EP0334742B1 - Liquid phase selective hydrogenation of a normally gaseous feedstock containing ethylene, acetylene and naptha - Google Patents

Liquid phase selective hydrogenation of a normally gaseous feedstock containing ethylene, acetylene and naptha Download PDF

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EP0334742B1
EP0334742B1 EP89400781A EP89400781A EP0334742B1 EP 0334742 B1 EP0334742 B1 EP 0334742B1 EP 89400781 A EP89400781 A EP 89400781A EP 89400781 A EP89400781 A EP 89400781A EP 0334742 B1 EP0334742 B1 EP 0334742B1
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weight
hydrocarbons
process according
cut
hydrogenated
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EP0334742A1 (en
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Jean Cosyns
Jean-Paul Boitiaux
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used

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  • Thermal conversion processes such as steam cracking, for example, produce olefinic compounds of interest for petrochemicals, but their recovery requires a selective hydrogenation of the acetylene and diolefinic impurities co-produced by these processes.
  • the catalysts used in this hydrogenation are quickly fouled by these polymerization products and the cycle times are therefore disadvantageously very short.
  • Patent application EP-A-135,442 describes a process for the selective hydrogenation of acetylene contained in a mixture of acetylene and ethylene in which said mixture is circulated through a fixed bed of supported palladium catalyst, characterized in that one operates in the presence of a liquid phase containing at least one aromatic hydrocarbon and at least one amino compound dissolved in said liquid phase.
  • US Pat. No. 3,537,981 describes a process for stabilizing pyrolysis gasolines, a two-step process in which the hydrogenation of diolefins and styrenes is carried out and part of the effluents from the first reaction zone are recycled .
  • the object of the present invention is the development of a new process for selective catalytic hydrogenation in the liquid phase of a normally gaseous hydrocarbon charge (that is to say in vapor form at normal temperature and pressure ) containing in particular acetylene, ethylene, gasoline (hydrocarbons C 5 to C 9 ), the liquid phase (or liquid diluent), in the presence of which (which) one operates, comprising at least a portion of the condensable fraction of said charge, that is to say at least part of the gasoline cut (C 5 - C 9 ) hydrogenated, condensed and recycled of said charge.
  • This process allows both the production of a hydrogenated petrol cut and the production of practically pure ethylene (i.e. practically free of acetylene).
  • This hydrogenated cut can also contain a small amount of carbon monoxide, for example between 0.01 and 1% by weight, preferably between 0.02 and 0.2% by weight.
  • the charge to be hydrogenated can, for example, consist of the effluent from an ethane steam cracker.
  • the presence of hydrogen in the feed to be hydrogenated can advantageously avoid working with an external source of hydrogen.
  • the method according to the invention allows more satisfactory operation of the installation, the cycle times being increased in significant proportions and, surprisingly, the quality of the liquid which is recycled to the hydrogenation reactor is improved.
  • the hydrogenated cuts produced in the process meet the most stringent specifications: indeed, the C 2 cut (after hydrogenation and separation) can easily contain less than 5 ppm by weight of acetylene, and the gasoline cut (after hydrogenation and separation) has a "Maleic Anhydride Value" (MAV), which is a measure of the content of conjugated diolefins, determined according to UOP standard No. 356, preferably less than 3.
  • MAV Meleic Anhydride Value
  • the hydrogenation catalyst consists of at least supported palladium.
  • Palladium is generally deposited in an amount of 0.01 to 1% by weight on a suitable support such as, for example, alumina or silica or a mixture of these two constituents.
  • Palladium can be associated with at least one additional metal chosen, for example, from the group formed by silver and gold, with contents which may generally be between 0.01 and 1% of the weight of catalyst.
  • the Au / Pd or Ag / Pd or (Au + Ag) / Pd weight ratio is less than 1.
  • the hydrogenation can be carried out in at least one reactor in which the catalyst is preferably placed in a fixed bed.
  • Figure 1 shows a non-limiting example of application of the invention.
  • the (normally gaseous) cup to be hydrogenated (1) for example the effluent from an ethane steam cracker
  • the liquid diluent (8) and possibly hydrogen (13) in the case where the cup to be hydrogenated does not contain or contains only a very small amount
  • the effluent from said reactor (4) is sent, via line (11), to a distillation column (5) making it possible to separate a gas cut at the top (7) (which contains excess hydrogen and hydrocarbons with less than five carbon atoms, for example methane, the incondensable gas containing excess hydrogen, hydrogenated C 2 , C 3 and C 4 cuts (i.e.
  • This hydrogenated and sampled petrol cut can be used directly as fuel, therefore without transformation, because it contains an extremely small amount of diolefins and therefore of undesirable gums, diolefins which are in fact mainly hydrogenated during the process according to the invention. .
  • the entire catalyst is permanently sprayed with the liquid phase (or liquid diluent) constituting the flow (8) and entering the reactor (4) towards its top.
  • the fresh charge to be hydrogenated can be injected towards the top of the reactor (4), via the pipe (2) and / or halfway up the catalyst by a pipe (3).
  • the recycled liquid (or liquid diluent) phase generally contains at least 25%, preferably 50 to 85% and, even more preferably, 60 to 75% by weight of aromatic hydrocarbons (styrene is not included in the aromatic hydrocarbons).
  • the ratio, at the inlet of the reactor (4), between the weight flow rate of recycled liquid and the weight flow rate of gaseous feed to be hydrogenated is usually between 0.5 and 20, preferably between 1.0 and 10 and, even more preferably, between 1.5 and 5.
  • the catalyst contains 500 ppm by weight of palladium deposited on an alumina support with a specific surface area equal to 9 m 2 / g and a pore volume equal to 0.5 cm 3 / g.
  • the catalyst is placed in a fixed bed in a tubular reactor.
  • the catalyst is rapidly deactivated by fouling and that the hydrogenation reaction is insufficient: in fact, on the one hand, the conversion of acetylene is only 80% after 15 days of operation (acetylene content in cut C 2 : 1.0% by weight at the inlet, 0.2% by weight at the outlet) and, on the other hand, the conversion of the diolefins (and of styrene ) has clearly decreased after 15 days of operation (content of diolefins (and styrene) in the petrol cut: 0.3% by weight after 2 days of operation, 6.0% by weight after 15 days of operation).
  • This catalyst is placed in a fixed bed in a tubular reactor; the unit also includes a distillation column containing 10 trays, the operation of this column is such that the gasoline cut (C 5 - C 9 ) and therefore all the benzene from the feed is found in the bottom racking and at least most of the C 4 - (hydrocarbons with four carbon atoms at most) is found at the top.
  • the bottom liquid is taken up by a pump and constitutes the liquid inlet of the reactor, the cut to be hydrogenated being mixed with this liquid at the inlet of the reactor.
  • the loop is filled with toluene and a small continuous purge on the liquid drawn off at the bottom of the column is carried out during operation, in order to have a constant liquid level in the column.
  • the weight flow rate of recycled liquid is equal to approximately 2.8 times the weight flow rate of gaseous feed to be hydrogenated.
  • Samples to analyze the purged liquid were taken and give the results presented in FIG. 2 (content (% weight) of toluene (continuous curve) and benzene (discontinuous curve) in the withdrawal liquid as a function of time (hour) ). It is noted that after 200 hours the liquid phase has a constant composition which corresponds to the condensable part of the cup to be hydrogenated.
  • the weight composition of the gaseous and liquid effluents respectively at the head and at the bottom of the column after 10 days and after 2 months of operation is indicated respectively in Tables 8 and 9.

