EP0685552A1 - Process and installation for the selective hydrogenation of catalytic cracking gasoline - Google Patents
Process and installation for the selective hydrogenation of catalytic cracking gasoline Download PDFInfo
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- EP0685552A1 EP0685552A1 EP95401244A EP95401244A EP0685552A1 EP 0685552 A1 EP0685552 A1 EP 0685552A1 EP 95401244 A EP95401244 A EP 95401244A EP 95401244 A EP95401244 A EP 95401244A EP 0685552 A1 EP0685552 A1 EP 0685552A1
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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
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
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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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
Definitions
- the decrease in the concentration of olefins is often obtained by etherification of 2-methyl butenes into tertioamylmethyl ether or even sometimes of 2-methylpentenes and 3-methylpentene-2 into tertiohexylmethylether.
- Etherification is therefore an elegant way of reducing the content of olefins while transforming them into ethers with high research and motor octane numbers.
- a process has therefore been developed which makes it possible to selectively hydrogenate the diolefins to corresponding olefins, and to carry out, together with the hydrogenation of the diolefins, isomerization at least in part of the primary and / or secondary olefins to tertiary olefins and for example the isomerization of non-etherifiable 3-methylbutene-1 into etherifiable 2-methylbutene-2.
- the subject of the invention is a method of treatment by selective hydrogenation of catalytic cracking gasoline, by bringing the C5 -210 ° C cut into contact with a catalyst comprising 0.1 to 1% of palladium deposited on a support, under a pressure of 4-25 bar, at a temperature of 80-200 ° C, with an hourly space velocity of the liquid (LHSV) from 1 to h ⁇ 1.
- a catalyst comprising 0.1 to 1% of palladium deposited on a support, under a pressure of 4-25 bar, at a temperature of 80-200 ° C, with an hourly space velocity of the liquid (LHSV) from 1 to h ⁇ 1.
- the catalyst must comprise palladium (0.1 to 1% by weight, and preferably 0.2-0.5% by weight) deposited on a support containing at least 50% of alumina, and preferably at least 90%, and advantageously this support is pure alumina.
- Another metal can be combined to form a bimetallic catalyst, such as gold (Au / Pd expressed by weight greater than or equal to 0.1 and less than 1, and preferably between 0.2 and 0.8).
- a bimetallic catalyst such as gold (Au / Pd expressed by weight greater than or equal to 0.1 and less than 1, and preferably between 0.2 and 0.8).
- the catalyst thus essentially comprises palladium or palladium and gold.
- the choice of operating conditions is particularly important. Most generally, it will be operated under pressure in the presence of a quantity of hydrogen in slight excess relative to the stoichiometric value necessary for hydrogenating the diolefins.
- the hydrogen and the feed to be treated are injected in ascending or descending currents into a reactor preferably with a fixed bed of catalyst.
- the temperature is most generally between 80 and 200 ° C, in particular between 130 and 200 ° C and preferably between 150 and 170 ° C.
- the pressure is sufficient to keep most of the gasoline to be treated in the liquid phase in the reactor, namely most generally between 4 and 25 bar and preferably above 10 bar.
- An advantageous pressure is between 10-20 bar, and preferably between 12-16 bar.
- the space speed is in these conditions established between 1-10 h ⁇ 1, preferably less than 10 h ⁇ 1 and better between 4 and less than -10 h ⁇ 1.
- the invention relates exclusively to catalytic cracking gasolines.
- the catalytic cracking gasoline fraction generally contains from 15 to 40% of olefins (olefins, diolefins and cycloolefins) with a content of conjugated diolefins of less than 5% and generally of at least plus 4%.
- olefins olefins, diolefins and cycloolefins
- conjugated diolefins of less than 5% and generally of at least plus 4%.
- the content of dienes is reduced to less than 1000 ppm.
- the diene content in cuts C5 and C6 after selective hydrogenation is generally reduced to less than 250 ppm.
- the content of cyclopentadiene in a catalytic cracking gasoline is less than 1% by weight, and generally less than 0.5% by weight, while it can be 20% by weight in a steam cracking gasoline.
- the mercaptan content is between 1 and 300 ppm, and generally less than 200 ppm.
- the subject of the invention is also an installation for the treatment by selective hydrogenation of a catalytic cracking gasoline comprising a catalytic cracking unit followed by a fractionation unit for separating the fraction C3-210 ° C, a debutanizer, then a separation unit chosen from a depentanizer and a dehexanizer, said installation comprising a selective hydrogenation unit placed between the debutanizer and the separation unit.
- Figure 1 shows schematically the method and the installation according to the invention.
- an effluent leaves which is fractionated in a unit 2 for fractionation into a diesel cut (LCO), a heavy cut (HCO) and a cut containing the hydrocarbons.
- LCO diesel cut
- HCO heavy cut
- the cut C5-180 ° C obtained (or the cut C5-160 ° C or C5-210 ° C depending on the fractionation carried out), called gasoline cut C 5 + of catalytic cracking, is introduced into a zone (or unit) 4 of selective hydrogenation according to the invention, hydrogen is also introduced for example by line 5.
