EP0610168A1 - Process for the production of high octane number gasolines - Google Patents
Process for the production of high octane number gasolines Download PDFInfo
- Publication number
- EP0610168A1 EP0610168A1 EP94870015A EP94870015A EP0610168A1 EP 0610168 A1 EP0610168 A1 EP 0610168A1 EP 94870015 A EP94870015 A EP 94870015A EP 94870015 A EP94870015 A EP 94870015A EP 0610168 A1 EP0610168 A1 EP 0610168A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- transalkylation
- fraction
- process according
- heavy
- reforming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000010555 transalkylation reaction Methods 0.000 claims abstract description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 19
- 238000001833 catalytic reforming Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052680 mordenite Inorganic materials 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- 238000002407 reforming Methods 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
Images
Classifications
-
- 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
- C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
- C10G63/02—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only
-
- 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
- C10G59/00—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha
- C10G59/02—Treatment of naphtha by two or more reforming processes only or by at least one reforming process and at least one process which does not substantially change the boiling range of the naphtha plural serial stages only
Definitions
- the present invention relates to a process for improving the yield of gasoline with a high octane number.
- the present invention relates to a process for increasing the yield of gasolines with a high octane number during the step of reforming naphtha.
- Naphtha is a fraction that has a boiling temperature between 80 and 200 ° C and which consists mainly of paraffins, naphthenes and aromatics.
- the most important reaction that takes place during the reforming of naphtha is the dehydrocyclization of paraffins to aromatics.
- catalytic reforming tends to increase the end point of the reformate compared to naphtha and to favor the formation of benzene.
- these phenomena are all the more marked.
- those skilled in the art know that the end point of the reformate must be sufficiently low and that the benzene content must be limited
- the object of the present invention is a process which makes it possible to increase the yield of gasolines with a high octane number, namely the intermediate fraction originating from the step of reforming naphtha.
- FIG. 1 represents a schematic diagram of the process of the invention.
- a charge of naphtha is introduced via line (11). This charge is subjected to a reforming step (2) during which it is brought into contact with a reforming catalyst under appropriate conditions.
- the effluent recovered from the reforming step via line (21) is introduced into the separation step (3) and separated into three fractions: the light fraction (31), rich in benzene, and whose temperature boiling is generally less than 90 ° C, the intermediate fraction (32) whose boiling temperature is generally between 90 and 180 ° C and the heavy fraction (33) whose boiling temperature is generally greater than 180 ° C .
- the heavy and light fractions are then mixed and introduced into a transalkylation reactor (4) in which it is brought into contact with a transalkylation catalyst under suitable conditions.
- This transalkylation step can be carried out in ascending or descending mode.
- the effluent from this transalkylation step is sent via line (41) to line (21) where it is mixed with the effluent from catalytic reforming.
- the whole is sent to the separation step at the end of which a larger intermediate fraction is recovered.
- the pipes (311) and (331) indicated in FIG. 1 are not essential; in certain cases they allow the relative proportions of the heavy and light fractions to be adjusted before introduction into the transalkylation reactor.
- Catalytic reforming of hydrocarbons is well known to those skilled in the art.
- the objective of catalytic reforming is the selective conversion of saturated hydrocarbons to aromatics. This process makes it possible to obtain gasolines with high octane number as well as aromatic hydrocarbons. Many reactions take place during catalytic reforming, the main one being dehydrogenation.
- the catalysts generally used have a double function: a metallic element makes it possible to catalyze dehydrogenation / hydrogenation and an acid function catalyzes the rearrangements of hydrocarbons.
- These catalysts usually contain a small amount of highly dispersed platinum (preferably less than 1% by weight) supported on alumina with a high specific surface (of the order of 150-300m2 / g); a second metal such as rhenium is also often used. It also happens that the catalyst used is dispersed on a basic support.
- the operating conditions used are generally a temperature between 400 and 550 ° C and a pressure between 0.3 and 3.5 MPa.
- the reaction is generally carried out in reactors with fixed or moving beds.
- the Applicant has unexpectedly found that by subjecting the mixture of heavy and light fractions to a transalkylation step and by reintroducing the resulting effluent in the separation step, the total amount of intermediate fraction is increased. ie the yield of gasoline with a high octane number.
- step c step of mixing the light fraction and the heavy fraction
- any other source of dilute benzene and / or any other source of polyalkylbenzene any other source of dilute benzene and / or any other source of polyalkylbenzene.
- This patent describes a process for transalkylating a feedstock containing at least one polyalkylbenzene in a reactor in the presence of a transalkylation catalyst in order to produce at least one monoalkylbenzene characterized in that the reaction is carried out in the presence of hydrogen.
