y dont l'ouverture est a 12 ponts a oxygene et dont le rapport Si/Al est compris entre 2,5 et 10. Dans un mode de realisation prefere, 1'aluminosilicate cristallin microporeux est de preference choisi dans le groupe forme par les ZSM-5, modifiee ou non au phosphore, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, TS-1, TS-2, SSZ-46, MCM-22, MCM-49, FU-9, PSH-3, ITQ-1, EU- 1, NU-10, la silicalite-1, la silicalite-2, la boralite C, la boralite D, la ferrierite, la chabasite et theta-1, et leurs melanges. Parmi celles-ci, la zeolithe ZSM-5, modifiee ou non au phosphore, est particulierement preferee, et une zeolithe ZSM-5 modifiee au phosphore est encore plus preferee. Les diametres des pores des composants formant la composition catalytique sont optimises afin de favoriser la diffusion et le craquage des grosses molecules hydrocarbonees. Ainsi les grosses molecules, qui sont les plus difficiles a craquer, subissent generalement dans un premier temps faction du composant catalytique mesoporeux et/ou macroporeux (1), et deviennent ainsi aptes a diffuser dans le reseau  Examples of materials that can be used as amorphous catalytic component (1) are the BCA product marketed by Intercat, the BCMT 100 from Albermarl and the Converter product marketed by Engelhard. According to the invention, the crystalline catalyst component (2) generally contains less than 100%, and preferably from 5% to 75% by weight of at least one microporous crystalline aluminosilicate, the complement being formed by at least one binder and / or or diluent having substantially no catalytic activity. The microporous crystalline aluminosilicate is preferably a zeolite generally having at least one ten-bridge oxygen opening. This distinguishes it from the. zeolite Y whose opening is at 12 oxygen bridges. The crystalline microporous aluminosilicate is preferably a zeolite generally having an Si / Al ratio greater than 10. This distinguishes it from zeolite Y whose Si / Al ratio is between 2.5 and 10. More preferably, The microporous crystalline aluminosilicate is preferably a zeolite having at least one aperture having ten oxygen bridges and having an Si / Al ratio greater than 10. This distinguishes it from the zeolite Y whose opening is at 12 oxygen bridges and whose ratio If / Al is between 2.5 and 10. In a preferred embodiment, the microporous crystalline aluminosilicate is preferably selected from the group formed by ZSM-5, modified or not with phosphorus, ZSM-11, ZSM- 22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, TS-1, TS-2, SSZ-46, MCM-22, MCM-49, FU-9, PSH-3, ITQ-1, EU-1, NU-10, silicalite-1, silicalite-2, boralite C, boralite D, ferrierite, chabasite and theta-1, and mixtures thereof. Of these, zeolite ZSM-5, modified or not with phosphorus, is particularly preferred, and a ZSM-5 zeolite modified with phosphorus is even more preferred. The pore diameters of the components forming the catalytic composition are optimized to promote the diffusion and cracking of large hydrocarbon molecules. Thus the large molecules, which are the most difficult to crack, generally undergo firstly faction of the catalyst component mesoporous and / or macroporous (1), and thus become able to diffuse into the network

cristallin du composant catalytique (2) contenant la zeolithe microporeuse pour y subir un craquage complementaire. Dans le cas ou les composants catalytiques (1) et (2) sont mis en presence separement sous forme de deux types differents de particules (melange physique), ils peuvent are injectes dans 1'unite de FCC soit ensemble, soit de maniere separee. Dans le premier cas, l'injection est generalement celle d'un pre-melange en proportions determinees des deux composants au moyen d'une tremie unique de chargement. Dans le second cas, it y a generalement injection distincte de chacun des deux types de particules au moyen de deux tremies de chargement differentes. Ce dernier cas presence 1avantage d'offrir une grande flexibilite dans le choix des rapports entre les deux composants a injecter et permet ainsi d'orienter les rendements des produits en fonction de 1'interet economique.  crystalline component of the catalyst component (2) containing the microporous zeolite for further cracking. In the case where the catalyst components (1) and (2) are separately present as two different types of particles (physical mixing), they may be injected into the FCC unit either together or separately. In the first case, the injection is generally that of premixing in fixed proportions of the two components by means of a single loading tremie. In the second case, there is usually a distinct injection of each of the two types of particles by means of two different loading hoppers. This latter case has the advantage of offering a great flexibility in the choice of the ratios between the two components to be injected and thus makes it possible to orient the returns of the products according to the economic interest.

Le procede utilise selon l'invention permet de produire davantage de GPL contenant en outre plus d'olefines en C3 et C4. Ainsi la teneur en propylene dans la fraction totale de C3 est generalement d'au moins 90 % en poids, et la teneur en butenes dans la fraction totale de C4 est generalement d'au moins 80 % en poids. D'autre part, generalement, la teneur en isobutenes dans la fraction butenes est generalement au moins egale a 35 % en poids, en particulier de 35 a 40 % en poids. La Demanderesse a par ailleurs generalement constate une augmentation de la production de LCO, cette fraction LCO presentant generalement en outre un indice de cetane ameliore, typiquement au moins egal a 23. La composition de la fraction aromatique du LCO est generalement atypique puisqu'on note une fraction de composes monoaromatiques generalement superieure a la fraction de composes polyaromatiques. Le rapport ponderal des composes monoaromatiques aux composes polyaromatiques (HAP) est donc generalement superieur a 1 et le plus souvent compris de 1 a 2,5. La valeur relativement elevee de ce rapport facilite la valorisation de la fraction LCO en tant que base pour gazole moteur. Par ailleurs, la repartition generalement atypique en composes mono et polyaromatiques associee a la densite plus faible (moins 5 0/0 environ) et a la teneur plus importante en hydrogene de la fraction LCO obtenue par le procede de l'invention permet un hydrotraitement moins  The process according to the invention makes it possible to produce more LPG containing in addition more C 3 and C 4 olefins. Thus, the propylene content in the total C 3 fraction is generally at least 90% by weight, and the butenes content in the total C 4 fraction is generally at least 80% by weight. On the other hand, generally, the isobut content in the butenes fraction is generally at least 35% by weight, in particular 35 to 40% by weight. The Applicant has also generally noted an increase in the production of LCO, this LCO fraction generally also having an improved cetane number, typically at least equal to 23. The composition of the aromatic fraction of LCO is generally atypical since we note a fraction of monoaromatic compounds generally greater than the fraction of polyaromatic compounds. The weight ratio of monoaromatic compounds to polyaromatic compounds (PAHs) is therefore generally greater than 1 and most often from 1 to 2.5. The relatively high value of this ratio facilitates the recovery of the LCO fraction as the basis for diesel fuel. On the other hand, the generally atypical distribution of mono and polyaromatic compounds associated with the lower density (less than about 5%) and the higher hydrogen content of the LCO fraction obtained by the process of the invention allows for less hydrotreatment.