- the hydrogenated cut obtained enters the separation unit 6 which is a depentanizer (C5 separation) or a dehexanizer (C5-C6 separation).
- C5 separation a depentanizer
- C5-C6 separation a dehexanizer
- a C5 fraction or a C5-C6 fraction is therefore obtained, which is advantageously sent to the etherification unit, and a C 7 fraction. + sent to petrol storage.
- the catalytic hydrogenation reactor 10 comprises a crossed catalytic reaction zone by the total charge and the quantity of hydrogen necessary to carry out the desired reactions.
- the catalytic hydrogenation reactor 10 is arranged in a particular way as indicated in FIG. 2, namely two catalytic zones 11 and 12, the first 11 being crossed by the liquid charge (and a quantity of hydrogen, supplied by a pipe 5, less than the stoichiometry necessary to convert all the diolefins into mono olefins) entering through the pipe 15; in this first zone, softening also takes place; the second 12 receiving the liquid charge coming from the first zone (as well as the rest of the hydrogen, that is to say a quantity of hydrogen sufficient to convert the remaining diolefins into mono olefins and to at least partially isomerize the primary and secondary olefins into tertiary olefins) for example injected through a lateral tube 13 and dispersed using an appropriate diffuser 14.
- the proportion of the first zone (by volume) is at most equal to 50% of the sum of the 2 zones and preferably from 15 to 30%.
- the hydrogenation unit can operate at pressures lower than those required by the debutanizer and since the depentanizer (or dehexanizer) does not require a pressure of 13 to 15 bar, the circulation of the charge through the installation is obtained by a slight depressurization at the outlet of the hydrogenation unit. This allows operation without additional pumps.
- the high temperature of the debutanizer base and the high activity of the catalysts used in the invention allow the selective hydrogenation unit to cut C 5 + catalytic cracking to operate without a charge preheating furnace and to be very compact. This leads to a unit with low investment and great flexibility which gives it unique advantages.
- the new process according to the invention for the selective hydrogenation of catalytic cracked petrol requires neither charge or recycling pumps, nor preheating furnace.
- the new process offers much greater flexibility by isolating the catalyst from the distillation column, allowing the catalyst to be replaced without stopping the units located downstream. It also allows the catalyst to provide greater activity, thanks to higher temperatures and pressures than those obtained in the depentaniser.
- the new process makes it possible to simultaneously treat cuts C5, C6 and C7-210 ° C. This therefore allows the pretreatment before etherification of the C5 and C6 cuts thanks to a selective flexible and inexpensive hydrogenation. This process makes it possible to obtain the maximum of precursors of ethers in C5 and C6 and moreover decreases the quantity of antioxidants to be used in the treated gasoline.
- This process therefore makes it possible to improve the quantity of etherifiable products, therefore the production yield of ethers such as tertioamyl ether for example. It also improves the quality of the gasoline produced, which has better oxidation stability and an improved octane number.
- catalyst LD265 from the company Procatalyse containing 0.3% by weight of palladium supported on alumina in a stainless steel tube 1.9 cm in diameter. This catalyst is commonly used for the hydrogenation of C3 and C4 cuts of FCC and steam cracking.
- the catalyst is activated by reduction under hydrogen at a flow rate of 30 l / h for 5 hours at 200 ° C.
- the installation is cooled under nitrogen to 150 ° C. before injecting the FCC gasoline having the properties indicated in table 1.
- the reactor is then pressurized to 14 bar and the gasoline is injected into the bottom of the reactor (100 cm3 / hour so a VVH of 1 h ⁇ 1).
- the effect of space velocity is determined by increasing the VVH at 5 h ⁇ 1 (example 2) then at 10 h ⁇ 1 (example 3) while keeping the H2 / diolefin molar ratio to 1.6.
- Example 4 The effect of reducing the H2 / diolefin molar ratio is shown in Example 4 where this ratio is 1.4 and the liquid VVH is 10 h ⁇ 1.
- the catalytic zone is cut into two separate beds, therefore 25 cm3 in the first zone and 75 cm3 of LD265 in the second.
- the procedure is as previously described in Example 4 except the quantity of hydrogen injected into the reactor with the feed represents a molar ratio of 0.9.
- An injection device between the two beds allows adding an additional quantity of hydrogen corresponding to a molar ratio of 0.5 relative to the quantity of diolefins initially present in the raw FCC gasoline, Example 5.
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Abstract
Description
La production d'essence reformulée répondant aux nouvelles normes d'environnement nécessite notamment que l'on diminue leur concentration en oléfines, en aromatiques (surtout le benzène) et en soufre.The production of reformulated petrol meeting new environmental standards requires in particular that their concentration of olefins, aromatics (especially benzene) and sulfur be reduced.
La diminution de la concentration en oléfines est souvent obtenue par éthérification des 2-méthyl butènes en tertioamylméthyléther voire parfois des 2-méthylpentènes et 3-méthylpentène-2 en tertiohexylméthyléther.The decrease in the concentration of olefins is often obtained by etherification of 2-methyl butenes into tertioamylmethyl ether or even sometimes of 2-methylpentenes and 3-methylpentene-2 into tertiohexylmethylether.