- the hydrogen: alkyl groups molar ratios are preferably between 1:10 and 1: 1.
- transalkylation catalysts can be used.
- Large pore molecular sieves will be particularly suitable; preferably those with a stress index less than 1.
- the definition of the stress index and its calculation are given in column 5 of US Pat. No. 4,211,886.
- mordenite type catalysts are used, in particular type catalysts. Mordenite slightly deficient in aluminum and having a silica / alumina molar ratio of up to 30, preferably up to 20.
- mordenite catalysts which can be used according to the present invention mention may also be made of those described in US Patents 4,665,258 and US 4,723,048.
- One of the advantages provided by the process of the present invention consists in the recovery of the heavy fraction resulting from the reforming step.
- Another advantage of the process of the present invention consists in that it makes it possible to treat charges of naphtha without treatment prior to reforming. Indeed, it is known to those skilled in the art that in order to minimize the amount of heavy fraction after reforming, it is preferable to treat the charge of starting naphtha by removing the compounds at high boiling temperatures. According to the process of the present invention, this step of pretreatment of naphtha is no longer necessary, which represents a considerable advantage.
- the light fraction obtained is rich in benzene.
- this light fraction was incorporated into gasolines which very often required treatment in order to limit the benzene content of the gasolines. This additional step is no longer necessary according to the process of the present invention since the benzene content is automatically limited following the conversion of the benzene during the transalkylation step.
- the catalyst used is based on nickel (1.6% by weight) deposited on a mordenite whose silica / alumina molar ratio is 8.8. This catalyst was activated in the following way: at 6 MPa, with a flow of hydrogen, the temperature gradually rose to 200 ° C. and maintained for 12 hours. Then, the temperature rose to 360 ° C and stabilized for 4 hours. Then, the reactor is cooled to 200 ° C.
- the operating conditions of the transalkylation are indicated in Table 2.
- the composition of the transalkylation effluent is also indicated in Table 2.
Abstract
Description
La présente invention se rapporte à un procédé pour améliorer le rendement en essences à haut indice d'octane. En particulier, la présente invention se rapporte à un procédé pour augmenter le rendement en essences à haut indice d'octane lors de l'étape de reforming du naphta.The present invention relates to a process for improving the yield of gasoline with a high octane number. In particular, the present invention relates to a process for increasing the yield of gasolines with a high octane number during the step of reforming naphtha.
Le reforming du naphta en vue d'améliorer la qualité des essences est un procédé bien connu. Le naphta est une fraction qui a sa température d'ébullition comprise entre 80 et 200°C et qui se compose essentiellement de paraffines, de naphtènes et d'aromatiques. La réaction la plus importante qui a lieu durant le reforming du naphta consiste en la déshydrocyclisation des paraffines en aromatiques. Il est connu que le reforming catalytique a tendance à augmenter le point final du réformat par rapport au naphta et à favoriser la formation de benzène. De plus, lorsqu'on travaille à de basses pressions (de l'ordre de 1MPa ou moins) et à haute sévérité, ce qui est souvent le cas, ces phénomènes sont d'autant plus marqués. Or, parmi les exigences relatives aux essences reformulées, l'homme de l'art sait que le point final du réformat doit être suffisamment bas et que la teneur en benzène doit être limitéeReforming naphtha to improve the quality of gasolines is a well-known process. Naphtha is a fraction that has a boiling temperature between 80 and 200 ° C and which consists mainly of paraffins, naphthenes and aromatics. The most important reaction that takes place during the reforming of naphtha is the dehydrocyclization of paraffins to aromatics. It is known that catalytic reforming tends to increase the end point of the reformate compared to naphtha and to favor the formation of benzene. In addition, when working at low pressures (of the order of 1 MPa or less) and at high severity, which is often the case, these phenomena are all the more marked. However, among the requirements relating to reformulated gasolines, those skilled in the art know that the end point of the reformate must be sufficiently low and that the benzene content must be limited
La Demanderesse a maintenant trouvé qu'il y avait moyen d'améliorer considérablement le rendement en essences à haut indice d'octane et à résoudre les problèmes évoqués ci-dessus.The Applicant has now found that there was a way of considerably improving the yield of gasoline with a high octane number and of solving the problems mentioned above.
La présente invention a pour but un procédé qui permette d'augmenter le rendement en essences à haut indice d'octane, à savoir la fraction intermédiaire provenant de l'étape de reforming du naphta.The object of the present invention is a process which makes it possible to increase the yield of gasolines with a high octane number, namely the intermediate fraction originating from the step of reforming naphtha.
