EP0685552B2 - Process and use of an installation for the selective hydrogenation of catalytic cracking gasoline - Google Patents
Process and use of an installation for the selective hydrogenation of catalytic cracking gasoline Download PDFInfo
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- EP0685552B2 EP0685552B2 EP95401244A EP95401244A EP0685552B2 EP 0685552 B2 EP0685552 B2 EP 0685552B2 EP 95401244 A EP95401244 A EP 95401244A EP 95401244 A EP95401244 A EP 95401244A EP 0685552 B2 EP0685552 B2 EP 0685552B2
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- Prior art keywords
- process according
- cut
- selective hydrogenation
- catalytic cracking
- gasoline
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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 to tertioamylmethylether or sometimes 2-methylpentenes and 3-methylpentene-2 in tertiohexylmethylether.
- Etherification is thus an elegant way of reducing the content of olefins while transforming them into High octane research and engine ethers.
- the subject of the invention is a method as described in claim 1.
- the catalyst must contain 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. We will generally operate under pressure in the presence of a quantity of hydrogen in small excess relative to the stoichiometric value required to hydrogenate diolefins.
- the hydrogen and the charge to be treated are injected in ascending or descending currents in a reactor preferably with a fixed bed of catalyst.
- the temperature is 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, more generally between 4 and 25 bar and preferably above 10 bar.
- 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 essence cut of catalytic cracking generally contains from 15 to 40% of olefins (olefins, diolefins and cycloolefins) with a content of conjugated diolefins less than 5% and generally not more than 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 cracked gasoline is less than 1% by weight, and generally less than 0.5% by weight, whereas 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 invention also relates to the use of an installation for a process for the treatment by selective hydrogenation of a catalytic cracking gasoline as described in claim 13 comprising a catalytic cracking unit followed by a fractionation unit for separating fraction C 3 -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.
- FIG 1 shows schematically the process and the installation used 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 C 5 -180 ° C cut obtained (or the C 5 -160 ° C or C 5 -210 ° C cut depending on the fractionation carried out), called the C 5+ catalytic cracking gasoline cut, is introduced into a zone (or l '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 (separation C 5 ) or a dehexanizer (separation C 5 -C 6 ).
- a C 5 fraction or a C 5 -C 6 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 reaction zone catalyst through which the entire charge and the quantity of hydrogen required to carry out the reactions desired.
- the catalytic hydrogenation reactor 10 is arranged so particular as shown in Figure 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 tube 5, less than the necessary stoichiometry to convert all the diolefins into mono olefins) entering via the pipe 15; in this first zone, the softening also takes place; the second 12 receiving the liquid charge coming from the first zone (as well as the rest hydrogen i.e.
- the proportion of the first zone (by volume) is at most equal to 50% of the sum of the 2 zones and preferably 15 to 30%.
- the hydrogenation unit can operate at pressures lower than those required by the debutanizer and since the depentaniser (or dehexanizer) does not require a pressure of 13 to 15 bar, the circulation charge through the installation is obtained by 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 of C 5+ cut of catalytic cracking to operate without a charge preheating oven 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 of selective hydrogenation catalytic cracked gasoline does not require charge or recycling pumps or a preheating oven.
- the new process offers flexibility much larger by isolating the catalyst from the distillation column, allowing the catalyst to be replaced without stop downstream units. It also allows the catalyst to provide more activity, thanks to higher temperatures and pressures than those obtained in the depentaniser.
- the new process makes it possible to simultaneously treat cuts C 5 , C 6 and C 7 -210 ° C. This therefore allows the pretreatment before etherification of cuts C 5 and C 6 by means of flexible and inexpensive selective hydrogenation. This process makes it possible to obtain the maximum of precursors of C 5 and C 6 ethers and moreover decreases the quantity of antioxidants to be used in the treated gasoline.
- ethers such as tertioamyl ether for example. It also improves the quality of the gasoline produced, which has a better oxidation stability as well as 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 cuts C 3 and C 4 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 cm 3 / hour therefore a VVH of 1 h -1 ).
- the effect of the space velocity is determined by increasing the WH at 5 h -1 (example 2) then at 10 h -1 (example 3) while keeping the H 2 / diolefin molar ratio at 1.6.