severe de cette fraction LCO necessitant en particulier moins d'hydrogene. Le procede utilise selon l'invention produit une fraction essence ayant generalement une temperature d'ebullition generalement de 15 a 221 C. Cette fraction essence se distingue de celles obtenues par des procedes FCC connus par le fait qu'elle contient le plus souvent moins de composes aromatiques que de composes olefiniques. La teneur en composes aromatiques dans les essences obtenues par le procede selon l'invention est en particulier inferieure a 20 % en volume et la teneur en composes olefiniques est generalement superieure a 50 % en volume, de preference superieure a 70 % en volume. Associe a la nature de la composition catalytique utilisee dans le procede utilise selon l'invention, le recyclage de certains produits issus du craquage vers la zone reactionnelle (d'ou le terme de "recycle") permet en general d'ameliorer encore le rendement en olefines legeres. En particulier, it est envisageable de recuperer une partie de 1'essence produite pour la traiter de nouveau et la convertir en essence plus Legere et en GPL. De meme, it est envisageable de valoriser une partie du slurry produit en le convertissant en fractions plus legeres par reinjection dans la zone reactionnelle. Par suite, le procede utilise selon l'invention comprend de preference la reinjection d'au moins une coupe de produit(s) issu(s) du craquage dans la zone reactionnelle de craquage, de preference une coupe essence ou une coupe slurry. Ainsi, le recyclage de tout ou partie de 1'essence et du slurry vers la zone reactionnelle du FCC permet d'accentuer encore davantage 1'atypisme des rendements obtenus par le procede utilise de l'invention. Les deux coupes sont reinjectees ensemble ou bien separement a des niveaux differents dans la zone reactionnelle. La reinjection de ces flux peut are realisee soit au meme niveau que 1'injection de la charge principale de 1'unite FCC, soit en amont de l'injection de la charge principale, soit en aval de l'injection de la charge principale. Par injecteur de charge, nous entendons generalement les injecteurs par lesquels sont injectees les charges lourdes dont le point d'ebullition est superieur a 350 C. Le procede utilise selon l'invention peut etre applique au traitement des coupes de distillation atmospherique, des coupes de  severe of this LCO fraction requiring in particular less hydrogen. The method used according to the invention produces a gasoline fraction generally having a boiling temperature of generally 15 to 221 C. This essence fraction is distinguished from those obtained by known FCC processes by the fact that it contains most often less than aromatic compounds as olefinic compounds. The content of aromatic compounds in the essences obtained by the process according to the invention is in particular less than 20% by volume and the content of olefinic compounds is generally greater than 50% by volume, preferably greater than 70% by volume. Associated with the nature of the catalytic composition used in the process used according to the invention, the recycling of certain products from cracking to the reaction zone (hence the term "recycle") generally makes it possible to further improve the yield. in light olefins. In particular, it is possible to recover some of the gasoline produced to treat it again and convert it to lighter gasoline and LPG. Similarly, it is possible to valorize a portion of the slurry produced by converting it into lighter fractions by reinjection in the reaction zone. As a result, the process according to the invention preferably comprises the reinjection of at least one product cut (s) resulting from cracking in the cracking reaction zone, preferably a gasoline cut or a slurry cut. Thus, recycling all or part of the gasoline and slurry to the reaction zone of the FCC further accentuates the attrition of the yields obtained by the process of the invention. The two sections are reinjected together or separately at different levels in the reaction zone. The reinjection of these flows can be carried out either at the same level as the injection of the main charge of the FCC unit, either upstream of the injection of the main charge, or downstream of the injection of the main charge. By charge injector, we generally mean the injectors by which the heavy charges whose boiling point is greater than 350 ° C. are injected. The process according to the invention can be applied to the treatment of atmospheric distillation cuts,

distillation sous vide, des residus de distillation atmospherique (RAT), des hydrocarbures paraffiniques issus de procedes d'hydrocraquage catalytique et des hydrocarbures issus des procedes Fischer-Tropsch, et de leurs melanges. L'invention concerne ainsi le produit hydrocarbons obtenu par le proceds utilise selon l'invention tel que decrit precedemment.  vacuum distillation, atmospheric distillation residues (RAT), paraffinic hydrocarbons from catalytic hydrocracking processes and Fischer-Tropsch hydrocarbons, and mixtures thereof. The invention thus relates to the hydrocarbon product obtained by the method used according to the invention as described above.

EXEMPLES Les exemples qui suivent servent a illustrer 1 'invention sans pour autant en limiter la portee. Dans ces exemples les % sont donnes en % en poids sauf mention contraire. On a realise sur une installation pilote ARCO des tests de craquage catalytique en lit fluidise d'une charge VGO ((, vacuum gasoil ) en utilisant, soit une composition catalytique utilisee selon 1'etat de la technique, soit une composition catalytique utilisee selon l'invention.  EXAMPLES The following examples serve to illustrate the invention without limiting its scope. In these examples% are given in% by weight unless otherwise indicated. On an ARCO pilot plant, fluidized catalytic cracking tests of a VGO ("vacuum gasoil") feed were carried out using either a catalytic composition used according to the state of the art, or a catalytic composition used according to US Pat. 'invention.

Exemple comparatif 1 Une composition catalytique, contenant 90% du catalyseur Kristal 212 (zeolithe Y) et 10% de booster commercial, connu dans le commerce sous 1'appellation Olefin Max de Grace Davison et contenant 25% de cristaux ZSM-5, a ete utilisee pour craquer une charge hydrotraitee type VGO.  Comparative Example 1 A catalyst composition, containing 90% of the Kristal 212 catalyst (zeolite Y) and 10% commercial booster, known commercially as Grace Davison's Olefin Max and containing 25% ZSM-5 crystals, was used to crack a hydrotreated load type VGO.

Exemple comparatif 2 Un catalyseur de craquage de fond (BCA) de la societe Intercat, connu dans le commerce sous 1'a_ppellation BCA 105, a ete utilise pour craquer une charge hydrotraitee type VGO.  Comparative Example 2 A bottom cracking catalyst (BCA) from Intercat, known commercially as BCA 105, was used to crack a VGO type hydrotreated feed.

Exemple 3 selon l'invention Une composition catalytique, contenant 90% de BCA105 et 10% de Olefin Max, a ets utilisee pour craquer une charge hydrotraitee type VGO Exemple comparatif 4 Une composition catalytique, contenant 90% du catalyseur Kristal 212, et 10% de booster Olefin Max, a ete utilisee pour craquer une charge hydrotraitee contenant 60% de VGO et 40% de residu atmospherique.  Example 3 According to the Invention A catalytic composition, containing 90% of BCA105 and 10% of Olefin Max, was used to crack a hydrotreated feed VGO type. Comparative Example 4 A catalyst composition, containing 90% of the Kristal 212 catalyst, and 10% Olefin Max booster, was used to crack a hydrotreated load containing 60% VGO and 40% atmospheric residue.

Exemple comparatif 5 Un catalyseur de craquage de fond BCA 105 a ete utilise pour craquer une charge hydrotraitee contenant 60% de VGO et 40% de residu atmospherique.  Comparative Example 5 A bottom cracking catalyst BCA 105 was used to crack a hydrotreated feed containing 60% VGO and 40% atmospheric residue.

Exemple 6 selon 1'invention Une composition catalytique contenant 90% de BCA 105 et 10% de Olefin Max a ete utilisee pour craquer une charge une charge hydrotraitee contenant 60% de VGO et 40% de residu atmospherique.  Example 6 According to the Invention A catalytic composition containing 90% BCA 105 and 10% Olefin Max was used to crack a hydrotreated feedstock containing 60% VGO and 40% atmospheric residue.

Les caracteristiques des charges sont donnees dans le tableau 1.  The characteristics of the loads are given in Table 1.

Les conditions operatoires et les rendements sont donnes dans le tableau 2 pour la charge hydrotraitee type VGO et dans le tableau 3 pour la charge contenant 40% de residu atmospherique. Le BCA 105 et le Olefin Max ont prealablement ete traites a la vapeur d'eau a 800 C pendant 5 heures.  The operating conditions and the yields are given in Table 2 for the hydrotreated feed type VGO and in Table 3 for the load containing 40% of atmospheric residue. BCA 105 and Olefin Max were previously treated with steam at 800 ° C for 5 hours.