Le procédé de la présente invention pour augmenter la fraction intermédiaire est caractérisé en ce qu'il comprend les étapes qui consistent à :
- a. Soumettre à un reforming catalytique une charge de naphta, par mise en contact avec un catalyseur de reforming catalytique, pour former trois fractions, une légère, une intermédiaire et une lourde.
- b. Séparer les trois fractions lors d'une étape de séparation.
- c. Mélanger au moins une partie de la fraction légère avec au moins une partie de la fraction lourde.
- d. Soumettre le mélange issu du point c à une étape de transalkylation.
- e. Introduire à l'étape b l'effluent provenant de l'étape d et récupérer une fraction intermédiaire plus importante après cette étape b.
- at. Subject a charge of naphtha to catalytic reforming, by contacting with a catalytic reforming catalyst, to form three fractions, a light, an intermediate and a heavy.
- b. Separate the three fractions during a separation step.
- vs. Mix at least part of the light fraction with at least part of the heavy fraction.
- d. Subject the mixture from point c to a transalkylation step.
- e. Introduce in step b the effluent from step d and recover a larger intermediate fraction after this step b.
La présente invention est également décrite à l'aide du dessin annexé, dans lequel la figure 1 représente un diagramme schématique du procédé de l'invention.The present invention is also described with the aid of the accompanying drawing, in which FIG. 1 represents a schematic diagram of the process of the invention.
En se référant à la figure 1, on introduit par la conduite (11) une charge de naphta. Cette charge est soumise à une étape de reforming (2) lors de laquelle il y a mise en contact avec un catalyseur de reforming dans des conditions appropriées. L'effluent récupéré de l'étape de reforming par la conduite (21) est introduit dans l'étape de séparation (3) et séparé en trois fractions : la fraction légère (31), riche en benzène, et dont la température d'ébullition est généralement inférieure à 90°C, la fraction intermédiaire (32) dont la température d'ébullition est généralement comprise entre 90 et 180°C et la fraction lourde (33) dont la température d'ébullition est généralement supérieure à 180°C.Referring to FIG. 1, a charge of naphtha is introduced via line (11). This charge is subjected to a reforming step (2) during which it is brought into contact with a reforming catalyst under appropriate conditions. The effluent recovered from the reforming step via line (21) is introduced into the separation step (3) and separated into three fractions: the light fraction (31), rich in benzene, and whose temperature boiling is generally less than 90 ° C, the intermediate fraction (32) whose boiling temperature is generally between 90 and 180 ° C and the heavy fraction (33) whose boiling temperature is generally greater than 180 ° C .
Les fractions lourdes et légères sont ensuite mélangées et introduites dans un réacteur de transalkylation (4) dans lequel il y a mise en contact avec un catalyseur de transalkylation dans des conditions appropriées. Cette étape de transalkylation peut être effectuée en mode ascendant ou descendant. L'effluent provenant de cette étape de transalkylation est envoyé par la conduite (41) dans la conduite (21) où il est mélangé avec l'effluent provenant du reforming catalytique. L'ensemble est envoyé à l'étape de séparation à l'issue de laquelle une fraction intermédiaire plus importante est récupérée.
Bien que ce ne soit pas indispensable au bon fonctionnement du procédé selon la présente invention, on préfère ajouter avant l'étape de transalkylation de l'hydrogène par la conduite (51), ce qui améliore généralement la stabilité du catalyseur notamment en diminuant la cokéfaction.
De même, les conduites (311) et (331) indiquées à la figure 1 ne sont pas indispensables; elles permettent dans certains cas d'ajuster les proportions relatives des fractions lourdes et légères avant introduction dans le réacteur de transalkylation.The heavy and light fractions are then mixed and introduced into a transalkylation reactor (4) in which it is brought into contact with a transalkylation catalyst under suitable conditions. This transalkylation step can be carried out in ascending or descending mode. The effluent from this transalkylation step is sent via line (41) to line (21) where it is mixed with the effluent from catalytic reforming. The whole is sent to the separation step at the end of which a larger intermediate fraction is recovered.
Although this is not essential for the proper functioning of the process according to the present invention, it is preferable to add before the step of transalkylation of hydrogen via line (51), which generally improves the stability of the catalyst, in particular by reducing coking. .
Likewise, the pipes (311) and (331) indicated in FIG. 1 are not essential; in certain cases they allow the relative proportions of the heavy and light fractions to be adjusted before introduction into the transalkylation reactor.