L'éthérification est ainsi une manière élégante de diminuer la teneur en oléfines tout en les transformant en éthers à hauts indices d'octane recherche et moteur.Etherification is therefore an elegant way of reducing the content of olefins while transforming them into ethers with high research and motor octane numbers.
Cependant, la présence de dioléfines dans les essences de craquage catalytique entraîne une désactivation du catalyseur d'éthérification par formation de gommes, celles-ci provoquant également une dégradation de la qualité de l'éther produit.However, the presence of diolefins in the catalytic cracking gasolines leads to deactivation of the etherification catalyst by the formation of gums, these also causing a degradation in the quality of the ether produced.
On a donc développé un procédé qui permet d'hydrogéner sélectivement les dioléfines en oléfines correspondantes, et de réaliser conjointement à l'hydrogénation des dioléfines l'isomérisation au moins en partie des oléfines primaires et/ou secondaires en oléfines tertiaires et par exemple l'isomérisation du 3-méthylbutène-1 non éthérifiable en 2-méthylbutène-2 éthérifiable.A process has therefore been developed which makes it possible to selectively hydrogenate the diolefins to corresponding olefins, and to carry out, together with the hydrogenation of the diolefins, isomerization at least in part of the primary and / or secondary olefins to tertiary olefins and for example the isomerization of non-etherifiable 3-methylbutene-1 into etherifiable 2-methylbutene-2.
On a aussi découvert qu'il est possible d'adoucir au moins en partie l'essence de craquage catalytique par transformation des mercaptans en autre produits sulfurés grâce aux conditions particulières de l'invention et un agencement particulier du réacteur catalytique de la présente invention. Par adoucissement, on comprend une réaction d'addition d'oléfine sur un mercaptan.It has also been discovered that it is possible to at least partially soften the gasoline of catalytic cracking by transformation of the mercaptans into other sulfurized products thanks to the particular conditions of the invention and a particular arrangement of the catalytic reactor of the present invention. By softening, we understand an olefin addition reaction on a mercaptan.
Plus précisément, l'invention a pour objet un procédé de traitement par hydrogénation sélective de l'essence de craquage catalytique, par mise au contact de la coupe C₅ -210°C avec un catalyseur comprenant 0,1 à 1 % de palladium déposé sur un support, sous une pression de 4-25 bar, à une température de 80-200 °C, avec un vitesse spatiale horaire du liquide (LHSV) de 1 à h⁻¹.More specifically, the subject of the invention is a method of treatment by selective hydrogenation of catalytic cracking gasoline, by bringing the C₅ -210 ° C cut into contact with a catalyst comprising 0.1 to 1% of palladium deposited on a support, under a pressure of 4-25 bar, at a temperature of 80-200 ° C, with an hourly space velocity of the liquid (LHSV) from 1 to h⁻¹.
Le catalyseur doit comporter du palladium (0,1 à 1 % poids, et de préférence 0,2-0,5 % poids) déposé sur un support contenant au moins 50% d'alumine, et de préférence au moins 90%, et avantageusement ce support est de l'alumine pure.The catalyst must comprise palladium (0.1 to 1% by weight, and preferably 0.2-0.5% by weight) deposited on a support containing at least 50% of alumina, and preferably at least 90%, and advantageously this support is pure alumina.
Un autre métal peut être associé pour former un catalyseur bimétallique, tel que l'or (Au/Pd exprimé en poids supérieur ou égal à 0,1 et inférieur à 1, et de préférence compris entre 0,2 et 0,8).Another metal can be combined to form a bimetallic catalyst, such as gold (Au / Pd expressed by weight greater than or equal to 0.1 and less than 1, and preferably between 0.2 and 0.8).
Le catalyseur comporte ainsi essentiellement du palladium ou du palladium et de l'or.The catalyst thus essentially comprises palladium or palladium and gold.
Le choix des conditions opératoires est particulièrement important. On opérera le plus généralement sous pression en présence d'une quantité d'hydrogène en faible excès par rapport à la valeur stoechiométrique nécessaire pour hydrogéner les dioléfines. L'hydrogène et la charge à traiter sont injectés en courants ascendants ou descendants dans un réacteur de préférence à lit fixe de catalyseur. La température est comprise le plus généralement entre 80 et 200 °C, en particulier entre 130 et 200 °C et de préférence entre 150 et 170 °C.The choice of operating conditions is particularly important. Most generally, it will be operated under pressure in the presence of a quantity of hydrogen in slight excess relative to the stoichiometric value necessary for hydrogenating the diolefins. The hydrogen and the feed to be treated are injected in ascending or descending currents into a reactor preferably with a fixed bed of catalyst. The temperature is most generally between 80 and 200 ° C, in particular between 130 and 200 ° C and preferably between 150 and 170 ° C.
La pression est suffisante pour maintenir la majeure partie de l'essence à traiter en phase liquide dans le réacteur à savoir le plus généralement entre 4 et 25 bar et de préférence au-dessus de 10 bar. Une pression avantageuse est comprise entre 10-20 bar, et de préférence entre 12-16 bar.The pressure is sufficient to keep most of the gasoline to be treated in the liquid phase in the reactor, namely most generally between 4 and 25 bar and preferably above 10 bar. An advantageous pressure is between 10-20 bar, and preferably between 12-16 bar.