Exemple comparatif 7 Un test de craquage a ete effectue dans une unite pilote ACE. Le catalyseur est constitue de 90% du BCA et 10% de Olefin-max. Les conditions de test ont ete les suivantes • C/O constant a 5,5 • masse de catalyseur = 9 g • temps d'injection de charge = 82 s • debit d'injection de charge == 1,5 mL/min • position injecteur = 2,125" (temps de craquage=1,5 s) • temperature de prechauffe charge=100 C La charge utilisee a ete la F742, decrite dans le tableau 1. Le tableau 4 montre les resultats qui ont ete obtenus.  Comparative Example 7 A cracking test was performed in an ACE pilot unit. The catalyst consists of 90% of BCA and 10% of Olefin-max. The test conditions were as follows: • Constant C / O at 5.5 • Catalyst mass = 9 g • Charge injection time = 82 s • Charge injection rate = 1.5 mL / min • injector position = 2.125 "(cracking time = 1.5 s) • preheating temperature = 100 C The load used was F742, described in Table 1. Table 4 shows the results that have been obtained.

Exemples 8 et 9 selon 1'invention Un catalyseur a ete prepare selon la methode decrite par le schema de la figure jointe. La preparation comprend le mode operatoire tel que schematise ci-dessous.  Examples 8 and 9 according to the invention A catalyst was prepared according to the method described by the scheme of the attached figure. The preparation includes the operative mode as schematized below.

A est le catalyseur de depart a base de ZSM-5, it subit des traitements successifs B puis C puis D, ce qui permet d'obtenir un catalyseur E a base de zeolithe modifiee.  A is the starting catalyst based on ZSM-5, it undergoes successive treatments B, then C and then D, which makes it possible to obtain a modified zeolite-based catalyst E.

A : ZSM-5 (Tricat) Si/Al =11,66 Na20 = 136 ppm  A: ZSM-5 (Tricat) Si / Al = 11.66 Na2O = 136 ppm

B : Traitement a la vapeur a 550 C, 100 vol % vapeur pendant 48 heures  B: Steam treatment at 550 C, 100 vol% steam for 48 hours

C : H3PO4 traitement a temperature d'ebullition pendant 18 heures : 10 mol PO43-/MO1 Al, 4.2 L solution aqueuse/kg zeolithe.  C: H3PO4 treatment at boiling temperature for 18 hours: 10 mol PO43- / MO1 Al, 4.2 L aqueous solution / kg zeolite.

D : Filtration pour enlever 1'aluminium dissous et 1'exces de H3PO4.  D: Filtration to remove dissolved aluminum and excess H3PO4.

E: Si/Al = 27 Na20 = 46 ppm P = 5,6 % poids  E: Si / Al = 27 Na 2 O = 46 ppm P = 5.6% by weight

Deux types de traitement ont alors eu lieu, permettant d'obtenir une zeolithe ZMS-5 finale avec plus ou moins de Phosphore. Les deux 25 zeolithes ainsi obtenues sont des zeolithes ZSM-5 modifiees au phosphore utilisees selon l'invention. Le premier type de traitement comprend la realisation des etapes successives F (qui permet d'obtenir un catalyseur a base de zeolithe modifiee G), puis H, J et L pour obtenir une zeolithe ZSM-5 contenant beaucoup de phosphore (M). 30 F: lavage avec de 1'eau desionisee 6 fois 2 L d'eau par 1 kg de zeolithe  Two types of treatment then took place, making it possible to obtain a final ZMS-5 zeolite with more or less phosphorus. The two zeolites thus obtained are phosphorus-modified ZSM-5 zeolites used according to the invention. The first type of treatment comprises carrying out the successive steps F (which makes it possible to obtain a modified zeolite catalyst G), then H, J and L to obtain a ZSM-5 zeolite containing a large amount of phosphorus (M). F: Wash with deionized water 6 times 2 L of water per 1 kg of zeolite

G : Si/Al = 29,5 Na20 = 108 ppm 35 P = 0,174 % en poids  G: Si / Al = 29.5 Na 2 O = 108 ppm P = 0.174% by weight

H : Melanger avec le liant : 20H: Mix with the binder: 20

500 g de zeolithe G + 2 L de 1 % HNO3 + 250 g de kaolin + 250 g de pseudo-boehmite.  500 g of G + 2 L zeolite of 1% HNO3 + 250 g of kaolin + 250 g of pseudo-boehmite.

J : Atomisation (atomiseur de Marque NIRO)  J: Atomization (Brand Atomizer NIRO)

L : Calcination a 600 C pendant 10 heures.  L: calcination at 600 ° C. for 10 hours.

M : Catalyseur final lave (ZSM-5 partiellement dopee au phosphore, avec lipide phosphor&).  M: Final catalyst washes (ZSM-5 partially doped with phosphorus, with phosphor lipid).

Le second type de traitement comprend la realisation des &tapes successives I, K et N pour obtenir une zeolithe ZMS-5 contenant peu de Phosphore (0).  The second type of treatment comprises carrying out successive stages I, K and N to obtain a ZMS-5 zeolite containing little phosphorus (O).

15 I : Melanger avec le liant : 500 g de zeolithe E + 2 L de 1 % HNO3 + 250 g de kaolin + 250 g de pseudo-boehmite.  I: Mix with the binder: 500 g E + 2 L zeolite 1% HNO3 + 250 g kaolin + 250 g pseudo-boehmite.

K : Atomisation (atomiseur de Marque NIRO)  K: Atomization (NIRO Brand Atomizer)

20 N : Calcination a 600 C pendant 10 heures.  N: calcination at 600 ° C. for 10 hours.

^ : Catalyseur final non-lave (ZSM-5 partiellement dopee au phosphore comprenant un peu de phosphore) 25 Cette preparation (B a D, puis F, H, J et L, ou bien B a D puis I, K et N) a abouti a l'obtention d'un catalyseur contenant une zeolithe ZSM-5 desaluminee et partiellement dopee a 1'oxyde de phosphore (M ou 0), lesdits catalyseurs ayant ete utilises (10 %) en combinaison avec le 30 catalyseur BCA (90%).  Catalyst non-washes (partially phosphorus-doped ZSM-5 comprising a little phosphorus) This preparation (B a D, then F, H, J and L, or B a D then I, K and N) resulted in the production of a catalyst containing a ZSM-5 zeolite desaluminated and partially doped with phosphorus oxide (M or O), said catalysts having been used (10%) in combination with the catalyst BCA (90). %).

Les tests de craquage ont ete effectues dans une unite pilote ACE. Les conditions de test ont ete les suivantes : • C/O constant a 5,5 35 • masse de catalyseur = 9g • temps d'injection de charge = 82s • debit d' inj ection de charge 1,5 mL/mn • position injecteur = 2,125" (temps de craquage=1,5 s) 10 • temperature de prechauffe charge = 100 C La charge utilisee a ete la F742, decrite dans le tableau 1. Le tableau 4 montre les resultats qui ont ete obtenus.  The cracking tests were performed in an ACE pilot unit. The test conditions were as follows: • Constant C / O at 5.5 • Catalyst mass = 9g • Charge injection time = 82s • Charge injection rate 1.5 mL / min • Position injector = 2.125 "(cracking time = 1.5 s) 10 • preheating temperature load = 100 C. The load used was F742, described in Table 1. Table 4 shows the results that were obtained.