Le reforming catalytique des hydrocarbures est bien connu de l'homme de l'art. L'objectif du reforming catalytique est la conversion sélective des hydrocarbures saturés en aromatiques. Ce procédé permet d'obtenir des essences à haut indice d'octane ainsi que des hydrocarbures aromatiques. De nombreuses réactions ont lieu lors du reforming catalytique, la principale étant la déshydrogénation. Les catalyseurs généralement utilisés sont à double fonction : un élément métallique permet de catalyser la déshydrogénation/hydrogénation et une fonction acide catalyse les réarrangements des hydrocarbures. Ces catalyseurs contiennent habituellement une petite quantité de platine hautement dispersé (de préférence moins de 1% en poids) supporté sur de l'alumine à haute surface spécifique (de l'ordre de 150-300m²/g) ; un deuxième métal tel que le rhénium est également souvent utilisé. Il arrive également que le catalyseur utilisé soit dispersé sur un support basique. Les conditions opératoires utilisées sont généralement une température comprise entre 400 et 550°C et une pression comprise entre 0,3 et 3,5 MPa. La réaction s'effectue en général dans des réacteurs à lits fixes ou mouvants.Catalytic reforming of hydrocarbons is well known to those skilled in the art. The objective of catalytic reforming is the selective conversion of saturated hydrocarbons to aromatics. This process makes it possible to obtain gasolines with high octane number as well as aromatic hydrocarbons. Many reactions take place during catalytic reforming, the main one being dehydrogenation. The catalysts generally used have a double function: a metallic element makes it possible to catalyze dehydrogenation / hydrogenation and an acid function catalyzes the rearrangements of hydrocarbons. These catalysts usually contain a small amount of highly dispersed platinum (preferably less than 1% by weight) supported on alumina with a high specific surface (of the order of 150-300m² / g); a second metal such as rhenium is also often used. It also happens that the catalyst used is dispersed on a basic support. The operating conditions used are generally a temperature between 400 and 550 ° C and a pressure between 0.3 and 3.5 MPa. The reaction is generally carried out in reactors with fixed or moving beds.
La Demanderesse a trouvé d'une manière inattendue qu'en soumettant le mélange des fractions lourde et légère à une étape de transalkylation et en réintroduisant l'effluent résultant dans l'étape de séparation, on accroissait la quantité totale de fraction intermédiaire c'est-à-dire le rendement en essences à haut indice d'octane.The Applicant has unexpectedly found that by subjecting the mixture of heavy and light fractions to a transalkylation step and by reintroducing the resulting effluent in the separation step, the total amount of intermediate fraction is increased. ie the yield of gasoline with a high octane number.
Bien que ce ne soit pas nécessaire pour effectuer le procédé selon la présente invention, on peut également introduire à l'étape c (étape de mélange de la fraction légère et de la fraction lourde) toute autre source de benzène dilué et/ou toute autre source de polyalkylbenzène.Although it is not necessary to carry out the process according to the present invention, it is also possible to introduce in step c (step of mixing the light fraction and the heavy fraction) any other source of dilute benzene and / or any other source of polyalkylbenzene.
Conformément à la présente invention, on peut utiliser toutes sortes de procédés de transalkylation de polyalkylbenzènes en monoalkylbenzènes. Ces procédés dans lesquels on fait réagir une charge comprenant du benzène et des polyalkylbenzènes dans un réacteur de transalkylation, en présence d'un catalyseur, pour former des monoalkylbenzènes sont bien connus de l'homme de l'art. De préférence, selon la présente invention, on utilisera un procédé semblable à celui décrit dans la demande de brevet W089/12613 au nom de Lummus Crest Inc. qui est incorporé par référence. Ce brevet décrit un procédé de transalkylation d'une charge contenant au moins un polyalkylbenzène dans un réacteur en présence d'un catalyseur de transalkylation afin de produire au moins un monoalkylbenzène caractérisé en ce que la réaction s'effectue en présence d'hydrogène. Les rapports molaire hydrogène:groupes alkyls sont de préférence compris entre 1:10 et 1:1.In accordance with the present invention, all kinds of processes for transalkylation of polyalkylbenzenes to monoalkylbenzenes can be used. These processes in which a charge comprising benzene and polyalkylbenzenes is reacted in a transalkylation reactor, in the presence of a catalyst, to form monoalkylbenzenes are well known to those skilled in the art. Preferably, according to the present invention, a process similar to that described in patent application WO89 / 12613 in the name of Lummus Crest Inc. will be used which is incorporated by reference. This patent describes a process for transalkylating a feedstock containing at least one polyalkylbenzene in a reactor in the presence of a transalkylation catalyst in order to produce at least one monoalkylbenzene characterized in that the reaction is carried out in the presence of hydrogen. The hydrogen: alkyl groups molar ratios are preferably between 1:10 and 1: 1.