La vitesse spatiale est dans ces conditions établie entre 1-10 h⁻¹, de préférence inférieure à 10 h⁻¹ et mieux entre 4 et moins de -10 h⁻¹.The space speed is in these conditions established between 1-10 h⁻¹, preferably less than 10 h⁻¹ and better between 4 and less than -10 h⁻¹.
On peut également injecter avec cette essence des traces d'oxygène en très faible concentration à savoir de l'ordre de 100 à 500 ppm mole.It is also possible to inject with this essence traces of oxygen in very low concentration, namely of the order of 100 to 500 ppm mole.
L'invention concerne exclusivement des essences de craquage catalytique.The invention relates exclusively to catalytic cracking gasolines.
Contrairement aux essences de pyrolyse qui contiennent environ 50% de dioléfines la coupe essence de craquage catalytique contient généralement de 15 à 40 % d'oléfines (oléfines, dioléfines et cyclooléfines) avec une teneur en dioléfines conjuguées inférieure à 5% et généralement d'au plus 4%. Après hydrogénation, la teneur en diènes est réduite à moins de 1000 ppm. La teneur en diène dans les coupes C5 et C6 après hydrogénation sélective est généralement réduite à moins de 250 ppm.Unlike pyrolysis essences which contain around 50% of diolefins, the catalytic cracking gasoline fraction generally contains from 15 to 40% of olefins (olefins, diolefins and cycloolefins) with a content of conjugated diolefins of less than 5% and generally of at least plus 4%. After hydrogenation, the content of dienes is reduced to less than 1000 ppm. The diene content in cuts C5 and C6 after selective hydrogenation is generally reduced to less than 250 ppm.
La teneur en cyclopentadiène dans une essence de craquage catalytique est inférieure à 1% pds, et généralement inférieure à 0,5% pds, alors qu'elle peut être de 20% pds dans une essence de vapocraquage.The content of cyclopentadiene in a catalytic cracking gasoline is less than 1% by weight, and generally less than 0.5% by weight, while it can be 20% by weight in a steam cracking gasoline.
La teneur en mercaptan est comprise entre 1 et 300 ppm, et généralement inférieure à 200 ppm.The mercaptan content is between 1 and 300 ppm, and generally less than 200 ppm.
Ces conditions particulières permettent d'opérer directement en aval du débutaniseur de l'essence de craquage catalytique sans qu'il soit nécessaire d'adjoindre un préchauffeur ou une pompe de charge, et avec de préférence un seul réacteur.These particular conditions make it possible to operate directly downstream of the debutanizer of the catalytic cracking gasoline without the need to add a preheater or a charge pump, and preferably with a single reactor.
L'invention a également pour objet une installation de traitement par hydrogénation sélective d'une essence de craquage catalytique comprenant une unité de craquage catalytique suivie d'une unité de fractionnement pour séparer la fraction C₃-210 °C, un débutaniseur, puis une unité de séparation choisie parmi un dépentaniseur et un déhexaniseur, ladite installation comportant une unité d'hydrogénation sélective placée entre le débutaniseur et l'unité de séparation.The subject of the invention is also an installation for the treatment by selective hydrogenation of a catalytic cracking gasoline comprising a catalytic cracking unit followed by a fractionation unit for separating the fraction C₃-210 ° C, a debutanizer, then a separation unit chosen from a depentanizer and a dehexanizer, said installation comprising a selective hydrogenation unit placed between the debutanizer and the separation unit.
La figure 1 schématise le procédé et l'installation selon l'invention.Figure 1 shows schematically the method and the installation according to the invention.
De l'unité de craquage catalytique 1 , par exemple un craquage catalytique en lit fluide, sort un effluent qui est fractionné dans une unité 2 de fractionnement en une coupe gazole (LCO), une coupe lourde (HCO) et une coupe contenant les hydrocarbures C₃ à 210 °C, de préférence C₃ à 180 °C et avantageusement C₃ à 160 °C et de façon la plus préférée C₃ à <160 °C (c'est-à-dire point final de coupe de 160 °C).From the
Dans la figure 1, une coupe C₃-180°C est envoyée au débutaniseur 3 pour séparer la fraction C₃-C₄.In Figure 1, a C₃-180 ° C section is sent to the
La coupe C₅-180°C obtenue (ou la coupe C₅-160 °C ou C₅-210 °C selon le fractionnement opéré), appelée coupe essence C5
La coupe hydrogénée obtenue entre dans l'unité 6 de séparation qui est un dépentaniseur (séparation C₅) ou un déhexaniseur (séparation C₅-C₆). Il est obtenu donc une fraction C₅ ou une fraction C₅-C₆ qui est avantageusement envoyée à l'unité d'éthérification, et une fraction C7
Selon une réalisation de l'invention, le réacteur catalytique d'hydrogénation 10 comprend une zone réactionnelle catalytique traversée par la totalité de la charge et la quantité d'hydrogène nécessaire pour effectuer les réactions désirées.According to one embodiment of the invention, the
Selon une réalisation préférée de l'invention, le réacteur catalytique d'hydrogénation 10 est agencé de manière particulière comme l'indique la figure 2, à savoir deux zones catalytiques 11 et 12, la première 11 étant traversée par la charge liquide (et une quantité d'hydrogène, amenée par une tubulure 5, inférieure à la stoechiométrie nécessaire pour convertir toutes les dioléfines en mono oléfines) entrant par la tubulure 15; dans cette première zone, l'adoucissement a également lieu; la seconde 12 recevant la charge liquide provenant de la première zone (ainsi que le reste de l'hydrogène c'est-à-dire une quantité d'hydrogène suffisante pour convertir les dioléfines restant en mono oléfines et pour isomériser au moins en partie les oléfines primaires et secondaires en oléfines tertiaires) par exemple injecté par une tubulure latérale 13 et dispersé à l'aide d'un diffuseur approprié 14.According to a preferred embodiment of the invention, the
La proportion de la première zone (en volume) est tout au plus égale à 50 % de la somme des 2 zones et de préférence de 15 à 30 %.The proportion of the first zone (by volume) is at most equal to 50% of the sum of the 2 zones and preferably from 15 to 30%.