Abstract

Process for selective hydrogenation in a liquid phase of an effluent originating from an ethane steam cracker, in which the said effluent is brought into contact with a catalyst consisting of at least supported palladium, characterised in that the operation is carried out in the presence of a liquid phase containing at least a proportion of the hydrogenated, condensed and recycled petrol cut of the said effluent. <??>The said effluent (1), the said liquid phase (8) and optionally hydrogen (13) pass through the hydrogenation reactor (4). The product obtained is fractionated (5) into a head gas cut (7) containing ethylene and a bottom liquid petrol cut which is partially recycled (8). <??>The process can be employed for the production of ethylene and for the production of petrol. <IMAGE>

Description

Les procédés thermiques de conversion tels que le vapocraquage, par exemple, produisent des composés oléfiniques intéressants pour la pétrochimie, mais leur valorisation exige une hydrogénation sélective des impuretés acétyléniques et dioléfiniques coproduites par ces procédés.Thermal conversion processes such as steam cracking, for example, produce olefinic compounds of interest for petrochemicals, but their recovery requires a selective hydrogenation of the acetylene and diolefinic impurities co-produced by these processes.

Ces hydrogénations sont généralement effectuées sur des coupes partielles comme, par exemple, la coupe C2 contenant l'éthylène et l'acétylène, la coupe C3 contenant le propylène, le propyne et le propadiène, la coupe C4 contenant les butènes et le butadiène et la coupe essence contenant des aromatiques, d'autres oléfines et d'autres dioléfines. [voir par exemple A. CHAUVEL et al. Procédés de Pétrochimie Caractéristiques techniques et économiques. Tome 1. Edition TECHNIP (1985)].These hydrogenations are generally carried out on partial cuts such as, for example, the C 2 cut containing ethylene and acetylene, the C 3 cut containing propylene, propyne and propadiene, the C 4 cut containing butenes and butadiene and the gasoline cut containing aromatics, other olefins and other diolefins. [see for example A. CHAUVEL et al. Petrochemical processes Technical and economic characteristics. Volume 1. TECHNIP Edition (1985)].