Conformément à la présente invention, on peut utiliser toutes sortes de catalyseurs de transalkylation. Parmi ceux-ci, on peut citer les catalyseurs à tamis moléculaire dopés avec des composés d'hydrogénation métalliques basés sur des métaux du groupe VIII du tableau périodique des éléments, tels que, en particulier, le nickel, le palladium et le platine. Les tamis moléculaires à larges pores seront particulièrement adaptés; on utilisera de préférence ceux ayant un indice de contrainte inférieur à 1. La définition de l'indice de contrainte et son calcul sont donnés à la colonne 5 du brevet US 4,211,886. On utilisera de préférence des catalyseurs de type mordénite, en particulier des catalyseurs de type mordénite légèrement déficients en aluminium et ayant un rapport molaire silice/alumine allant jusque 30, de préférence jusque 20. Parmi les catalyseurs de type mordénite qui peuvent être utilisés selon la présente invention, on peut également citer ceux décrits dans les brevets US 4,665,258 et US 4,723,048.In accordance with the present invention, all kinds of transalkylation catalysts can be used. Among these, mention may be made of molecular sieve catalysts doped with metal hydrogenation compounds based on metals from group VIII of the periodic table of the elements, such as, in particular, nickel, palladium and platinum. Large pore molecular sieves will be particularly suitable; preferably those with a stress index less than 1. The definition of the stress index and its calculation are given in column 5 of US Pat. No. 4,211,886. Preferably, mordenite type catalysts are used, in particular type catalysts. Mordenite slightly deficient in aluminum and having a silica / alumina molar ratio of up to 30, preferably up to 20. Among the mordenite catalysts which can be used according to the present invention, mention may also be made of those described in US Patents 4,665,258 and US 4,723,048.
Un des avantages apporté grâce au procédé de la présente invention consiste en la valorisation de la fraction lourde issue de l'étape de reforming.One of the advantages provided by the process of the present invention consists in the recovery of the heavy fraction resulting from the reforming step.
Un autre avantage du procédé de la présente invention consiste en ce qu'il permet de traiter des charges de naphta sans traitement préalable au reforming. En effet, il est connu de l'homme de l'art qu'afin de minimiser la quantité de fraction lourde après reforming, il est préférable de traiter la charge de naphta de départ en retirant les composés à hautes températures d'ébullition. Selon le procédé de la présente invention cette étape de prétraitement du naphta n'est plus nécessaire ce qui représente un avantage considérable.Another advantage of the process of the present invention consists in that it makes it possible to treat charges of naphtha without treatment prior to reforming. Indeed, it is known to those skilled in the art that in order to minimize the amount of heavy fraction after reforming, it is preferable to treat the charge of starting naphtha by removing the compounds at high boiling temperatures. According to the process of the present invention, this step of pretreatment of naphtha is no longer necessary, which represents a considerable advantage.
Après l'étape de reforming, la fraction légère obtenue est riche en benzène. Dans l'art antérieur, cette fraction légère était incorporée dans les essences ce qui nécessitait bien souvent un traitement afin de limiter la teneur en benzène des essences. Cette étape supplémentaire n'est plus nécessaire selon le procédé de la présente invention car la teneur en benzène est automatiquement limitée suite à la conversion du benzène lors de l'étape de transalkylation.After the reforming step, the light fraction obtained is rich in benzene. In the prior art, this light fraction was incorporated into gasolines which very often required treatment in order to limit the benzene content of the gasolines. This additional step is no longer necessary according to the process of the present invention since the benzene content is automatically limited following the conversion of the benzene during the transalkylation step.
Les exemples suivants sont donnés afin de mieux illustrer la présente invention, mais sans pour autant en limiter la portée.The following examples are given to better illustrate the present invention, but without limiting its scope.
Après avoir soumis une charge de naphta à une étape de reforming catalytique (les compositions respectives de la charge et de l'effluent sont indiquées au tableau 1) et après avoir procédé à la séparation par distillation des fractions légère, intermédiaire et lourde, on a mélangé la totalité des fractions légère et lourde. On a ajouté au mélange de l'hydrogène et on a introduit l'ensemble dans un réacteur de transalkylation.After having subjected a charge of naphtha to a catalytic reforming step (the respective compositions of the charge and of the effluent are indicated in Table 1) and after having carried out the separation by distillation of the light, intermediate and heavy fractions, we have mixed all of the light and heavy fractions. Hydrogen was added to the mixture and the whole was introduced into a transalkylation reactor.