- Example 4 The effect of reducing the H 2 / 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 cm 3 in the first zone and 75 cm 3 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 makes it possible to add an additional quantity of hydrogen corresponding to a molar ratio of 0.5 relative to the quantity of diolefins initially present in the raw gasoline of FCC, example 5.
- staged addition of hydrogen under the conditions recommended in the present invention makes it possible not only to improve the conversion of the diolefins (show by increasing the induction period) but also to increase the amount of precursors of TAME (ie 2-methylbutene-1 and 2-methylbutene-2) and to soften, at least partially, the essence of FCC.
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 decrease their concentration of olefins, aromatics (especially benzene) and sulfur.
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 to tertioamylmethylether or sometimes 2-methylpentenes and 3-methylpentene-2 in 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 thus an elegant way of reducing the content of olefins while transforming them into High octane research and engine ethers.
Cependant, la présence de dioléfines dans les essences de craquage catalytique entraíne une désactivation du catalyseur d'éthérification par formation de gommes, celles-ci provoquant également une dégradation de la qualité de l'éther produit. Divers procédés ont été proposés pour résoudre ce problème (EP-A-0 564 329, EP-A-0 554 151, FR-A-2 482 953, GB-A-1 346 778, GB-A-1 565 754).However, the presence of diolefins in catalytic cracking gasolines leads to deactivation of the etherification catalyst by the formation of gums, these also causing a degradation of the quality ether produced. Various methods have been proposed to solve this problem (EP-A-0 564 329, EP-A-0 554 151, FR-A-2 482 953, GB-A-1 346 778, GB-A-1 565 754).
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.We have therefore developed a process which makes it possible to selectively hydrogenate the diolefins to corresponding olefins, and to carry out, together with the hydrogenation of the diolefins, the isomerization at least in part of the olefins primary and / or secondary to tertiary olefins and for example the isomerization of 3-methylbutene-1 which cannot be etherified 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.We have also discovered that it is possible to at least partially soften the catalytic cracking gasoline by transformation of mercaptans into other sulfurized products thanks to the particular conditions of the invention and an arrangement particular of the catalytic reactor of the present invention. By softening, we understand a reaction addition of olefin on a mercaptan.
Plus précisément, l'invention a pour objet un procédé
comme décrit dans la revendication 1.More specifically, the subject of the invention is a method
as described in
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 contain 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 pou r 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. We will generally operate under pressure in the presence of a quantity of hydrogen in small excess relative to the stoichiometric value required to hydrogenate diolefins. The hydrogen and the charge to be treated are injected in ascending or descending currents in a reactor preferably with a fixed bed of catalyst. The temperature is 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, more generally between 4 and 25 bar and preferably above 10 bar. 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 in the range 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 about 50% of diolefins, the essence cut of catalytic cracking generally contains from 15 to 40% of olefins (olefins, diolefins and cycloolefins) with a content of conjugated diolefins less than 5% and generally not more than 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 cracked gasoline is less than 1% by weight, and generally less than 0.5% by weight, whereas 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 special conditions make it possible to operate directly downstream of the cracker gas debutanizer catalytic without the need to add a preheater or a charge pump, and preferably with a single reactor.
L'invention a également pour objet l'utilisation d'une installation pour un procédé de traitement par hydrogénation sélective d'une essence
de craquage catalytique comme décrit dans la revendication 13 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 invention also relates to the use of an installation for a process for the treatment by selective hydrogenation of a catalytic cracking gasoline as described in
La figure 1 schématise le procédé et l'installation utilisée selon l'invention.Figure 1 shows schematically the process and the installation used 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 section C 3 -180 ° C 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+ de craquage catalytique, est introduite dans une zone (ou l'unité) 4 d'hydrogénation sélective selon
l'invention, de l'hydrogène est également introduit par exemple par la conduite 5.The C 5 -180 ° C cut obtained (or the C 5 -160 ° C or C 5 -210 ° C cut depending on the fractionation carried out), called the C 5+ catalytic cracking gasoline cut, is introduced into a zone (or l 'unit) 4 of selective hydrogenation according to the invention, hydrogen is also introduced for example by
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+ envoyée au stockage essence.The hydrogenated cut obtained enters the
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 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 depentaniser (or dehexanizer) does not require a pressure of 13 to 15 bar, the circulation charge through the installation is obtained by 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+ de craquage catalytique de fonctionner sans four de préchauffage de la charge et d'être très compacte. Ceci conduit à une unité à faible investissement et à grande flexibilité ce qui lui confère des avantages uniques.The high temperature of the debutanizer base and the high activity of the catalysts used in the invention allow the selective hydrogenation unit of C 5+ cut of catalytic cracking to operate without a charge preheating oven and to be very compact. . This leads to a unit with low investment and great flexibility which gives it unique advantages.
