EP0832958A1 - Process and apparatus for the production of low sulphur catalytically cracked gasolines - Google Patents
Process and apparatus for the production of low sulphur catalytically cracked gasolines Download PDFInfo
- Publication number
- EP0832958A1 EP0832958A1 EP97402088A EP97402088A EP0832958A1 EP 0832958 A1 EP0832958 A1 EP 0832958A1 EP 97402088 A EP97402088 A EP 97402088A EP 97402088 A EP97402088 A EP 97402088A EP 0832958 A1 EP0832958 A1 EP 0832958A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- zone
- light
- cut
- pipe
- hydrotreatment
- 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
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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Definitions
- the present invention relates to a method and an installation for the production low sulfur catalytic cracking gasolines.
- the patent US-5,318,690 proposes a process with a fractionation of gasoline, a softening of the light fraction, while the heavy fraction is hydrodesulfurized, then converted to ZSM-5 and redesulfurized under mild conditions.
- This technique is based on a separation of the raw petrol in order to obtain a light cut practically free of sulfur compounds other than mercaptans, so as to treat the cut only with softening to remove the mercaptans.
- the heavy cut contains a relatively large amount of olefins which are in part saturated during hydrotreatment.
- the patent recommends cracking on ZSM-5 in order to produce olefins, but at detriment to performance.
- these olefins can be reconstituted in the presence of H2S to form mercaptans, which has the disadvantage of calling a additional softening, or desulfurization.
- the applicant has sought a process for producing gasoline with a low sulfur content at from catalytic cracking, which makes it possible to recover the entire petrol cut, reduce the sulfur content of the petrol cut to very low levels, without loss of petrol yield, and minimizing octane loss.
- the filler is a catalytic cracking gasoline, the range of boiling points of which typically extends from C5 to 220 ° C.
- the end point of the gasoline cut depends of course on the refinery and market constraints, but generally remains within the limits indicated above.
- the sulfur content of these gasoline cuts produced by catalytic cracking (FCC) depends on the sulfur content of the feed treated with FCC, as well as the end point of the cut. Light fractions naturally have a lower sulfur content than heavier cuts. Generally, the sulfur contents of the entire gasoline cut from the FCC are greater than 100 ppm by weight and most of the time greater than 500 ppm by weight.
- the sulfur contents are often greater than 1000 ppm by weight, possibly even in certain cases reaching values of the order of 4000 to 5000 ppm by weight.
- the crude petrol obtained from catalytic cracking is fractionated into at least one light cut and at least one heavy cut. Light cutting to a final boiling point less than or equal to 210 ° C, advantageously less than or equal to 180 ° C, preferably less than or equal to 160 ° C and even more preferably less than or equal to 145 ° C.
- the light fraction of the gasoline fraction contains relatively few sulfur compounds, which are present mainly in the form of mercaptans, while the sulfur compounds of the heavier fractions are present in the form of substituted or unsubstituted thiophenes, or of heterocyclic compounds such as benzothiophene , which, unlike mercaptans, cannot be removed by extractive processes. These sulfur compounds are therefore removed by hydrotreatment.
- the light cut is relatively rich in olefins, and the sulfur is mainly present in the form of mercaptans, while the heavier cut is relatively poor in olefins and is characterized by significantly higher sulfur contents. More generally, and unlike the prior art, the cutting point is chosen so as to maximize the olefin content in the light cut.
- the gasoline catalytic cracking (FCC) cut is thus split into at least two fractions, which are then subjected to different desulfurization treatments.
- the light fraction undergoes a desulfurization treatment consisting of hydrogenation sweet, possibly preceded by a selective hydrogenation of the diolefins.
- the hydrogenation conditions are chosen mild to minimize saturation of high octane olefins.
- Desulfurization is therefore not complete, but it eliminates virtually all sulfur compounds other than mercaptans from so that the mercaptans essentially stay in the cut. They are then softened.
- This softening step can be a softening extractive, or softening by catalytic oxidation of mercaptans in a fixed bed.
- the hydrogenation of the dienes is an optional but advantageous step which makes it possible to eliminate practically all of the dienes present in the light fraction before the mild hydrotreatment. It generally takes place in the presence of a catalyst comprising at least one metal from group VIII (and preferably Pt, Pd or Ni) and a support, at a temperature of 50-250 ° C under a pressure of 4-50 bar. This step does not necessarily cause softening. It is particularly advantageous to operate under conditions such that at least partial softening of the gasoline is obtained, that is to say with the reduction of the mercaptan content.