Le catalyseur utilisé est à base de nickel (1,6% en poids) déposé sur une mordénite dont le rapport molaire silice/alumine est de 8,8. Ce catalyseur a été activé de la façon suivante : sous 6 MPa, avec un débit d'hydrogène, la température est montée progressivement à 200°C et maintenue 12 heures. Puis, la température est montée à 360°C et stabilisée 4 heures. Ensuite, le réacteur est refroidi à 200°C.The catalyst used is based on nickel (1.6% by weight) deposited on a mordenite whose silica / alumina molar ratio is 8.8. This catalyst was activated in the following way: at 6 MPa, with a flow of hydrogen, the temperature gradually rose to 200 ° C. and maintained for 12 hours. Then, the temperature rose to 360 ° C and stabilized for 4 hours. Then, the reactor is cooled to 200 ° C.
Les conditions opératoires de la transalkylation sont indiquées au tableau 2. La composition de l'effluent de transalkylation est également indiquée au tableau 2.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE9300104 | 1993-02-02 | ||
| BE9300104A BE1006675A3 (en) | 1993-02-02 | 1993-02-02 | Method for producing species high octane. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0610168A1 true EP0610168A1 (en) | 1994-08-10 |
| EP0610168B1 EP0610168B1 (en) | 1999-04-07 |
Family
ID=3886829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94870015A Expired - Lifetime EP0610168B1 (en) | 1993-02-02 | 1994-01-31 | Process for the production of high octane number gasolines |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6281398B1 (en) |
| EP (1) | EP0610168B1 (en) |
| JP (1) | JP3469625B2 (en) |
| AT (1) | ATE178647T1 (en) |
| BE (1) | BE1006675A3 (en) |
| DE (1) | DE69417607T2 (en) |
| DK (1) | DK0610168T3 (en) |
| ES (1) | ES2131660T3 (en) |
| GR (1) | GR3030656T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0763002A1 (en) * | 1993-03-08 | 1997-03-19 | Mobil Oil Corporation | Process for producing gasoline having lower benzene content and distillation end point |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7708956B2 (en) * | 2007-09-07 | 2010-05-04 | Uop Llc | Combination hot separator and reactor vessel for simultaneously desulfurizing two vapor streams |
| CN104321412B (en) | 2012-05-02 | 2016-08-17 | 沙特阿拉伯石油公司 | Farthest produce aromatic hydrocarbons from hydrocracked naphtha |
| FR3014894B1 (en) * | 2013-12-17 | 2017-02-10 | Ifp Energies Now | CATALYTIC REFORMING PROCESS |
| FR3014895B1 (en) * | 2013-12-17 | 2017-02-10 | Ifp Energies Now | CATALYTIC REFORMING PROCESS |
| DK3167026T3 (en) * | 2014-07-07 | 2019-07-01 | Albemarle Europe Sprl | ALKYLING PROCEDURE USING A CATALYST INCLUDING THE RARE EARTH RIGHT AT CERIUM CONTAINING ZEOLITTERS AND A HYDROGENERATION METAL. |
| US10633596B2 (en) * | 2016-06-17 | 2020-04-28 | Basf Corporation | FCC catalyst having alumina derived from crystalline boehmite |
| US10093873B2 (en) | 2016-09-06 | 2018-10-09 | Saudi Arabian Oil Company | Process to recover gasoline and diesel from aromatic complex bottoms |
| US11066344B2 (en) | 2017-02-16 | 2021-07-20 | Saudi Arabian Oil Company | Methods and systems of upgrading heavy aromatics stream to petrochemical feedstock |
| JP2020510742A (en) * | 2017-03-01 | 2020-04-09 | アルベマール ヨーロッパ エスアールエル | Alkylation process with improved octane number |
| FR3068967B1 (en) * | 2017-07-13 | 2019-06-28 | IFP Energies Nouvelles | METHOD AND METHOD FOR CONVERTING ETHYLENE PRESENT IN THE HEAD EFFLUENT OF AN FCC TO INCREASE PROPYLENE PRODUCTION |
| US11613714B2 (en) | 2021-01-13 | 2023-03-28 | Saudi Arabian Oil Company | Conversion of aromatic complex bottoms to useful products in an integrated refinery process |
| US11591526B1 (en) | 2022-01-31 | 2023-02-28 | Saudi Arabian Oil Company | Methods of operating fluid catalytic cracking processes to increase coke production |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3927136A (en) * | 1974-07-05 | 1975-12-16 | Texaco Inc | Treatment of hydrocarbons |
| US4078990A (en) * | 1977-03-04 | 1978-03-14 | Mobil Oil Corporation | Manufacture of lower aromatic compounds |
| US4211886A (en) * | 1978-09-25 | 1980-07-08 | Mobil Oil Corporation | Manufacture of benzene, toluene and xylene |
| EP0422727A1 (en) * | 1989-10-06 | 1991-04-17 | Enichem Anic S.r.l. | Method for recovering trimethylbenzenes from mixtures which contain them |
| US5053573A (en) * | 1990-09-14 | 1991-10-01 | Mobil Oil Corporation | Reduction of benzene content of reformate by reaction with cycle oils |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989012613A1 (en) | 1988-06-23 | 1989-12-28 | Lummus Crest Inc. | Improved process for the transalkylation of polyalkylbenzenes |