De tels traitements séparés ne sont possibles que si les quantités relatives de ces coupes sont voisines, ce qui est le cas lorsque la charge du vapocraqueur est du naphta ou du gazole. Lorsque la charge est constituée par de l'éthane, l'effluent du vapocraqueur comprend essentiellement des hydrocarbures en C2 (hydrocarbures à 2 atomes de carbone), les coupes les plus lourdes (C4 et essence) étant nettement minoritaires. Il est d'une pratique courante de séparer alors grossièrement les liquides condensables et d'envoyer l'ensemble de l'effluent gazeux sur un catalyseur d'hydrogénation pour valoriser l'éthylène produit. La composition pondérale de cet effluent de vapocraqueur d'éthane est donnée dans le tableau 1.

Figure imgb0001
Such separate treatments are only possible if the relative amounts of these cuts are close, which is the case when the charge of the steam cracker is naphtha or diesel. When the charge consists of ethane, the steam cracker effluent essentially comprises C 2 hydrocarbons (hydrocarbons with 2 carbon atoms), the heaviest cuts (C 4 and petrol) being clearly in the minority. It is common practice to roughly separate the condensable liquids and to send all of the gaseous effluent to a hydrogenation catalyst to recover the ethylene produced. The weight composition of this ethane steam cracker effluent is given in Table 1.
Figure imgb0001

A 15°C, sous 20 bars (2000 KPa) de pression, un tel effluent est entièrement gazeux : l'hydrogénation doit donc être effectuée en phase gazeuse. Or, les parties les plus lourdes de cette coupe (C4 et essence) contiennent des composés hautement polymérisables tels que le butadiène, l'isoprène et le styrène comme l'indiquent les tableaux 2 et 3 dans lesquels on donne les compositions types des coupes C4 et essence.

Figure imgb0002
At 15 ° C, under 20 bars (2000 KPa) of pressure, such an effluent is entirely gaseous: the hydrogenation must therefore be carried out in the gas phase. However, the heaviest parts of this cut (C 4 and gasoline) contain highly polymerizable compounds such as butadiene, isoprene and styrene as indicated in Tables 2 and 3 in which the typical compositions of the cuts are given. C 4 and gasoline.
Figure imgb0002

Les catalyseurs utilisés dans cette hydrogénation sont rapidement encrassés par ces produits de polymérisation et les durées de cycle sont, alors, désavantageusement très courtes.The catalysts used in this hydrogenation are quickly fouled by these polymerization products and the cycle times are therefore disadvantageously very short.

La demande de brevet EP-A-135.442 décrit un procédé d'hydrogénation sélective de l'acétylène contenu dans un mélange d'acétylène et d'éthylène dans lequel ledit mélange est mis en circulation à travers un lit fixe de catalyseur de palladium supporté, caractérisé en ce que l'on opère en présence d'une phase liquide renfermant au moins un hydrocarbure aromatique et au moins un composé aminé dissous dans ladite phase liquide.Patent application EP-A-135,442 describes a process for the selective hydrogenation of acetylene contained in a mixture of acetylene and ethylene in which said mixture is circulated through a fixed bed of supported palladium catalyst, characterized in that one operates in the presence of a liquid phase containing at least one aromatic hydrocarbon and at least one amino compound dissolved in said liquid phase.

Le brevet US-A-3,537,981 décrit un procédé de stabilisation des essences de pyrolyse, procédé à deux étapes dans lequel on procède à l'hydrogénation des dioléfines et des styrènes et à un recyclage d'une partie des effluents de la première zone de réaction.US Pat. No. 3,537,981 describes a process for stabilizing pyrolysis gasolines, a two-step process in which the hydrogenation of diolefins and styrenes is carried out and part of the effluents from the first reaction zone are recycled .

L'objet de la présente invention est la mise au point d'un nouveau procédé d'hydrogénation catalytique sélective en phase liquide d'une charge d'hydrocarbures normalement gazeuse (c'est-à-dire sous forme vapeur à température et pression normales) contenant notamment de l'acétylène, de l'éthylène, de l'essence (hydrocarbures C5 à C9), la phase liquide (ou diluant liquide), en présence de laquelle (duquel) on opère, comprenant au moins une partie de la fraction condensable de ladite charge, c'est-à-dire au moins une partie de la coupe essence (C5 - C9) hydrogénée, condensée et recyclée de ladite charge. Ce procédé permet à la fois la production d'une coupe essence hydrogénée et la production d'éthylène pratiquement pur (c'est-à-dire pratiquement exempt d'acétylène).