Puisque l'unité d'hydrogénation peut fonctionner à des pressions plus basses que celles exigées par le débutaniseur et puisque le dépentaniseur (ou déhexaniseur) ne demande pas une pression de 13 à 15 bar, la circulation de la charge à travers l'installation est obtenue grâce à une légère dépressurisation à la sortie de l'unité d'hydrogénation. Ceci permet un fonctionnement sans pompes additionnelles.Since the hydrogenation unit can operate at pressures lower than those required by the debutanizer and since the depentanizer (or dehexanizer) does not require a pressure of 13 to 15 bar, the circulation of the charge through the installation is obtained by a slight depressurization at the outlet of the hydrogenation unit. This allows operation without additional pumps.
La température élevée du fond de débutaniseur et la grande activité des catalyseurs utilisés dans l'invention permettent à l'unité d'hydrogénation sélective de coupe C5
Comparé à des unités classiques d'hydrogénation, le nouveau procédé selon l'invention d'hydrogénation sélective de l'essence de craquage catalytique ne requiert ni pompes de charge ou de recyclage, ni four de préchauffage. Comparé à une unité d'hydrogénation sélective dans une colonne de distillation, le nouveau procédé offre une flexibilité bien plus grande en isolant le catalyseur de la colonne de distillation, ce qui permet de remplacer le catalyseur sans arrêter les unités situées en aval. Il permet aussi au catalyseur de fournir une activité plus importante, grâce à des températures et pressions plus élevées que celles obtenues dans le dépentaniseur.Compared with conventional hydrogenation units, the new process according to the invention for the selective hydrogenation of catalytic cracked petrol requires neither charge or recycling pumps, nor preheating furnace. Compared to a selective hydrogenation unit in a distillation column, the new process offers much greater flexibility by isolating the catalyst from the distillation column, allowing the catalyst to be replaced without stopping the units located downstream. It also allows the catalyst to provide greater activity, thanks to higher temperatures and pressures than those obtained in the depentaniser.
Par ailleurs, le nouveau procédé permet de traiter simultanément les coupes C₅, C₆ et C₇-210°C. Ceci permet donc le prétraitement avant éthérification des coupes C₅ et C₆ grâce à une hydrogénation sélective flexible et peu coûteuse. Ce procédé permet d'obtenir le maximum de précurseurs d'éthers en C₅ et C₆ et de plus diminue la quantité d'antioxydants à utiliser dans l'essence traitée.In addition, the new process makes it possible to simultaneously treat cuts C₅, C₆ and C₇-210 ° C. This therefore allows the pretreatment before etherification of the C₅ and C₆ cuts thanks to a selective flexible and inexpensive hydrogenation. This process makes it possible to obtain the maximum of precursors of ethers in C₅ and C₆ and moreover decreases the quantity of antioxidants to be used in the treated gasoline.
Il est en effet réalisé, selon la présente invention, non seulement l'hydrogénation sélective des dioléfines mais également l'isomérisation des oléfines primaires et secondaires en oléfines tertiaires (ex. 3-méthylbutène-1 en 2-méthylbutène-2 et 2-méthylbutène-1).According to the present invention, it is indeed carried out not only the selective hydrogenation of diolefins but also the isomerization of primary and secondary olefins into tertiary olefins (eg 3-methylbutene-1 into 2-methylbutene-2 and 2-methylbutene -1).
Ce procédé permet donc d'améliorer la quantité de produits éthérifiables, donc le rendement de production d'éthers tel que le tertioamyléther par exemple. Il améliore aussi la qualité de l'essence produite, qui présente une meilleure stabilité à l'oxydation ainsi qu'un indice d'octane amélioré.This process therefore makes it possible to improve the quantity of etherifiable products, therefore the production yield of ethers such as tertioamyl ether for example. It also improves the quality of the gasoline produced, which has better oxidation stability and an improved octane number.
L'exemple ci-après illustre l'invention.The example below illustrates the invention.