TABLEAU 1 VGO 60% VGO + 40% RAT Reference F672 F742 Nombre AcideTotal (mg KOH/100 g) 0,13 0,24 Densite g/ml @ 15 C 0,9058 0,9178 Soufre % en poids @ rayons X 0,142 0,3 Azote de base ppm en poids 167 479 Azote Total ppm en poids < 0.5 Carbone Conradson % en poids 0,12 2,01 Point Aniline C 91 92,6 Viscosite Cinetique cSt @ 100 C 8,13 12,36 Ni ppm en poids 4 V ppm en poids 4 SOARA Satures+olefins (% mol) 49,6 48,1 SOARA Olefines (% mol) 0,3 0,3 SOARA Aromatiques ( % mol) 47 44,4 SOARA Mono aromatiques (% mol) 30 22,8 SOARA Di aromatiques (% mol ) Resins (% en poids) 3,4 7,5 Asphaltenes (% en poids) 0,08 0,35 D 1160 vol % T IBP 274 252 354 349 377 377 20 404 408 30 422 428 40 438 448 50 454 469 60 471 489 70 489 511 80 508 540 90 533 592 95 552 654 FBP 597 697 (97%) 16 ABLEAU 2 VOG (F672) Exemple comparatif 1 Exemple comparatif 2 Exemple selon I'invention 3 Catalyseur Kristal 212 10% OLEFIN MAX C BCA 105 BCA 105 + 10 A, OLEFIN MAX C Test No. K3422 K3423 . ~ w .... K3410 K3411 K3412 K3413 K3414 K34 A G K34L4 1 5 Trx C 530 530 530 530 530 530 530 530 530 Cat/Oil 4,61 5,65 _ 6,61 4,61 5,59 6,66 4,67 5,65 _ 6,64 _ 0,33 0,33 0,33 _ 0,30 0,29 0,30 0,27 H2 0,29 0,27 H2S 0,04 0,04 0,04 0,02 0,02 0,02 0,03 0,02 0,02 0H4 0,56 0,60 0,630,77 0,76 0,77 0,69 0,66 0,69 C2H4 0,69 075 0,80 0,68 0,68 0,70 0,83 0,79 0,85 02H6 0,34 0,36 0,38 0,57 0,55 - 0,53 0,47 0,44 0,46 C3H6 (C3= totaux) 7,89 8,30 8,71 4,83 5,30 5,74 8,49 8,41 9,01 C3H8 1,00 _ 1,20 0,53 0,56 0,57 0,69 0,67 0,71 1,11 C3 totaux 8,89 9,41 9,91 5,36 5,86 6,31 9,18 9,08 9,72 C4H6 (04 == donc 04 =) 0,04 0,04 0,03 0,10 0,09 0,09 0,10 0,08 0,08 104H8 (04 =) 1,91 1,99 1,99 1,49 1,59 1,70 1,92 1,94 2,05 i C4H8 (iC4 = donc 04 =) 2,67 2,71 2,67 2,81 2,98 3,17 _ 385 3,88 4,07 2 (ct) C4H8 (04 =) 4,04 4,25 _ 3,09 3,34 3,56 4,05 4,15 4, 36 4,25 nC4H10 0,72 0,80 0,84 0,31 0,33 0,35 0,37 0,37 0,38 1C4H10 3,84 4,23 4,48 1,24 1,39 1,49 1,47 1,54 1,63 C4 = totaux 8,66 8,99 8,94 7,49 8,00 8,52 9,92 10,05 10,56 C4 totaux 13,22 14,02 14,26 9,04 9,72 10,36 _ 11,76 11,96 _ 12,57 47,39 47,04 46,93 34,71 38,41 40,16 32,48 34,91 34,56 Essence Totale FIA satures (%vol) 30,90 29,50 34,10 22,8 25,3 23,6 24,6 23,9 25,6 FIA olefines (%vol) 34,50 _ 32,70 62,4 60,2 61,1 62,1 62,1 60,3 32,80 FIA aromatiques (%vol) 34,60 37,70 33,20 14,8 14,5 15,3 13,3 14 14, 1 LCO total 16,21 15,45 14,60 20,99 21,11 20,19 20,45 20,08 19,76 Densite (g/ml) 0,97 0,97 0,98 0,93 0,93 0,94 0,93 0,93 0,94 S (ppm) 1990 2040 2110 15,00 1860 1780 1550 1590 1680 Fischer Monoaromatique (%pd) _ 23,90 27,70 14,60 Fischer Diaromatique (%pd) 53,80 40,70 43,00 Fischer Triaromatique (%pd) 8,90 7,10 4,40 Fischer Monoaromatiquel 0,23 0,50 0,58 Fischer Di et Triaromatique ( A.) Slurry total 10,3 9,8 9,4 26,0 20,8 18,6 22,2 20,0 19,1 0,95 _ 0,95 0,95 0,95 0,95 Densite (g/ml) 1,05 1,06 1,07 0,95 S (ppm) _ 4230 4350 24,90 25,00 2760 2570 2660 2780 4210 COKE 2,34 2,52 2,94 1,89 2,12 2,39 1,95 2,10 2,29 Gaz sec 1,92 2,02 2,12 2,38 2,35 2,35 2,32 2,20 2,32 Conversion standard 73,23 74,57 75,90 52,75 57,83 60,93 57,13 59,69 _ 60,91 Conversion liquide 85,13 85,44 85,43 69,39 74,40 76,30 73,24 75,39 75,99 C3= / C3 totaux 0,89 0,88 0,88 0,90 0,90 0,91 0,92 0,93 0,93 C4= / C4 totaux 0,66 0,64 0,63 0,83 0,82 0,82 0,84 0,84 0,84 0,19 0,19 0,31 0, 31 0,31 0,33 0,32 0,32 iC4= / C4 totaux 0,20 17 TABLEAU 3 60% VGO (F672) + 40 % RAT (F729) (F742 Exemple comparatif 4 Exemple comparatif 5 Exemple selon ('invention 6 Catal seur Kristal 212 +10% OLEFIN MAX C BCA 105 BCA 105 + 10 % OLEFIN MAX C Test K3419 K3420 K3421 K3407 K3408 K3409 K3416 K3417 K3418 530 530 530 530 530 Trx C 530 530 530 530 Cat/Oil 4,42 5,42 6,47 4,53 5,41 6,46 v 4,44 5,46 6,43 H2 0,25 0,26 0,30 0,37 0,38 037 0,33 0,34 0,35 0,10 0,10 0,09 H2S 0,12 0,12 0,12 0,09 0,08 0,08 CH4 0,61 0,65 0,69 0,92 0,89 0,87 0,91 0,83 _ 0,85 C2H4 0,65 0,69 0,73 0,72 0,70 _0,68 0,83 0,78 0,82 C2H6 0,38 0,40 0,41 0,73 0,68 0,63 0,66 0,59 0,58 C3H6 (C3 = totaux) 7,42 7,63 7,74 3,83 4,43 4,78 5,14 7,03 7,46 0,59 0,59 0,73 0,68 0,69 C3H8 0,86 0,88 0,99 0,58 C3 totaux 8,28 8,51 8,73 4,41 5,02 5,37 5, 87 7,71 8,15 C4H6 (C4 == donc C4=) 0,06 0,05 0,05 _0,10 0,10 0,09 0,10 0,09 0,08 1C4H8 (C4 =) 1,79 1,84 1,85 1,17 1,30 1,37 1,72 _ 1,66 1,73 1C4H8 (iC4 = donc C4 =) 2,90 2,98 2,79 2,20 2,47 2,62 3,49 3,37 3,49 2 (ct)C4H8 (C4 =) 3,82 4,02 3,94 2,39 2,68 2,86 3,58 3,51 3,64 0,29 0,30 0,31 0,36 0,34 _ 0,34 nC4H10 0,57 0,60 0,67 iC4H10 2,75 2,92 3,22 0,82 0,94 1,04 1,01 0,99 1,04 C4 = totaux 8,57 8,89 8,63 5,86 6,55 6,94 