-
1993
- 1993-02-02 BE BE9300104A patent/BE1006675A3/en not_active IP Right Cessation
-
1994
- 1994-01-31 DK DK94870015T patent/DK0610168T3/en active
- 1994-01-31 DE DE69417607T patent/DE69417607T2/en not_active Expired - Lifetime
- 1994-01-31 ES ES94870015T patent/ES2131660T3/en not_active Expired - Lifetime
- 1994-01-31 EP EP94870015A patent/EP0610168B1/en not_active Expired - Lifetime
- 1994-01-31 AT AT94870015T patent/ATE178647T1/en not_active IP Right Cessation
- 1994-02-01 JP JP02760294A patent/JP3469625B2/en not_active Expired - Fee Related
-
1999
- 1999-06-30 GR GR990401742T patent/GR3030656T3/en unknown
- 1999-10-28 US US09/429,678 patent/US6281398B1/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3927136A (en) * | 1974-07-05 | 1975-12-16 | Texaco Inc | Treatment of hydrocarbons |
| US4078990A (en) * | 1977-03-04 | 1978-03-14 | Mobil Oil Corporation | Manufacture of lower aromatic compounds |
| US4211886A (en) * | 1978-09-25 | 1980-07-08 | Mobil Oil Corporation | Manufacture of benzene, toluene and xylene |
| EP0422727A1 (en) * | 1989-10-06 | 1991-04-17 | Enichem Anic S.r.l. | Method for recovering trimethylbenzenes from mixtures which contain them |
| US5053573A (en) * | 1990-09-14 | 1991-10-01 | Mobil Oil Corporation | Reduction of benzene content of reformate by reaction with cycle oils |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0763002A1 (en) * | 1993-03-08 | 1997-03-19 | Mobil Oil Corporation | Process for producing gasoline having lower benzene content and distillation end point |
| EP0763002A4 (en) * | 1993-03-08 | 1998-07-08 | Mobil Oil Corp | Process for producing gasoline having lower benzene content and distillation end point |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06271871A (en) | 1994-09-27 |
| US6281398B1 (en) | 2001-08-28 |
| ATE178647T1 (en) | 1999-04-15 |
| ES2131660T3 (en) | 1999-08-01 |
| DE69417607D1 (en) | 1999-05-12 |
| DK0610168T3 (en) | 1999-10-18 |
| GR3030656T3 (en) | 1999-10-29 |
| BE1006675A3 (en) | 1994-11-16 |
| DE69417607T2 (en) | 1999-10-14 |
| EP0610168B1 (en) | 1999-04-07 |
| JP3469625B2 (en) | 2003-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0020240B1 (en) | Hydrocarbon hydrotreating catalysts and their use in the reforming and isomerisation of hydrocarbons in the presence of hydrogen | |
| EP0515256B1 (en) | Process for the isomerisation of Fischer-Tropsch paraffins with a catalyst based on zeolite H-Y | |
| EP0610168B1 (en) | Process for the production of high octane number gasolines | |
| EP0242260B1 (en) | Catalytic reforming process | |
| EP0789739B1 (en) | Selective hydroisomerisation method for straight and/or slightly branched long paraffins, using a molecular sieve catalyst | |
| EP0432235A1 (en) | Process for the production of improved octane numbers gasolines. | |
| FR2611739A1 (en) | PROCESS FOR ACTIVATING ISOMERIZATION CATALYST OF NORMAL PARAFFINS | |
| EP0781831B1 (en) | Process for lowering the content of benzene and of light unsaturated compounds in hydrocarbon fractions | |
| WO1996037577A1 (en) | Jet fuel and method for producing same | |
| EP0661095B1 (en) | Catalyst for lowering the benzene content in gasolines | |
| FR2676750A1 (en) | PROCESS FOR HYDROCRACKING PARAFFINS FROM THE FISCHER-TROPSCH PROCESS USING ZEOLITE H-Y CATALYSTS | |
| EP0661370B1 (en) | Catalyst for lowering the benzene content in gasolines | |
| EP0552070B1 (en) | Lowering of the benzene content in gasolines | |
| EP0440540B1 (en) | Process for the isomerization of normal paraffins in presence of at least a catalyst supported on a given zeolithe omega | |
| EP0552069B1 (en) | Lowering of the benzene content in gasolines by isomerisation | |
| EP0350367A1 (en) | Conversion process for durene into a hydrocarbon mixture having a boiling point between 30 and 300 degrees C | |
| EP0278851A2 (en) | Zeolithic catalyst, its preparation and its use in the conversion of hydrocarbons | |
| LU85406A1 (en) | CATALYTIC CRACKING PROCESS FOR LIGHT DISTILLES | |
| EP0552072A1 (en) | Lowering of the benzene contact of gasolines | |
| FR2600669A1 (en) | Hydrocracking process intended for the production of middle distillates | |
| WO2023117594A1 (en) | Unit for producing and separating aromatics with recovery of an extract and/or raffinate from a liquid-liquid extraction process | |
| EP0612564B1 (en) | Composite catalyst and its use for the aromatisation of C2-C12 hydrocarbon | |