On dispose de 100 cm³ de catalyseur LD265 de la société Procatalyse contenant 0,3 % poids de palladium supporté sur l'alumine dans un tube d'acier inoxydable de 1,9 cm de diamètre. Ce catalyseur est utilisé couramment pour l'hydrogénation des coupes C₃ et C₄ de FCC et de vapocraquage.We have 100 cm³ of catalyst LD265 from the company Procatalyse containing 0.3% by weight of palladium supported on alumina in a stainless steel tube 1.9 cm in diameter. This catalyst is commonly used for the hydrogenation of C₃ and C₄ cuts of FCC and steam cracking.
Le catalyseur est activé par réduction sous hydrogène à un débit de 30 l/h pendant 5 heures à 200 °C. L'installation est refroidie sous azote à 150 °C avant d'injecter l'essence de FCC ayant les propriétés indiquées dans le tableau 1. Le réacteur est ensuite pressurisé à 14 bar et l'essence est injectée dans le fond du réacteur (100 cm³/heure donc une VVH de 1 h⁻¹).The catalyst is activated by reduction under hydrogen at a flow rate of 30 l / h for 5 hours at 200 ° C. The installation is cooled under nitrogen to 150 ° C. before injecting the FCC gasoline having the properties indicated in table 1. The reactor is then pressurized to 14 bar and the gasoline is injected into the bottom of the reactor (100 cm³ / hour so a VVH of 1 h⁻¹).
Une quantité d'hydrogène correspondant à un rapport molaire H₂/dioléfines de 1,6 est injecté. Le mélange charge/hydrogène traverse le lit catalytique en écoulement ascendant. Les résultats obtenus selon l'invention sont montrés dans le tableau 2.A quantity of hydrogen corresponding to a H₂ / diolefin molar ratio of 1.6 is injected. The charge / hydrogen mixture crosses the catalytic bed in upward flow. The results obtained according to the invention are shown in Table 2.
L'effet de la vitesse spatiale est déterminé en augmentant la VVH à 5 h⁻¹ (exemple 2) puis à 10 h⁻¹ (exemple 3) tout en gardant le rapport molaire H₂/dioléfines à 1,6.The effect of space velocity is determined by increasing the VVH at 5 h⁻¹ (example 2) then at 10 h⁻¹ (example 3) while keeping the H₂ / diolefin molar ratio to 1.6.
L'effet de diminuer le rapport molaire H₂/dioléfines est montré dans l'exemple 4 où ce rapport est de 1,4 et la VVH liquide est de 10 h⁻¹.The effect of reducing the H₂ / diolefin molar ratio is shown in Example 4 where this ratio is 1.4 and the liquid VVH is 10 h⁻¹.
Une autre série de tests catalytiques a été effectuée pour illustrer la présente invention. La zone catalytique est coupée en deux lits séparés, donc 25 cm³ dans la première zone et 75 cm³ de LD265 dans la deuxième. On procède comme précédemment décrit dans l'exemple 4 sauf la quantité d'hydrogène injectée dans le réacteur avec la charge représente un rapport molaire de 0,9. Un dispositif d'injection entre les deux lits permet l'ajout d'une quantité supplémentaire d'hydrogène correspondante à un rapport molaire de 0,5 par rapport à la quantité de dioléfines initialement présentes dans l'essence brut de FCC, exemple 5.Another series of catalytic tests was carried out to illustrate the present invention. The catalytic zone is cut into two separate beds, therefore 25 cm³ in the first zone and 75 cm³ of LD265 in the second. The procedure is as previously described in Example 4 except the quantity of hydrogen injected into the reactor with the feed represents a molar ratio of 0.9. An injection device between the two beds allows adding an additional quantity of hydrogen corresponding to a molar ratio of 0.5 relative to the quantity of diolefins initially present in the raw FCC gasoline, Example 5.
On constate que l'addition étagée de l'hydrogène dans les conditions préconisées dans la présente invention permet non seulement d'améliorer la conversion des dioléfines (montrer par une augmentation de la période d'induction) mais également d'augmenter la quantité de précurseurs de TAME (i.e. 2-méthylbutène-1 et 2-méthylbutène-2) et d'adoucir, au moins partiellement, l'essence de FCC.