Figure imgb0003
The object of the present invention is the development of a new process for selective catalytic hydrogenation in the liquid phase of a normally gaseous hydrocarbon charge (that is to say in vapor form at normal temperature and pressure ) containing in particular acetylene, ethylene, gasoline (hydrocarbons C 5 to C 9 ), the liquid phase (or liquid diluent), in the presence of which (which) one operates, comprising at least a portion of the condensable fraction of said charge, that is to say at least part of the gasoline cut (C 5 - C 9 ) hydrogenated, condensed and recycled of said charge. This process allows both the production of a hydrogenated petrol cut and the production of practically pure ethylene (i.e. practically free of acetylene).
Figure imgb0003

En général, la charge (sous forme vapeur) à hydrogéner peut renfermer :

  • * 0 à 6 %, de préférence 1 à 2,5 % en poids d'hydrogène ;
  • * 0 à 40 %, de préférence 15 à 30 % en poids de méthane ;
  • * 25 à 80 %, de préférence 30 à 45 % en poids d'hydrocarbures en C2 et, en particulier, 0,1 à 5 %, de préférence 0,2 à 2 % en poids d'acétylène et 15 à 75 %, de préférence 20 à 35 % en poids d'éthylène (et par exemple 0 à 25% en poids d'éthane) ;
  • * 0 à 40 %, de préférence 15 à 35 % en poids d'hydrocarbures en C3 ;
  • * 0 à 10 %, de préférence 1 à 6 % en poids d'hydrocarbures en C4, et
  • * 1 à 20 %, de préférence 1 à 7 % en poids d'essence, c'est-à-dire d'hydrocarbures de 5 à 9 atomes de carbone (C5 +) et, en particulier, 0,4 à 11 %, de préférence 0,8 à 6 % en poids d'hydrocarbures aromatiques (à moins de 9 atomes de carbone).
In general, the charge (in vapor form) to be hydrogenated can contain:
  • * 0 to 6%, preferably 1 to 2.5% by weight of hydrogen;
  • * 0 to 40%, preferably 15 to 30% by weight of methane;
  • * 25 to 80%, preferably 30 to 45% by weight of C 2 hydrocarbons and, in particular, 0.1 to 5%, preferably 0.2 to 2% by weight of acetylene and 15 to 75% , preferably 20 to 35% by weight of ethylene (and for example 0 to 25% by weight of ethane);
  • * 0 to 40%, preferably 15 to 35% by weight of C 3 hydrocarbons;
  • * 0 to 10%, preferably 1 to 6% by weight of C 4 hydrocarbons, and
  • * 1 to 20%, preferably 1 to 7% by weight of gasoline, that is to say of hydrocarbons of 5 to 9 carbon atoms (C 5 + ) and, in particular, 0.4 to 11 %, preferably 0.8 to 6% by weight of aromatic hydrocarbons (less than 9 carbon atoms).

Cette coupe à hydrogéner peut également contenir une faible quantité de monoxyde de carbone, par exemple comprise entre 0,01 et 1 % en poids, de préférence entre 0,02 et 0,2 % en poids.This hydrogenated cut can also contain a small amount of carbon monoxide, for example between 0.01 and 1% by weight, preferably between 0.02 and 0.2% by weight.

La charge à hydrogéner peut, par exemple, être constituée par l'effluent d'un vapocraqueur d'éthane.The charge to be hydrogenated can, for example, consist of the effluent from an ethane steam cracker.

La présence d'hydrogène dans la charge à hydrogéner peut éviter avantageusement de travailler avec une source extérieure d'hydrogène.The presence of hydrogen in the feed to be hydrogenated can advantageously avoid working with an external source of hydrogen.

Le procédé selon l'invention permet un fonctionnement plus satisfaisant de l'installation, les durées de cycle étant augmentées dans des proportions importantes et, de façon surprenante, la qualité du liquide que l'on recycle au réacteur d'hydrogénation est améliorée. Les coupes hydrogénées produites dans le procédé répondent aux spécifications les plus sévères : en effet, la coupe C2 (après hydrogénation et séparation) peut aisément renfermer moins de 5 ppm en poids d'acétylène, et la coupe essence (après hydrogénation et séparation) a une "Maleic Anhydride Value" (MAV), qui est une mesure de la teneur en dioléfines conjuguées, déterminée selon la norme UOP n° 356, de préférence inférieure à 3.The method according to the invention allows more satisfactory operation of the installation, the cycle times being increased in significant proportions and, surprisingly, the quality of the liquid which is recycled to the hydrogenation reactor is improved. The hydrogenated cuts produced in the process meet the most stringent specifications: indeed, the C 2 cut (after hydrogenation and separation) can easily contain less than 5 ppm by weight of acetylene, and the gasoline cut (after hydrogenation and separation) has a "Maleic Anhydride Value" (MAV), which is a measure of the content of conjugated diolefins, determined according to UOP standard No. 356, preferably less than 3.

Le catalyseur d'hydrogénation est constitué par au moins du palladium supporté. Le palladium est en général déposé à raison de 0,01 à 1 % en poids sur un support approprié tel que, par exemple, l'alumine ou la silice ou un mélange de ces deux constituants.The hydrogenation catalyst consists of at least supported palladium. Palladium is generally deposited in an amount of 0.01 to 1% by weight on a suitable support such as, for example, alumina or silica or a mixture of these two constituents.