8,89 8,63 8,94 C4 totaux 11,89 12,41 12,52 6,97 7,79 8,29 10,26 9,96 10,32 Essence totale 40,35 41,44 43,85 34,54 36,76 38,17 30,11 31,41 32,17 21,9 24,1 25,9 28,3 24,9 67,3 FIA satures (%vol) 28,60 30,10 31,80 21,9 64 64,3 62 60,1 FIA olefines (%vol) 42,90 42,50 38,70 66 FIA aromatiques (%vol) 28,00 27,40 20,50 12,1 10,8 11,9 9,80 9,70 15,00 LCO total 19,93 18,85 15,97 20,51 20,23 20,07 20,33 20,09 20,70 Densite (g/ml) 0,95 0,95 0,96 0,92 0,92 0, 92 0,92 0,93 0,93 S (ppm) 3400 3380 3450 2210 2387 2418 2660 2730 2870 Cetane calcule 17,80 23,60 23,40 Fischer Monoaromat (% pd) 17,60 27,70 27,00 Fischer Diaromat (% pd) 53,20 36,20 38,70 Fischer Triaromat (% pd) 7,20 4,90 4,90 Fischer Monoaromatiques 0,29 0,67 0,62 I Fischer Di+Triaromatiques (%) Slurry total 13,60 12,46 12,01 26,75 23,21 21,21 26,52 24,02 21,36 Densite (g/ml) 1,02 1,03 1,05 0,94 0,95 0,96 0,94 0,94 0,95 S (ppm) 5470 5690 5980 2906 3104 3321 3180 3320 3490 COKE 3,95 4,22 4,66 4,00 4,27 4,26 4,00 4,18 _ 4,63 Gaz sec 2,00 _ _ _ 2,72 2,64 2,81 2,63 2,69 2,12 2,25 2,82 Conversion standard 66,06 68,33 71,76 52,28 56, 12 58,28 52,72 55,47 57,53 71,46 66,15 _ 70,91 68,75 Conversion liquide 80, 04 80,83 80,82 65,97 _ 69,35 C3= / C3 totaux 0,90 0,90 - 0,87 0,88 0,89 0,88 0,91 0,92 0,89 0,72 0,72 0,69 0,84 0,84 0,84 0,87 0,87 0,87 C4= / C4 totaux iC4 = I C4 totaux 0,23 0,24 0,22 0,32 0,32 0,32 0,34 0,34 0,34 TABLEAU 4 Exemple 7 Exemple 8 selon Exemple 9 Comparatif l'invention selon l'invention BCA+Olefinmax BCA+haut P ZSM-5 _ M BCA+bas P ZSM-5 0 Reaction T [ C] 525 525 525 H2 0.27 0.32 0.29 H2S 0.87 0.87 0.87 Cl 0.62 0.63 _ 0.64 C2 0.41 0.43 _ 0.44 C2= 0.56 0.91 _ 0.90 H2-C2 2.72 3.16 _ 3.15 C3 0.58 0.75 0.74 C3= 5.19 7.77 7.34 C4 0.27 _ 0.37 0.38 'C4 0.98 0.97 0.95 C4= totaux 5.71 8.78 8.28 1'C4= 1.00 _ _ 1.35 1.31 . C4= 2.35 _ 3.15 3.34 cis C4= 0.96 1.64 1.54 rans C4= 1.39 _ 2.28 2.45 C3 totaux 5.77 8.52 8.08 C4 totaux 6.95 10.14 9.59 GLP (Total C4 + C3)_ 12.72 18.65 _ 17.67 Gasoline C5-221 26.69 23.03 22.98 LCO 221-360 20.58 18.44 18.22 Bottoms 360+ 31.84 30.23 31.58 Coke 5.45 6.49 _ 6.41 Delta Coke 0.99 1.18 1.16 Conversion -221 47.58 51.34 50.20 Liq. Conversion 59.99 60.12 58.87 Cat/ Oil 5.50 5.50 5.50 _ C3=/C3's 0.90 0.91 0.91 _ C4=/C4's 0.82 _ 0.87 0.86 LCO/ Slurry 0.65 0.61 0.58 100-slurry/slurry 2.14 2.31 2.17  TABLE 1 VGO 60% VGO + 40% RAT Reference F672 F742 Total Acid Number (mg KOH / 100 g) 0.13 0.24 Density g / ml @ 15 C 0.9058 0.9178 Sulfur% by weight @ x-rays 0.142 0 , 3 Nitrogen base ppm by weight 167 479 Nitrogen Total ppm by weight <0.5 Conradson carbon% by weight 0.12 2.01 Aniline point C 91 92.6 Cinetic viscosity cSt @ 100 C 8.13 12.36 Ni ppm weight 4 V ppm by weight 4 SOARA Saturates + olefins (% mol) 49.6 48.1 SOARA Olefins (% mol) 0.3 0.3 SOARA Aromatic (% mol) 47 44.4 SOARA Mono aromatic (% mol) 22.8 SOARA Di aromatics (mol%) Resins (wt.%) 3,4 7,5 Asphaltenes (% by weight) 0,08 0,35 D 1160 vol% T IBP 274 252 354 349 377 377 20 404 408 ## STR1 ## Kristal Catalyst 212 10% OLEFIN MAX C BCA 105 BCA 105 + 10A, OLEFIN MAX C Test No. K3422 K3423. ~ w .... K3410 K3411 K3412 K3413 K3414 K34 AG K34L4 1 5 Trx C 530 530 530 530 530 530 530 530 530 Cat / Oil 4.61 5.65 _ 6.61 4.61 5.59 6.66 4 , 5.65, 6.64, 0.33, 0.33, 0.33, 0.30, 0.29, 0.30, 0.27, H2 0.29, 0.27, H2S, 0.04, 0.04, 0.04, 0. , 02 0.02 0.02 0.03 0.02 0.02 0H4 0.56 0.60 0.630.77 0.76 0.77 0.69 0.66 0.69 C2H4 0.69 075 0.80 0.68 0.68 0.70 0.83 0.79 0.85 02H6 0.34 0.36 0.38 0.57 0.55 - 0.53 0.47 0.44 0.46 C3H6 (C3 = totals) 7.89 8.30 8.71 4.83 5.30 5.74 8.49 8.41 9.01 C3H8 1.00 _ 1.20 0.53 0.56 0.57 0.69 0.67 0.71 1.13 C3 totals 8.89 9.41 9.91 5.36 5.86 6.31 9.18 9.08 9.72 C4H6 (04 == so 04 =) 0.04 0.04 0.03 0.10 0.09 0.09 0.10 0.08 0.08 104H8 (04 =) 1.91 1.99 1.99 1.49 1.59 1.70 1.92 1.94 2.05 i C4H8 (iC4 = therefore 04 =) 2.67 2.71 2.67 2.81 2.98 3.17 385 3.88 4.07 2 (ct) C4H8 (04 =) 4.04 4.25 3.09 3.34 3.56 4.05 4.15 4.36 0.45 nC4H10 0.72 0.80 0.84 0.31 0.33 0.35 0.37 0.37 0.38 1C4H10 3.84 4.23 4.48 1.24 1.39 1.49 1.47 1.54 1.63 C4 = totals 8.66 8.99 8.94 7.49 8 , 00 8.52 9.92 10.05 10, 56 C4 totals 13.22 14.02 14.26 9.04 9.72 10.36 _ 11.76 11.96 _ 12.57 47.39 47.04 46.93 34.71 38.41 40.16 32.48 34.91 34.56 Total Gasoline FIA saturated (% vol) 30.90 29.50 34.10 22.8 25.3 23.6 24.6 23.9 25.6 FIA Olefins (% vol) 34,50 _ 32,70 62,4 60,2 61,1 62,1 62,1 60,3 32,80 FIA Aromatic (% vol) 34,60 37,70 33,20 14,8 14,5 15 , 3 13.3 14 14, 1 Total LCO 16.21 15.45 14.60 20.99 21.11 20.19 20.45 20.08 