Claims (14)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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DE1995614957 DE69514957T3 (en) | 1994-06-01 | 1995-05-29 | Process and use of a plant for the selective hydrogenation of catalytic cracking gas |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9406708A FR2720754B1 (en) | 1994-06-01 | 1994-06-01 | Method and installation for the treatment by selective hydrogenation of a catalytic cracked gasoline. |
FR9406708 | 1994-06-01 |
Publications (3)
Publication Number | Publication Date |
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EP0685552A1 true EP0685552A1 (en) | 1995-12-06 |
EP0685552B1 EP0685552B1 (en) | 2000-02-09 |
EP0685552B2 EP0685552B2 (en) | 2002-11-27 |
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EP95401244A Expired - Lifetime EP0685552B2 (en) | 1994-06-01 | 1995-05-29 | Process and use of an installation for the selective hydrogenation of catalytic cracking gasoline |
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---|---|
EP (1) | EP0685552B2 (en) |
DE (1) | DE69514957T3 (en) |
ES (1) | ES2144587T5 (en) |
FR (1) | FR2720754B1 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0831140A1 (en) * | 1996-09-24 | 1998-03-25 | Institut Francais Du Petrole | Process and apparatus for the purification of catalytically cracked gasolines |
FR2753717A1 (en) * | 1996-09-24 | 1998-03-27 | Inst Francais Du Petrole | PROCESS AND PLANT FOR THE PRODUCTION OF CATALYTIC CRACKS WITH LOW SULFUR CONTENT |
FR2764210A1 (en) * | 1997-06-09 | 1998-12-11 | Inst Francais Du Petrole | SELECTIVE HYDROGENATION CATALYST FOR USE IN THE TREATMENT OF ESSENCE CUTTINGS CONTAINING DIOLEFINS AND STYRENIC COMPOUNDS |
FR2764299A1 (en) * | 1997-06-09 | 1998-12-11 | Inst Francais Du Petrole | Treatment of petrols containing di:olefins and styrenic compounds |
EP0884373A1 (en) * | 1997-06-09 | 1998-12-16 | Institut Français du Pétrole | Process for the treatment of gasoline fractions containing diolefins, styrenic compounds and eventually mercaptans |
US6118034A (en) * | 1996-03-04 | 2000-09-12 | Basf Aktiengesellschaft | Process for the selective hydrogenation of dienes in reformate flows |
US6709639B1 (en) | 1996-09-24 | 2004-03-23 | Institut Francais Du Petrole | Apparatus for purification of raw gasoline from catalytic cracking |
EP3317238A4 (en) * | 2015-06-30 | 2019-02-27 | Uop Llc | Process and apparatus for selectively hydrogenating diolefins |
CN114763493A (en) * | 2021-01-13 | 2022-07-19 | 中国石油化工股份有限公司 | Method and system for producing gasoline blend oil by using carbon five raffinate oil |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2797639B1 (en) | 1999-08-19 | 2001-09-21 | Inst Francais Du Petrole | PROCESS FOR PRODUCING LOW SULFUR ESSENCE |
FR2807061B1 (en) | 2000-03-29 | 2002-05-31 | Inst Francais Du Petrole | PROCESS FOR FUEL DESULFURIZATION COMPRISING DESULFURIZATION OF HEAVY AND INTERMEDIATE FRACTIONS FROM A FRACTIONATION IN AT LEAST THREE CUT |
FR2935389B1 (en) | 2008-09-04 | 2012-05-11 | Inst Francais Du Petrole | SELECTIVE HYDROGENATION PROCESS USING SULFIDE CATALYST OF SPECIFIC COMPOSITION |
FR2963359B1 (en) | 2010-07-29 | 2012-07-27 | IFP Energies Nouvelles | METHOD FOR SELECTIVE HYDROGENATION OF A PETROL CUTTING IN THE PRESENCE OF A SUPPORTED SULFIDE CATALYST PREPARED BY MEANS OF AT LEAST ONE CYCLIC OLIGOSACCHARIDE |
CN104560135B (en) * | 2013-10-24 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of method of hydrotreating of reformed oil |
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GB1346778A (en) * | 1971-02-11 | 1974-02-13 | British Petroleum Co | Selective hydrogenation of gasolines |
GB1565754A (en) * | 1978-03-08 | 1980-04-23 | British Petroleum Co | Selective hydrogenation |
GB2053959A (en) * | 1979-07-06 | 1981-02-11 | Inst Francais Du Petrole | Purification of aromatic hydrocarbon cuts |
FR2482953A1 (en) * | 1980-05-22 | 1981-11-27 | Inst Francais Du Petrole | METHOD FOR SELECTIVE HYDROGENATION OF DI-OLEFIN IN A MIXTURE OF HYDROCARBONS COMPRISING AT LEAST 4 ATOMS OF CARBON AND CONTAINING OLEFIN -A |
EP0554151A1 (en) * | 1992-01-28 | 1993-08-04 | Institut Francais Du Petrole | Selective hydrogenation process, particularly of steam cracking gasolines, with a catalyst in several sequentially used beds |
EP0564329A1 (en) * | 1992-04-02 | 1993-10-06 | Institut Francais Du Petrole | Catalyst containing group VIII metal and group IIIA metal on a support |
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US3470085A (en) † | 1967-11-20 | 1969-09-30 | Universal Oil Prod Co | Method for stabilizing pyrolysis gasoline |