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 to conventional hydrogenation units, the new process according to the invention of selective hydrogenation catalytic cracked gasoline does not require charge or recycling pumps or a preheating oven. Compared to a selective hydrogenation unit in a distillation column, the new process offers flexibility much larger by isolating the catalyst from the distillation column, allowing the catalyst to be replaced without stop downstream units. It also allows the catalyst to provide more 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 C 5 , C 6 and C 7 -210 ° C. This therefore allows the pretreatment before etherification of cuts C 5 and C 6 by means of flexible and inexpensive selective hydrogenation. This process makes it possible to obtain the maximum of precursors of C 5 and C 6 ethers 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 in fact carried out not only the selective hydrogenation of diolefins but also the isomerization of primary and secondary olefins to tertiary olefins (eg 3-methylbutene-1 to 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. ethers such as tertioamyl ether for example. It also improves the quality of the gasoline produced, which has a better oxidation stability as well as 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 cm 3 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 cuts C 3 and C 4 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 cm 3 / hour therefore 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 an H 2 / 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 WH 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 the space velocity is determined by increasing the WH at 5 h -1 (example 2) then at 10 h -1 (example 3) while keeping the H 2 / diolefin molar ratio at 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 H 2 / 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 cm 3 in the first zone and 75 cm 3 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 makes it possible to add an additional quantity of hydrogen corresponding to a molar ratio of 0.5 relative to the quantity of diolefins initially present in the raw gasoline of FCC, 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)
- A process for treatment by selective hydrogenation of catalytic cracking gasoline having a diolefins content of less than 5%, a cyclopentadiene content of less than 1% and a mercaptan content of between 1 and 300 ppm, characterised in that the C5-210°C gasoline cut is brought into contact, at a pressure of 4-25 bars, at a temperature of 80-200°C, and with a LHSV (liquid hourly space velocity) of 1-10h-1, in the presence of a slight excess of hydrogen of up to 1.6 times the stoichiometry (1.0) required to hydrogenate the diolefins, with a catalyst comprising from 0.1 to 1% by weight of palladium deposited on a support containing at least 50% alumina, to reduce the mercaptan content in the gasoline.
- A process according to claim 1, characterised in that the catalyst contains 0.2-0.5% by weight of palladium.
- A process according to one of the preceding claims, characterised in that the support contains at least 90% of alumina.
- A process according to one of the preceding claims, characterised in that the support is pure alumina.
- A process according to one of the preceding claims, characterised in that the catalyst comprises mainly palladium.
- A process according to one of the preceding claims, characterised in that the temperature is between 130 and 200°C.
- A process according to one of the preceding claims, characterised in that the temperature is between 150 and 170°C.
- A process according to one of the preceding claims, characterised in that the pressure is between 10 and 20 bars.
- A process according to one of the preceding claims, characterised in that the pressure is between 12 and 16 bars.
- A process according to one of the preceding claims, characterised in that the LHSV is between 4 and 10 h-1.
- A process according to one of the preceding claims, characterised in that the end point of the cut is 180°C.
- A process according to one of the preceding claims, characterised in that the end point of the cut is 160°C.
- Use of a facility for a process for treatment by selective hydrogenation of a catalytic cracking gasoline according to one of the preceding claims, the facility comprising a catalytic cracking unit followed by a fractionating unit for separating a C3-210°C cut and a debutaniser for separating the C3-C4 cut to obtain the C5-210°C cut, and a selective hydrogenation unit which is disposed between the debutaniser and a separation unit selected from a depentaniser and a dehexaniser.