19.76 Density (g / ml) 0.97 0.97 0.98 0.93 0.93 0.94 0.93 0.93 0.94 S (ppm) 1990 2040 2110 15.00 1860 1780 1550 1590 1680 Monoaromatic Fischer (% pd) _ 23.90 27.70 14 , 60 Fischer Diaromatic (% pd) 53.80 40.70 43.00 Triaromatic Fischer (% pd) 8.90 7.10 4.40 Fischer Monoaromatiquel 0.23 0.50 0.58 Fischer Di and Triaromatic (A. ) Total slurry 10.3 9.8 9.4 26.0 20.8 18.6 22.2 20.0 19.1 0.95 _ 0.95 0.95 0.95 0.95 Density (g / ml) 1.05 1.06 1.07 0.95 S (ppm) _ 4230 4350 24.90 25.00 2760 2570 2660 2780 4210 COKE 2.34 2.52 2.94 1.89 2.12 2, 39 1.95 2.10 2.29 Dry gas 1.92 2.02 2.12 2.38 2.35 2.35 2.22 2.20 2.32 Standard conversion 73.23 74.57 75.90 52.75 57.83 60.93 57.13 59.69 _ 60.91 Liquid conversion 85.13 85.44 85.43 69.39 74.40 76.30 73.24 75.39 75.99 C3 = / C3 total 0.89 0.88 0.88 0.90 0.90 0.91 0.92 0.93 0.93 C4 = / Total C4 0.66 0.64 0.63 0.83 0.82 0.82 0.84 0.84 0.84 0.19 0.19 0.31 0.31 0.33 0.32 0.32 iC4 = / C4 total 0.20 17 TABLE 3 60% VGO (F672) + 40% RAT (F729) (F742 Comparative Example 4 Comparative Example 5 Example According to (Invention 6 Catalyst Kristal 212 + 10% OLEFIN MAX C BCA 105 BCA 105 + 10% OLEFIN MAX C Test K3419 K3420 K3421 K3407 K3408 K3409 K3416 K3417 K3418 530 530 530 530 530 Trx C 530 530 530 530 Cat / Oil 4.42 5.42 6.47 4.53 5.41 6.46 v 4.44 5.46 6.43 H2 0.25 0.26 0.30 0.37 0.38 0.337 0.33 0.34 0.35 0.10 0.10 0.09 H2S 0 , 12 0.12 0.19 0.09 0.08 0.08 CH4 0.61 0.65 0.69 0.92 0.89 0.87 0.91 0.83 0.85 C2H4 0.65 0.69 0.73 0.72 0.70 _0.68 0.83 0.78 0.82 C2H6 0.38 0.40 0.41 0.73 0.68 0.63 0.66 0.59 0 , 58 C3H6 (C3 = totals) 7.42 7.63 7.74 3.83 4.43 4.78 5, 14 7.03 7.46 0.59 0.59 0.73 0.68 0.69 C3H8 0.86 0.88 0.99 0.58 C3 total 8.28 8.51 8.73 4.41 5 , 02 5.37 5, 87 7.71 8.15 C4H6 (C4 == so C4 =) 0.06 0.05 0.05 0.01 0.10 0.09 0.10 0.09 0.08 1C4H8 (C4 =) 1.79 1.84 1.85 1.17 1.30 1.37 1.72 1.66 1.73 1C4H8 (iC4 = therefore C4 =) 2.90 2.98 2.79 2.20 2.47 2.62 3.49 3.37 3.49 2 (ct) C4H8 (C4 =) 3.82 4.02 3.94 2.39 2.68 2.86 3.58 3, 51 3.64 0.29 0.30 0.31 0.36 0.34 0.34 nC4H10 0.57 0.60 0.67 iC4H10 2.75 2.92 3.22 0.82 0.94 1 , 04 1.01 0.99 1.04 C4 = totals 8.57 8.89 8.63 5.86 6.55 6.94 8.89 8.63 8.94 C4 total 11.89 12.41 12 , 52 6.97 7.79 8.29 10.26 9.96 10.32 Total petrol 40.35 41.44 43.85 34.54 36.76 38.17 30.11 31.41 32.17 21 , 9 24.1 25.9 28.3 24.9 67.3 FIA saturated (% vol) 28.60 30.10 31.80 21.9 64 64.3 62 60.1 FIA olefins (% vol) 42 , 90 42,50 38,70 66 FIA aromatics (% vol) 28,00 27,40 20,50 12,1 10,8 11,9 9,80 9,70 15,00 Total LCO 19,93 18,85 15.97 20.51 20.23 20.07 20.33 20.09 20.70 Density (g / ml) 0.95 0.95 0.96 0.92 0.92 0, 92 0.92 0, 93 0.93 S ( ppm) 3400 3380 3450 2210 2387 2418 2660 2730 2870 Cetane calculates 17.80 23.60 23.40 Fischer Monoaromat (% w) 17.60 27.70 27.00 Fischer Diaromat (% w) 53.20 36.20 38 , 70 Fischer Triaromat (% pd) 7.20 4.90 4.90 Fischer Monoaromatic 0.29 0.67 0.62 I Fischer Di + Tri-aromatic (%) Total slurry 13.60 12.46 12.01 26.75 23.21 21.21 26.52 24.02 21.36 Density (g / ml) 1.02 1.03 1.05 0.94 0.95 0.96 0.94 0.94 0.95 S ( ppm) 5470 5690 5980 2906 3104 3321 3180 3320 3490 COKE 3.95 4.22 4.66 4.00 4.27 4.26 4.00 4.18 _ 4.63 Dry gas 2.00 _ _ _ 2 72 2.64 2.81 2.63 2.69 2.12 2.25 2.82 Standard conversion 66.06 68.33 71.76 52.28 56, 12 58.28 52.72 55.47 57, 53 71.46 66.15 _ 70.91 68.75 Liquid conversion 80, 04 80.83 80.82 65.97 _ 69.35 C3 = / C3 total 0.90 0.90 - 0.87 0.88 0.89 0.88 0.91 0.92 0.89 0.72 0.72 0.69 0.84 0.84 0.84 0.87 0.87 0.87 C4 = / C4 total iC4 = I C4 total 0.23 0.24 0.22 0.32 0.32 0.32 0.34 0.34 0.34 TABLE 4 Example 7 Example 8 according to Example 9 Comparative the invention according to the invention BC A + Olefinmax BCA + high P ZSM-5 _ M BCA + low P ZSM-5 0 Reaction T [C] 525 525 525 H2 0.27 0.32 0.29 H2S 0.87 0.87 0.87 Cl 0.62 0.63 _ 0.64 C2 0.41 0.43 _ 0.44 C2 = 0.56 0.91 _ 0.90 H2-C2 2.72 3.16 _ 3.15 C3 0.58 0.75 0.74 C3 = 5.19 7.77 7.34 C4 0.27 _ 0.37 0.38 'C4 0.98 0.97 0.95 C4 = total 5.71 8.78 8.28 1'C4 = 1.00 _ _ 1.35 1.31. C4 = 2.35 _ 3.15 3.34 cis C4 = 0.96 1.64 1.54 rans C4 = 1.39 _ 2.28 2.45 C3 total 5.77 8.52 8.08 C4 total 6.95 10.14 9.59 GLP (Total C4 + C3) _ 12.72 18.65 _ 17.67 Gasoline C5-221 26.69 23.03 22.98 LCO 221 -360 20.58 18.44 18.22 Bottoms 360+ 31.84 30.23 31.58 Coke 5.45 6.49 _ 6.41 Delta Coke 0.99 1.18 1.16 Conversion -221 47.58 51.34 50.20 Liq. Conversion 59.99 60.12 58.87 Cat / Oil 5.50 5.50 5.50 _ C3 = / C3's 0.90 0.91 0.91 _ C4 = / C4's 0.82 _ 0.87 0.86 LCO / Slurry 0.65 0.61 0.58 100-slurry / slurry 2.14 2.31 2.17