US5254789A (en) † | 1990-02-08 | 1993-10-19 | Uop | Process for isomerizing olefins in gasoline streams |
US5266188A (en) † | 1991-04-22 | 1993-11-30 | Amoco Corporation | Selective hydrotreating |
-
1994
- 1994-06-01 FR FR9406708A patent/FR2720754B1/en not_active Expired - Lifetime
-
1995
- 1995-05-29 EP EP95401244A patent/EP0685552B2/en not_active Expired - Lifetime
- 1995-05-29 ES ES95401244T patent/ES2144587T5/en not_active Expired - Lifetime
- 1995-05-29 DE DE1995614957 patent/DE69514957T3/en not_active Expired - Lifetime
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GB1346778A (en) * | 1971-02-11 | 1974-02-13 | British Petroleum Co | Selective hydrogenation of gasolines |
GB1565754A (en) * | 1978-03-08 | 1980-04-23 | British Petroleum Co | Selective hydrogenation |
GB2053959A (en) * | 1979-07-06 | 1981-02-11 | Inst Francais Du Petrole | Purification of aromatic hydrocarbon cuts |
FR2482953A1 (en) * | 1980-05-22 | 1981-11-27 | Inst Francais Du Petrole | METHOD FOR SELECTIVE HYDROGENATION OF DI-OLEFIN IN A MIXTURE OF HYDROCARBONS COMPRISING AT LEAST 4 ATOMS OF CARBON AND CONTAINING OLEFIN -A |
EP0554151A1 (en) * | 1992-01-28 | 1993-08-04 | Institut Francais Du Petrole | Selective hydrogenation process, particularly of steam cracking gasolines, with a catalyst in several sequentially used beds |
EP0564329A1 (en) * | 1992-04-02 | 1993-10-06 | Institut Francais Du Petrole | Catalyst containing group VIII metal and group IIIA metal on a support |
Cited By (17)
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US6118034A (en) * | 1996-03-04 | 2000-09-12 | Basf Aktiengesellschaft | Process for the selective hydrogenation of dienes in reformate flows |
US6709639B1 (en) | 1996-09-24 | 2004-03-23 | Institut Francais Du Petrole | Apparatus for purification of raw gasoline from catalytic cracking |
US6187173B1 (en) | 1996-09-24 | 2001-02-13 | Institut Francais Du Petrole | Process for purification of raw gasoline from catalytic cracking |
EP0832958A1 (en) * | 1996-09-24 | 1998-04-01 | Institut Francais Du Petrole | Process and apparatus for the production of low sulphur catalytically cracked gasolines |
US6838060B1 (en) | 1996-09-24 | 2005-01-04 | Institut Francais Dupetrole | Process and apparatus for the production of catalytic cracking gasoline with a low sulphur content |
FR2753717A1 (en) * | 1996-09-24 | 1998-03-27 | Inst Francais Du Petrole | PROCESS AND PLANT FOR THE PRODUCTION OF CATALYTIC CRACKS WITH LOW SULFUR CONTENT |
EP0831140A1 (en) * | 1996-09-24 | 1998-03-25 | Institut Francais Du Petrole | Process and apparatus for the purification of catalytically cracked gasolines |
FR2753718A1 (en) * | 1996-09-24 | 1998-03-27 | Inst Francais Du Petrole | PROCESS AND PLANT FOR PURIFYING CRUDE GASOLINE FROM CATALYTIC CRACKING |
US6007704A (en) * | 1996-09-24 | 1999-12-28 | Institut Francais Du Petrole | Process for the production of catalytic cracking gasoline with a low sulphur content |
EP0884373A1 (en) * | 1997-06-09 | 1998-12-16 | Institut Français du Pétrole | Process for the treatment of gasoline fractions containing diolefins, styrenic compounds and eventually mercaptans |
FR2764299A1 (en) * | 1997-06-09 | 1998-12-11 | Inst Francais Du Petrole | Treatment of petrols containing di:olefins and styrenic compounds |
US6686309B1 (en) | 1997-06-09 | 2004-02-03 | Institut Francais Du Petrole | Catalyst for treating gasoline cuts containing diolefins, styrenic compounds and possibly mercaptans |
EP0884102A1 (en) * | 1997-06-09 | 1998-12-16 | Institut Français du Pétrole | Catalyst for the treatment of gasoline fractions containing diolefins, styrenic compounds and eventually mercaptans |
FR2764210A1 (en) * | 1997-06-09 | 1998-12-11 | Inst Francais Du Petrole | SELECTIVE HYDROGENATION CATALYST FOR USE IN THE TREATMENT OF ESSENCE CUTTINGS CONTAINING DIOLEFINS AND STYRENIC COMPOUNDS |
EP3317238A4 (en) * | 2015-06-30 | 2019-02-27 | Uop Llc | Process and apparatus for selectively hydrogenating diolefins |
CN114763493A (en) * | 2021-01-13 | 2022-07-19 | 中国石油化工股份有限公司 | Method and system for producing gasoline blend oil by using carbon five raffinate oil |
CN114763493B (en) * | 2021-01-13 | 2024-01-12 | 中国石油化工股份有限公司 | Method and system for producing gasoline blend oil by using carbon five raffinate oil |
Also Published As
Publication number | Publication date |
---|---|
DE69514957D1 (en) | 2000-03-16 |
DE69514957T3 (en) | 2011-08-18 |
ES2144587T5 (en) | 2003-06-16 |
DE69514957T2 (en) | 2000-10-12 |
ES2144587T3 (en) | 2000-06-16 |
FR2720754A1 (en) | 1995-12-08 |
FR2720754B1 (en) | 1996-07-26 |
EP0685552B2 (en) | 2002-11-27 |
EP0685552B1 (en) | 2000-02-09 |
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