Au palladium peut être associé au moins un métal additionnel choisi, par exemple, dans le groupe formé par l'argent et l'or, à des teneurs qui pourront être comprises en général entre 0,01 et 1 % du poids de catalyseur. De préférence, le rapport pondéral Au/Pd ou Ag/Pd ou (Au + Ag)/Pd est inférieur à 1.Palladium can be associated with at least one additional metal chosen, for example, from the group formed by silver and gold, with contents which may generally be between 0.01 and 1% of the weight of catalyst. Preferably, the Au / Pd or Ag / Pd or (Au + Ag) / Pd weight ratio is less than 1.

L'hydrogénation peut être réalisée dans au moins un réacteur dans lequel le catalyseur est de préférence disposé en lit fixe. La figure 1 présente un exemple non limitatif d'application de l'invention.The hydrogenation can be carried out in at least one reactor in which the catalyst is preferably placed in a fixed bed. Figure 1 shows a non-limiting example of application of the invention.

La coupe (normalement gazeuse) à hydrogéner (1) (par exemple l'effluent d'un vapocraqueur d'éthane), le diluant liquide (8) et éventuellement de l'hydrogène (13) (dans le cas où la coupe à hydrogéner n'en contient pas ou n'en contient qu'une très faible quantité) sont introduits dans le réacteur d'hydrogénation (4). Après refroidissement dans l'échangeur (10), l'effluent dudit réacteur (4) est envoyé, par la conduite (11), dans une colonne à distiller (5) permettant de séparer une coupe gazeuse en tête (7) (qui renferme l'hydrogène en excès et les hydrocarbures à moins de cinq atomes de carbone, par exemple le méthane, la gaz incondensable contenant l'hydrogène en excès, les coupes C2, C3 et C4 hydrogénées (c'est-à-dire la coupe C4 - hydrogénée)) d'une coupe essence (C5 - C9) en fond (éventuellement accompagnée d'une faible quantité des C4 les moins volatils), coupe essence qui va constituer au moins en partie le diluant liquide. Ce diluant liquide est en partie recyclé, c'est-à-dire renvoyé vers le réacteur (4) par la canalisation (8) à travers une pompe (12). L'autre partie de ce solvant est de préférence prélevée (donc purgée) avant son passage par la pompe (12), afin que la quantité totale d'essence contenue dans le système (réacteur (4) + conduites + colonne à distiller (5)) soit sensiblement constante, ce prélèvement (6) constituant la coupe essence hydrogénée du procédé.The (normally gaseous) cup to be hydrogenated (1) (for example the effluent from an ethane steam cracker), the liquid diluent (8) and possibly hydrogen (13) (in the case where the cup to be hydrogenated does not contain or contains only a very small amount) are introduced into the hydrogenation reactor (4). After cooling in the exchanger (10), the effluent from said reactor (4) is sent, via line (11), to a distillation column (5) making it possible to separate a gas cut at the top (7) (which contains excess hydrogen and hydrocarbons with less than five carbon atoms, for example methane, the incondensable gas containing excess hydrogen, hydrogenated C 2 , C 3 and C 4 cuts (i.e. cut C 4 - hydrogenated)) of a gasoline cut (C 5 - C 9 ) at the bottom (possibly accompanied by a small amount of the least volatile C 4 ), gasoline cut which will constitute at least in part the liquid diluent . This liquid diluent is partly recycled, that is to say returned to the reactor (4) by the pipe (8) through a pump (12). The other part of this solvent is preferably removed (therefore purged) before it passes through the pump (12), so that the total amount of gasoline contained in the system (reactor (4) + lines + distillation column (5 )) is substantially constant, this sample (6) constituting the hydrogenated gasoline cut of the process.

Cette coupe essence hydrogénée et prélevée est utilisable directement comme carburant, donc sans transformation, du fait qu'elle contient une quantité extrêmement faible de dioléfines et donc de gommes indésirables, dioléfines qui sont en effet en majeure partie hydrogénées lors du procédé selon l'invention.This hydrogenated and sampled petrol cut can be used directly as fuel, therefore without transformation, because it contains an extremely small amount of diolefins and therefore of undesirable gums, diolefins which are in fact mainly hydrogenated during the process according to the invention. .

On peut de plus facilement, par des méthodes de distillation connues de l'homme de l'art, séparer la coupe C2, puis l'éthylène (qui est un mélange d'éthylène contenu dans la charge de départ et d'éthylène produit par l'hydrogénation de l'acétylène) contenu dans la coupe gazeuse déchargée en tête de la colonne (5) : le procédé selon l'invention permet donc de produire également de l'éthylène.It is more easily possible, by distillation methods known to those skilled in the art, to separate the cut C 2 , then the ethylene (which is a mixture of ethylene contained in the starting charge and of ethylene produced by the hydrogenation of acetylene) contained in the gas fraction discharged at the top of the column (5): the process according to the invention therefore also makes it possible to produce ethylene.