- Use according to claim 13, characterised in that the selective hydrogenation unit is formed by a reactor which comprises two catalytic zones, the first being traversed by the liquid feed and a quantity of hydrogen which is less than stoichiometry, and the second receiving the liquid feed deriving from the first zone and the remainder of the hydrogen which is injected by way of a lateral pipe.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
---|---|---|---|
FR9406708 | 1994-06-01 | ||
FR9406708A FR2720754B1 (en) | 1994-06-01 | 1994-06-01 | Method and installation for the treatment by selective hydrogenation of a catalytic cracked gasoline. |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0685552A1 EP0685552A1 (en) | 1995-12-06 |
EP0685552B1 EP0685552B1 (en) | 2000-02-09 |
EP0685552B2 true EP0685552B2 (en) | 2002-11-27 |
Family
ID=9463769
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
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 |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0685552B2 (en) |
DE (1) | DE69514957T3 (en) |
ES (1) | ES2144587T5 (en) |
FR (1) | FR2720754B1 (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19608241A1 (en) * | 1996-03-04 | 1997-09-18 | Basf Ag | Process for the selective hydrogenation of dienes |
US6709639B1 (en) | 1996-09-24 | 2004-03-23 | Institut Francais Du Petrole | Apparatus for purification of raw gasoline from catalytic cracking |
FR2753718B1 (en) | 1996-09-24 | 1999-05-14 | PROCESS AND PLANT FOR PURIFYING CRUDE GASOLINE FROM CATALYTIC CRACKING | |
FR2753717B1 (en) | 1996-09-24 | 1998-10-30 | PROCESS AND PLANT FOR THE PRODUCTION OF LOW SULFUR CATALYTIC CRACKING ESSENCES | |
EP0884373B1 (en) * | 1997-06-09 | 2003-03-19 | Institut Français du Pétrole | Process for the treatment of gasoline fractions containing diolefins, styrenic compounds and possibly mercaptans |
FR2764210B1 (en) * | 1997-06-09 | 1999-07-16 | Inst Francais Du Petrole | SELECTIVE HYDROGENATION CATALYST FOR USE IN THE TREATMENT OF ESSENCE CUTTINGS CONTAINING DIOLEFINS AND STYRENIC COMPOUNDS |
FR2764299B1 (en) * | 1997-06-09 | 1999-07-16 | Inst Francais Du Petrole | PROCESS FOR TREATING ESSENCE CUTTINGS CONTAINING DIOLEFINS, STYRENIC COMPOUNDS AND MERCAPTANS |
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 |
EP3317238A4 (en) * | 2015-06-30 | 2019-02-27 | Uop Llc | Process and apparatus for selectively hydrogenating diolefins |
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 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
FR2460989A1 (en) * | 1979-07-06 | 1981-01-30 | Inst Francais Du Petrole | PROCESS FOR PURIFYING A CUTTING OF AROMATIC HYDROCARBONS CONTAINING OLEFINIC AND ACETYLENE UNSATURATED HYDROCARBONS |
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 |
FR2686617B1 (en) * | 1992-01-28 | 1994-03-18 | Institut Francais Petrole | PROCESS FOR SELECTIVE HYDROGENATION OF HYDROCARBON CHARGE WITH CATALYTIC LETS CARRIED OUT SUCCESSIVELY. |
FR2689419B1 (en) * | 1992-04-02 | 1994-09-30 | Inst Francais Du Petrole | Catalyst containing a group VIII metal and a group III metal deposited on a support, applicable to the selective hydrogenation of hydrocarbons. |
-
1994
- 1994-06-01 FR FR9406708A patent/FR2720754B1/en not_active Expired - Lifetime
-
1995
- 1995-05-29 ES ES95401244T patent/ES2144587T5/en not_active Expired - Lifetime
- 1995-05-29 EP EP95401244A patent/EP0685552B2/en not_active Expired - Lifetime
- 1995-05-29 DE DE1995614957 patent/DE69514957T3/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Also Published As
Publication number | Publication date |
---|---|
EP0685552A1 (en) | 1995-12-06 |
DE69514957T2 (en) | 2000-10-12 |
DE69514957T3 (en) | 2011-08-18 |
EP0685552B1 (en) | 2000-02-09 |
ES2144587T3 (en) | 2000-06-16 |
ES2144587T5 (en) | 2003-06-16 |
FR2720754B1 (en) | 1996-07-26 |
FR2720754A1 (en) | 1995-12-08 |
DE69514957D1 (en) | 2000-03-16 |
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