| FR2738243A1 (en) | Hydro-isomerising straight and/or slightly branched long chain hydrocarbon(s) | |
| FR3104575A1 (en) | Device and method for converting aromatic compounds by alkylation of benzene with CO | |
| FR2597496A1 (en) | Catalytic reforming process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE |
|
| 17P | Request for examination filed |
Effective date: 19950127 |
|
| 17Q | First examination report despatched |
Effective date: 19970204 |
|
| APAB | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPE |
|
| APAB | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPE |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE |
|
| REF | Corresponds to: |
Ref document number: 178647 Country of ref document: AT Date of ref document: 19990415 Kind code of ref document: T |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19990413 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: FRENCH |
|
| REF | Corresponds to: |
Ref document number: 69417607 Country of ref document: DE Date of ref document: 19990512 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: LUCHS & PARTNER PATENTANWAELTE |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2131660 Country of ref document: ES Kind code of ref document: T3 |
|
| REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 19990514 |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IE Payment date: 19991214 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 19991223 Year of fee payment: 7 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010131 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20010131 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: RN |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: FC |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PFA Owner name: TOTAL PETROCHEMICALS RESEARCH FELUY Free format text: FINA RESEARCH S.A.#ZONE INDUSTRIELLE C#B-7181 SENEFFE (FELUY) (BE) -TRANSFER TO- TOTAL PETROCHEMICALS RESEARCH FELUY#ZONE INDUSTRIELLE C#7181 SENEFFE (FELUY) (BE) |
|
| NLT1 | Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1 |
Owner name: TOTAL PETROCHEMICALS RESEARCH FELUY Owner name: ATOFINA RESEARCH |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20091223 Year of fee payment: 17 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20100118 Year of fee payment: 17 Ref country code: ES Payment date: 20100125 Year of fee payment: 17 Ref country code: DK Payment date: 20100113 Year of fee payment: 17 Ref country code: CH Payment date: 20100125 Year of fee payment: 17 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20100127 Year of fee payment: 17 Ref country code: FR Payment date: 20100218 Year of fee payment: 17 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20100121 Year of fee payment: 17 Ref country code: DE Payment date: 20100121 Year of fee payment: 17 Ref country code: AT Payment date: 20100114 Year of fee payment: 17 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20100118 Year of fee payment: 17 Ref country code: BE Payment date: 20100315 Year of fee payment: 17 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GR Payment date: 20100126 Year of fee payment: 17 |
|
| BERE | Be: lapsed |
Owner name: S.A. *FINA RESEARCH Effective date: 20110131 |
|
| REG | Reference to a national code |
Ref country code: PT Ref legal event code: MM4A Free format text: LAPSE DUE TO NON-PAYMENT OF FEES Effective date: 20110801 |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: V1 Effective date: 20110801 |
|
| REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20110131 |
|
| REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20110930 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110131 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110131 Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110801 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110131 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110802 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110131 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110131 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110131 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 69417607 Country of ref document: DE Effective date: 20110802 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110801 Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110131 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20120220 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110201 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110201 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110802 |