L'ensemble du catalyseur est en permanence arrosé par la phase liquide (ou diluant liquide) constituant le flux (8) et pénètrant dans le réacteur (4) vers son sommet. La charge fraîche à hydrogéner peut être injectée vers le sommet du réacteur (4), par la canalisation (2) et/ou à mi-hauteur du catalyseur par une canalisation (3). Cette disposition permet de faire varier, en cours de fonctionnement, la quantité de catalyseur qui travaille, ce qui rend possible l'ajustement de la réactivité de la masse totale de catalyseur.The entire catalyst is permanently sprayed with the liquid phase (or liquid diluent) constituting the flow (8) and entering the reactor (4) towards its top. The fresh charge to be hydrogenated can be injected towards the top of the reactor (4), via the pipe (2) and / or halfway up the catalyst by a pipe (3). This arrangement makes it possible to vary, during operation, the quantity of catalyst which works, which makes it possible to adjust the reactivity of the total mass of catalyst.

L'implantation éventuelle sur l'entrée liquide du réacteur (4) d'un échangeur à vapeur (9) peut permettre d'ajuster les températures d'entrée dudit réacteur.The possible installation on the liquid inlet of the reactor (4) of a steam exchanger (9) can make it possible to adjust the inlet temperatures of the said reactor.

La phase liquide (ou diluant liquide) recyclée contient généralement au moins 25 %, de préférence 50 à 85 % et, de manière encore plus préférée, 60 à 75 % en poids d'hydrocarbures aromatiques (le styrène n'étant pas comptabilisé dans la catégorie des hydrocarbures aromatiques).The recycled liquid (or liquid diluent) phase generally contains at least 25%, preferably 50 to 85% and, even more preferably, 60 to 75% by weight of aromatic hydrocarbons (styrene is not included in the aromatic hydrocarbons).

Les conditions opératoires de l'hydrogénation, selon l'invention, selon utilement choisies comme suit :

  • pression totale : 10 à 50 bars ;
  • température : 10 à 150 °C ;
  • vitesse spatiale exprimée en débit volumique de coupe gazeuse à hydrogéner, à température et pression normales (TPN), par volume de catalyseur et par heure (VVH gaz) : 500 à 20000, de préférence 1000 à 10000 ;
  • débit volumique de liquide recyclé à température et pression normales (TPN), par volume de catalyseur et par heure (VVH liquide) : 1 à 15, de préférence entre 4 et 12.
The operating conditions for hydrogenation, according to the invention, according to usefully chosen as follows:
  • total pressure: 10 to 50 bars;
  • temperature: 10 to 150 ° C;
  • space speed expressed in volume flow rate of gas cut to be hydrogenated, at normal temperature and pressure (TPN), by volume of catalyst and per hour (VVH gas): 500 to 20,000, preferably 1,000 to 10,000;
  • volume flow rate of recycled liquid at normal temperature and pressure (TPN), by volume of catalyst and per hour (VVH liquid): 1 to 15, preferably between 4 and 12.

Dans ces conditions de VVH gaz et de VVH liquide, le rapport, à l'entrée du réacteur (4), entre le débit pondéral de liquide recyclé et le débit pondéral de charge gazeuse à hydrogéner est habituellement compris entre 0,5 et 20, de préférence entre 1,0 et 10 et, de manière encore plus préférée, entre 1,5 et 5.Under these VVH gas and VVH liquid conditions, the ratio, at the inlet of the reactor (4), between the weight flow rate of recycled liquid and the weight flow rate of gaseous feed to be hydrogenated is usually between 0.5 and 20, preferably between 1.0 and 10 and, even more preferably, between 1.5 and 5.

Les exemples suivants illustrent de manière non limitative la présente invention.The following examples illustrate, without limitation, the present invention.

Exemple 1.Example 1.

Dans cet exemple qui illustre une technique de l'art antérieur, on traite une coupe normalement gazeuse dont la composition en poids est donnée dans le tableau 4. On n'utilise pas de diluant liquide.

Figure imgb0004
Figure imgb0005
 In this example which illustrates a technique of the prior art, a normally gaseous cut is treated, the composition by weight of which is given in Table 4. No liquid diluent is used.
Figure imgb0004
Figure imgb0005

Le catalyseur contient 500 ppm en poids de palladium déposé sur un support d'alumine de surface spécifique égale à 9 m2/g et de volume poreux égal à 0,5 cm3/g. Le catalyseur est disposé en lit fixe dans un réacteur tubulaire.The catalyst contains 500 ppm by weight of palladium deposited on an alumina support with a specific surface area equal to 9 m 2 / g and a pore volume equal to 0.5 cm 3 / g. The catalyst is placed in a fixed bed in a tubular reactor.

On fait passer la coupe à hydrogéner dans ce réacteur dans les conditions opératoires suivantes :

  • VVH gaz : 2500 (TPN) ;
  • Pression : 20 bars ;
  • Température : 40°C.
The section to be hydrogenated is passed through this reactor under the following operating conditions:
  • VVH gas: 2500 (TPN);
  • Pressure: 20 bars;
  • Temperature: 40 ° C.