On a ainsi constate que l'utilisation de la composition catalytique selon l'invention a permis d'augmenter significativement a la fois le rendement en propylene, en butenes (surtout en isobutene) et en monoaromatiques par rapport aux polyaromatiques dans le LCO, tout en ameliorant les proprietes de c:es differentes fractions, c'est-a-dire la teneur en olefines de la coupe C3 et de la coupe C4, la teneur en aromatiques dans la coupe essence et la teneur en poly-aromatiques. D'autre part, les catalyseurs contenant du phosphore donnent avantageusement un rendement en propylene plus eleve et une purete de la coupe C3 et C4 plus riche en olefines par rapport de 1'additif Olefin-max.  It has thus been found that the use of the catalytic composition according to the invention has made it possible to significantly increase both the yield of propylene, butenes (especially in isobutene) and monoaromatics with respect to the polyaromatics in the LCO, while improving the properties of these different fractions, ie the olefin content of the C3 cut and the C4 cut, the aromatics content in the petrol cut and the polyaromatic content. On the other hand, the phosphorus-containing catalysts advantageously provide a higher propylene yield and purity of the C3 and C4 cutter richer in olefins than the Olefin-max additive.

Claims (21)

REVENDICATIONS 1. Produit hydrocarbons obtenu par un procede de craquage catalytique en lit mouvant ou fluidise circulant (FCC), d'au moins une charge hydrocarbonee ayant une temperature d'ebullition superieure ou egale a 350 C, utilisant, en tant que seul catalyseur de craquage dans une zone reactionnelle de craquage, la composition catalytique constituee : - de 50% a 99,5% en poids, rapportes a la somme de (1) et (2), d'au moins un composant catalytique amorphe (1) contenant au moins un oxyde metallique amorphe mesoporeux et/ ou macroporeux choisi parmi la silice, 1'alumine et les aluminosilicates, et - de 0,5% a 50 /0 en poids, rapportes a la somme de (1) et (2), d'au moins un composant catalytique cristallin (2) contenant au moins un aluminosilicate cristallin microporeux, et exempte de zeolithe Y.  1. A hydrocarbon product obtained by a catalytic cracking process in fluid bed or circulating fluidizing (FCC), of at least one hydrocarbon feed having a boiling point greater than or equal to 350 ° C., using, as sole cracking catalyst in a cracking reaction zone, the catalytic composition constitutes: from 50% to 99.5% by weight, relative to the sum of (1) and (2), of at least one amorphous catalytic component (1) containing at least minus a mesoporous and / or macroporous amorphous metal oxide selected from silica, alumina and aluminosilicates, and from 0.5% to 50% by weight, based on the sum of (1) and (2), at least one crystalline catalyst component (2) containing at least one microporous crystalline aluminosilicate, and free from zeolite Y. 2. Produit hydrocarbons selon la revendication 1, tel que la composition catalytique est constituee : - de 50% a 95% en poids, rapportes a la somme de (1) et (2), d'au moins un composant catalytique amorphe (1) contenant au moins un oxyde metallique amorphe mesoporeux et/ou macroporeux choisi parmi la silice, 1'alumine et les aluminosilicates, et - de 5% a 50% en poids, rapportes a la somme de (1) et (2), d'au moins un composant catalytique cristallin (2) contenant au moins un aluminosilicate cristallin microporeux, et qu'elle est exempte de zeolithe Y.  2. A hydrocarbon product according to claim 1, such that the catalytic composition consists of: from 50% to 95% by weight, based on the sum of (1) and (2), of at least one amorphous catalytic component (1 ) containing at least one mesoporous and / or macroporous amorphous metal oxide selected from silica, alumina and aluminosilicates, and - from 5% to 50% by weight, based on the sum of (1) and (2), of at least one crystalline catalyst component (2) containing at least one microporous crystalline aluminosilicate, and which is free from zeolite Y. 3. Produit hydrocarbone selon rune des revendications 1 ou 2, tel que la composition catalytique comporte au moins une matiere particulaire comprenant des particules contenant chacune du composant catalytique (1) et du composant catalytique (2).  3. Hydrocarbon product according to one of claims 1 or 2, such that the catalytic composition comprises at least one particulate material comprising particles each containing catalytic component (1) and catalytic component (2). 4. Produit hydrocarbone selon la revendication 1 a 3, tel que la composition catalytique comporte au moins une matiere particulaire comprenant des particules contenant du composant catalytique (1) et des particules contenant du composant catalytique (2).  A hydrocarbon product according to claim 1 to 3, wherein the catalytic composition comprises at least one particulate material comprising particles containing catalytic component (1) and particles containing catalytic component (2). 5. Produit hydrocarbons selon rune des revendications precedentes, tel que le composant catalytique (1) contient de 5 % a 75 en poids d'oxyde metallique amorphe mesoporeux et/ou macroporeux choisi parmi la silice, 1'alumine et les aluminosilicates, le complement etant forme par au moins un liant et/ou diluant n'ayant sensiblement aucune activite catalytique.  5. A hydrocarbon product according to one of the preceding claims, such that the catalytic component (1) contains from 5% to 75% by weight of amorphous metal oxide mesoporous and / or macroporous selected from silica, alumina and aluminosilicates, the complement being formed by at least one binder and / or diluent having substantially no catalytic activity. 6. Produit hydrocarbons selon rune des revendications precedentes, tel que 1'oxyde metallique amorphe du composant catalytique (1) contient de 10 % en poids a 90 % en poids d'oxyde d'aluminium, et contient de 0 % en poids a 30 % en poids d'oxyde de silicium.  Hydrocarbon product according to one of the preceding claims, such that the amorphous metal oxide of the catalyst component (1) contains from 10% by weight to 90% by weight of aluminum oxide, and contains from 0% by weight to 30% by weight. % by weight of silicon oxide. 7. Produit hydrocarbons selon 1'une des revendications precedentes, tel que 1'oxyde metallique amorphe du composant catalytique (1) contient en outre un ou plusieurs elements metalliques M choisis parmi le magnesium, le calcium, le zinc, le bore, le titane, le zirconium et le phosphore.  7. The hydrocarbon product according to one of the preceding claims, such that the amorphous metal oxide of the catalytic component (1) additionally contains one or more metallic elements M chosen from magnesium, calcium, zinc, boron and titanium. , zirconium and phosphorus. 8. Produit hydrocarbons selon rune des revendications precedentes, tel que 1'oxyde metallique amorphe du composant catalytique (1) presente une surface specifique de 50 a 700 m2/g.  