La composition pondérale de l'effluent sortant du réacteur après 2 jours et 15 jours de fonctionnement est indiquée dans le tableau 6 pour la coupe C2 et le tableau 7 pour l'essence produite (C5 - C9).

Figure imgb0006
Figure imgb0007
 The weight composition of the effluent leaving the reactor after 2 days and 15 days of operation is shown in Table 6 for section C 2 and Table 7 for the gasoline produced (C 5 - C 9 ).
Figure imgb0006
Figure imgb0007

On constate ainsi que, dans ces conditions, le catalyseur est rapidement désactivé par encrassement et que la réaction d'hydrogénation est insuffisante : en effet, d'une part la conversion de l'acétylène n'est plus que de 80 % au bout de 15 jours de fonctionnement (teneur en acétylène dans la coupe C2 : 1,0 % en poids à l'entrée, 0,2 % en poids à la sortie) et, d'autre part, la conversion des dioléfines (et du styrène) a nettement diminué après 15 jours de fonctionnement (teneur en dioléfines (et styrène) dans la coupe essence : 0,3 % en poids après 2 jours de fonctionnement, 6,0 % en poids après 15 jours de fonctionnement).It can thus be seen that, under these conditions, the catalyst is rapidly deactivated by fouling and that the hydrogenation reaction is insufficient: in fact, on the one hand, the conversion of acetylene is only 80% after 15 days of operation (acetylene content in cut C 2 : 1.0% by weight at the inlet, 0.2% by weight at the outlet) and, on the other hand, the conversion of the diolefins (and of styrene ) has clearly decreased after 15 days of operation (content of diolefins (and styrene) in the petrol cut: 0.3% by weight after 2 days of operation, 6.0% by weight after 15 days of operation).

La seule possibilité d'augmenter la conversion serait d'élever la température de fonctionnement, ce qui nuirait inévitablement au rendement en oléfines et accélèrerait encore l'encrassement du catalyseur.The only possibility to increase the conversion would be to raise the operating temperature, which would inevitably harm the olefin yield and further accelerate fouling of the catalyst.

Exemple 2 (selon l'invention). Example 2 (according to the invention).

On traite la même charge que dans l'exemple 1, le catalyseur utilisé étant également le même.The same charge is treated as in Example 1, the catalyst used also being the same.

Ce catalyseur est disposé en lit fixe dans un réacteur tubulaire ; l'unité comporte également une colonne à distiller contenant 10 plateaux, le fonctionnement de cette colonne est tel que la coupe essence (C5 - C9) et donc tout le benzène de l'alimentation se retrouvent dans le soutirage de fond et au moins la majeure partie des C4 - (hydrocarbures à quatre atomes de carbone au plus) se retrouve en tête. Le liquide de fond est repris par une pompe et constitue l'entrée liquide du réacteur, la coupe à hydrogéner étant mélangée à ce liquide à l'entrée du réacteur.This catalyst is placed in a fixed bed in a tubular reactor; the unit also includes a distillation column containing 10 trays, the operation of this column is such that the gasoline cut (C 5 - C 9 ) and therefore all the benzene from the feed is found in the bottom racking and at least most of the C 4 - (hydrocarbons with four carbon atoms at most) is found at the top. The bottom liquid is taken up by a pump and constitutes the liquid inlet of the reactor, the cut to be hydrogenated being mixed with this liquid at the inlet of the reactor.

Au démarrage de l'unité, la boucle est remplie de toluène et une petite purge en continu sur le liquide soutiré en fond de colonne est effectuée en cours d'opération, afin d'avoir un niveau liquide constant dans la colonne.When the unit starts, the loop is filled with toluene and a small continuous purge on the liquid drawn off at the bottom of the column is carried out during operation, in order to have a constant liquid level in the column.

Les conditions opératoires sont les suivantes :

  • VVH gaz : 2500 (TPN) ;
  • Pression : 20 bars ;
  • Température : 40 °C ;
  • VVH liquide : 10 (TPN).
The operating conditions are as follows:
  • VVH gas: 2500 (TPN);
  • Pressure: 20 bars;
  • Temperature: 40 ° C;
  • Liquid VVH: 10 (TPN).

Avec ces conditions de VVH gaz et liquide, le débit pondéral de liquide recyclé est égal à environ 2,8 fois le débit pondéral de charge gazeuse à hydrogéner. Des prélèvements pour analyser le liquide purgé ont été effectués et donnent les résultats présentés sur la figure 2 (teneur (% poids) de toluène (courbe continue) et de benzène (courbe discontinue) dans le liquide de soutirage en fonction du temps (heure)). On constate qu'au bout de 200 heures la phase liquide a une composition constante qui correspond à la partie condensable de la coupe à hydrogéner. La composition pondérale des effluents gazeux et liquide respectivement en tête et en fond de colonne après 10 jours et après 2 mois de fonctionnement est indiquée respectivement dans les tableaux 8 et 9.

Figure imgb0008
Figure imgb0009
 With these VVH gas and liquid conditions, the weight flow rate of recycled liquid is equal to approximately 2.8 times the weight flow rate of gaseous feed to be hydrogenated. Samples to analyze the purged liquid were taken and give the results presented in FIG. 2 (content (% weight) of toluene (continuous curve) and benzene (discontinuous curve) in the withdrawal liquid as a function of time (hour) ). It is noted that after 200 hours the liquid phase has a constant composition which corresponds to the condensable part of the cup to be hydrogenated. The weight composition of the gaseous and liquid effluents respectively at the head and at the bottom of the column after 10 days and after 2 months of operation is indicated respectively in Tables 8 and 9.
Figure imgb0008
Figure imgb0009

On constate que contrairement à l'exemple 1, les performances de l'hydrogénation sont stables. En effet, au bout de 2 mois, les résultats sont voisins des résultats initiaux (voir tableau 10).

Figure imgb0010
It can be seen that, unlike Example 1, the hydrogenation performance is stable. Indeed, after 2 months, the results are close to the initial results (see Table 10).
Figure imgb0010

Claims (10)

1 Process for producing hydrogenated gasoline cut and pure ethylene from a normally gaseous hydrocarbon feed containing at least ethylene, acetylene and from 1 to 20% by weight of a gasoline cut (hydrocarbons from C5 to C9) comprising among others aromatic hydrocarbons and diolefins and/or styrene, said process including :
a) the selective hydrogenation of said feed in vapor form by contact with a catalyst consisting of at least supported palladium, in the presence of a liquid phase containing at least part of the hydrogenated gasoline cut, Condensed and recycled, said hydrogenation being carried out at a total pressure comprised between 10 and 50 bars, a temperature comprised between 10 and 150°C, a space velocity expressed as volume flow rate of the cut to be hydrogenated per volume of catalyst and per hour comprised between 500 and 20 000, a volume flow rate of the recycled liquid per volume of catalyst and per hour comprised between 1 and 15, and a ratio of the weight flow rate of said liquid diluent to the weight flow rate of the feed to be hydrogenated comprised between 0,5 and 20,
b) the separation from the effluent from the hydrogenation step of a gaseous cut comprising hydrocarbons from C1 to C4 and a gasoline cut comprising hydrocarbons from C5 to C9,
c) the recycle of a part of the gasoline cut to the hydrogenation reactor.
2. Process according to claim 1 wherein said hydrocarbon feed contains 0 to 6 % in weight of hydrogen, 0 to 40 % in weight of methane, 25 to 80 % in weight of C2 hydrocarbons, in particular 0.1 to 5 % in weight of acetylene and 15 to 75 % in weight of ethylene, 0 to 40 % in weight of C3 hydrocarbons, 0 to 10 % in weight of C4 hydrocarbons.
3. Process according to claim 1 wherein said hydrocarbon feed contains 1 to 2.5 % in weight of hydrogen, 15 to 30 % in weight of methane, 30 to 45 % in weight of C2 hydrocarbons, in particular 0.2 to 2 % in weight of acetylene and 20 to 35 % in weight of ethylene, 15 to 35 % in weight of C3 hydrocarbons, 1 to 6 % in weight of C4 hydrocarbons and 1 to 7 % in weight of gasoline.
4. Process according to one of claims 1 to 3 wherein said hydrocarbon feed is an effluent originating from an ethane steam cracker.
5. Process according to one of claims 1 to 4 characterized in that said liquid phase contains at least 25 % in weight of aromatic hydrocarbons.
6. Process according to claim 5 characterized in that said liquid phase contains 50 to 85 % in weight of aromatic hydrocarbons.
7. Process according to one of claims 1 to 6 wherein said catalyst consist of palladium and at least one additional metal chosen from the group formed by gold and silver, the mixture of palladium and at least one additional metal being deposited on at least one support chosen from the group formed by alumina and silica.
8. Process according to one of claims 1 to 7 characterized in that the ratio of weight flow rate of said liquid phase to the weight flow rate of said feed to be hydrogenated is ranging from 0.5 to 20.
9. Process according to claim 8 characterized in that said ratio is ranging from 1 to 10.
10. Use of the process according to one of claims 1 to 9 for the production of ethylene and for the production of gasoline.
EP89400781A 1988-03-23 1989-03-20 Liquid phase selective hydrogenation of a normally gaseous feedstock containing ethylene, acetylene and naptha Expired - Lifetime EP0334742B1 (en)

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FR8803909A FR2629094B1 (en) 1988-03-23 1988-03-23 PROCESS FOR THE SELECTIVE CATALYTIC HYDROGENATION IN THE LIQUID PHASE OF A NORMALLY GASEOUS FILLER CONTAINING ETHYLENE, ACETYLENE AND GASOLINE

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JP2736799B2 (en) 1998-04-02
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