Hydrocarbon product according to one of the preceding claims, such that the amorphous metal oxide of the catalytic component (1) has a specific surface area of 50 to 700 m 2 / g. 9. Produit hydrocarbons selon rune des revendications precedentes, tel que 1'oxyde metallique amorphe du composant catalytique (1) est tel que 75 % de ses pores ont un diametre superieur a 2 nm.  9. The hydrocarbon product according to one of the preceding claims, such that the amorphous metal oxide of the catalytic component (1) is such that 75% of its pores have a diameter greater than 2 nm. 10. Produit hydrocarbons selon 1'une des revendications precedentes, tel que le composant catalytique (2) contient de 5 % a 75 % en poids d'au moins un alurninosilicate cristallin microporeux, le complement etant forme par au moins un liant et/ou diluant n'ayant sensiblement aucune activite catalytique.  10. A hydrocarbon product according to one of the preceding claims, such that the catalytic component (2) contains from 5% to 75% by weight of at least one microporous crystalline aluminosilicate, the complement being formed by at least one binder and / or diluent having substantially no catalytic activity. 11. Produit hydrocarbons selon rune des revendications precedentes, tel que 1'aluminosilicate cristallin microporeux du composant catalytique (2) est une zeolithe qui presente un rapport Si/Al superieur a 10.  Hydrocarbon product according to one of the preceding claims, such that the microporous crystalline aluminosilicate of the catalytic component (2) is a zeolite which has an Si / Al ratio greater than 10. 12. Produit hydrocarbons selon rune des revendications precedentes, tel que 1'aluminosilicate cristallin microporeux du composant catalytique (2) est une zeolithe qui presente au moins une ouverture a dix ponts a oxygene.  12. The hydrocarbon product according to one of the preceding claims, such that the microporous crystalline aluminosilicate of the catalytic component (2) is a zeolite which has at least one aperture with ten oxygen bridges. 13. Produit hydrocarbons selon rune des revendications precedentes, tel que 1'aluminosilicate cristallin microporeux du composant catalytique (2) est choisi dans le groupe forme par les ZSM- 5, modifiee ou non au phosphore, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, TS-1, TS-2, SSZ-46, MCM-22, MCM-49, FU-9, PSH-3, ITQ-1, EU-1, NU-10, la silicalite-1, la silicalite-2, la boralite C, la boralite D, la ferrierite, la chabasite et la theta-1, et leurs melanges, 1'aluminosilicate cristallin microporeux stant de fawn prefer& une ZSM-5, modifiee ou non au phosphore, et de facon encore plus preferee une ZSM-5 modifiee au phosphore.  13. The hydrocarbon product according to one of the preceding claims, such that the microporous crystalline aluminosilicate of the catalytic component (2) is selected from the group consisting of ZSM-5, modified or not with phosphorus, ZSM-11, ZSM-22, ZSM -23, ZSM-35, ZSM-48, ZSM-50, TS-1, TS-2, SSZ-46, MCM-22, MCM-49, FU-9, PSH-3, ITQ-1, EU-1 , NU-10, silicalite-1, silicalite-2, boralite C, boralite D, ferrierite, chabasite and theta-1, and mixtures thereof, the microporous crystalline aluminosilicate is preferably used in a ZSM-1. 5, modified or not with phosphorus, and even more preferably a phosphorus-modified ZSM-5. 14. Produit hydrocarbons selon rune des revendications precedentes, tel que le procsde comprend la reinjection d'au moins une coupe de produit(s) issu(s) du craquage dans la zone reactionnelle de craquage, de preference une coupe essence ou une coupe slurry.  14. A hydrocarbon product according to one of the preceding claims, such that the method comprises the reinjection of at least one cut of product (s) resulting from cracking in the cracking reaction zone, preferably a gasoline cut or a slurry cut. . 15. Produit hydrocarbons selon rune des revendications precedentes, tel que la charge hydrocarbonse ayant temperature d'ebullition superieure ou sgale a 350 C est choisie parmi les coupes de distillation atmospherique, les coupes de distillation sous vide, les residus de distillation atmospherique (RAT), les hydrocarbures paraffiniques issus de procedes d'hydrocraquage catalytique et les hydrocarbures issus des procedes Fischer-Tropsch, et leurs melanges.  15. A hydrocarbon product according to one of the preceding claims, such that the hydrocarbon feed having a boiling point greater than or equal to 350 ° C is selected from atmospheric distillation cups, vacuum distillation cups, atmospheric distillation residues (RAT). , paraffinic hydrocarbons derived from catalytic hydrocracking processes and hydrocarbons derived from Fischer-Tropsch processes, and mixtures thereof. 16. Produit hydrocarbons selon rune des revendications precedentes, tel que sa fraction C3 contient au moins 90 % en poids de propylene, et tel que sa fraction C4 contient au moins 80 % en poids de butenes.  16. A hydrocarbon product according to one of the preceding claims, such that its C3 fraction contains at least 90% by weight of propylene, and such that its C4 fraction contains at least 80% by weight of butenes. 17. Produit hydrocarbons selon rune des revendications precedentes, tel que sa fraction des butenes contient au moins 35 % en poids d'isobutenes.  17. The hydrocarbon product according to one of the preceding claims, such that its butenes fraction contains at least 35% by weight of isobutenes. 18. Produit hydrocarbons selon rune des revendications precedentes, tel qu'il contient une fraction LCO ( light cycle oil ayant un indice de cetane superieur ou egal a 23.  18. A hydrocarbon product according to one of the preceding claims, such that it contains a LCO (light cycle oil) fraction having a cetane number greater than or equal to 23. 19. Produit hydrocarbons selon rune des revendications precedentes, tel qu'il contient une fraction LCO ( light cycle oil presentant un rapport ponderal des composes monoaromatiques aux composes polyaromatiques superieur a 1, de preference compris de 1 A. 2,5.  19. A hydrocarbon product according to one of the preceding claims, such that it contains a LCO (light cycle oil) fraction having a weight ratio of monoaromatic compounds to polyaromatic compounds greater than 1, preferably of 1 A. 2.5. 20. Produit hydrocarbons selon rune des revendications precedentes, tel que sa fraction essence a une teneur en composes aromatiques inferieure a 20 % en volume.  20. The hydrocarbon product according to one of the preceding claims, such that its gasoline fraction has an aromatic compound content of less than 20% by volume. 21. Produit hydrocarbons selon 1'une des revendications precedentes, tel que sa fraction essence a une teneur en composes  21. The hydrocarbon product according to one of the preceding claims, such that its gasoline fraction has a content of compounds.
FR0610904A 2006-12-14 2006-12-14 Hydrocarbon product obtained by a moving/fluidized bed catalytic cracking of a hydrocarbon charge using a catalytic composition comprising an amorphous catalytic component and a crystalline catalytic component Pending FR2894975A1 (en)

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WO2016086781A1 (en) * 2014-12-03 2016-06-09 中国石油化工股份有限公司 Catalyst and preparation method thereof, and method for preparing isobutylene by applying the same

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