- a catalyst comprising 0.1 to 1% of palladium deposited on a support operating under a pressure of 4-25 bar, at a temperature of 50-250 ° C., with an hourly space velocity of the liquid ( LHSV) from 1 to 10 h -1 .
- the catalyst comprises palladium (0.1 to 1% by weight, and preferably 0.2-0.5% weight) deposited on an inert support such as alumina, silica, silica-alumina, or a support containing at least 50% alumina.
- an inert support such as alumina, silica, silica-alumina, or a support containing at least 50% alumina.
- Another metal can be combined to form a bimetallic catalyst, such as nickel (1-20% by weight, and preferably 5-15% by weight) or 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 nickel (1-20% by weight, and preferably 5-15% by weight) or 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 choice of operating conditions is particularly important. We will operate the most generally under pressure in the presence of a small amount of hydrogen by compared to the stoichiometric value necessary to hydrogenate the 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 included on more generally between 50 and 200 ° C, and preferably between 80 and 200 ° C, and preferably between 150 and 170 ° C.
- the pressure is sufficient to maintain more than 80% by weight, and preferably more than 95% by weight, of the gasoline to be treated in the liquid phase in the reactor, namely the most generally between 4 and 50 bar and preferably above 10 bar.
- a pressure advantageous is between 10-30 bar, and preferably between 12-25 bar.
- the space speed is in these conditions established between 1-10 h -1 , preferably between 4-10 h-1.
- the light fraction of the catalytic cracking gasoline fraction may contain around 1% by weight of diolefins.
- the diolefin content is reduced to less than 3000 ppm, or even less than 2500 ppm and better still less than 1500 ppm. In some cases it can be obtained less than 500 ppm.
- the content of dienes after selective hydrogenation can even be reduced to less than 250 ppm.
- the hydrogenation step takes place in a catalytic hydrogenation reactor which comprises a catalytic reaction zone traversed by the entire charge and the quantity of hydrogen necessary to carry out the desired reactions.
- the hydrogenation stage takes place in a catalytic hydrogenation reactor which is arranged in a particular manner, namely at least two catalytic zones, the first being crossed by the liquid charge (and a amount of hydrogen lower than the stoichiometry necessary to convert all the diolefins into mono-olefins), the second receiving the liquid charge coming from the first zone (as well as the rest of the hydrogen i.e. an amount of sufficient hydrogen to convert the remaining diolefins into mono-olefins and to at least partially isomerize the primary and secondary olefins into tertiary olefins) for example injected through a side tube and dispersed using an appropriate diffuser.
- the proportion of the first zone (by volume) is at most equal to 75% of the sum of the 2 zones and preferably from 15 to 30%.
- Another advantageous embodiment comprises a hydrogenation of the dienes on a catalyst different from Pd, a mild hydrotreatment and a final oxidative softening.
- the purpose of the mild hydrodesulfurization of the light fraction of the FCC gasoline fraction is, using a conventional hydrotreatment catalyst under mild conditions of temperature and pressure, to convert the sulfur compounds of the fraction other than H 2 S mercaptans, so as to obtain an effluent containing as sulfur compounds only mercaptans.
- the resulting cut has the same distillation range, and a slightly lower octane number due to the inevitable partial saturation of the olefins.
- the conditions of the hydrotreatment reactor must be adjusted to reach the desired level of desulphurization, and above all to minimize the loss of octane resulting from the saturation of the olefins.
- the temperature of the mild hydrotreatment stage is generally between 160 ° C and 380 ° C, preferably between 180 ° C and 360 ° C, and more preferably between 180 ° C and 320 ° C.
- Low to moderate pressures are generally sufficient, between 5 and 50 bar, preferably between 10 and 45 bar, and more preferably between 10 and 30 bar.
- the LHSV space speed is between 0.5 and 10 h -1, preferably between 1 and 6 h -1.
- the catalyst (s) used in the mild hydrotreatment reactor is a conventional hydrodesulfurization catalyst, comprising at least one group VI metal and / or at least one group VIII metal, on a suitable support .
- the group VI metal is generally molybdenum or tungsten
- the group VIII metal is generally nickel or cobalt. Combinations such as Ni-Mo or Co-Mo are typical.
- the catalyst support is usually a porous solid such as alumina, silica-alumina or other porous solids such as magnesia, silica or TiO2, alone or as a mixture with alumina or silica-alumina.
- the lighter fraction of the gasoline fraction is then subjected to a non-hydrogenating desulfurization aiming to remove the sulfur compounds remaining in the form of mercaptans.
- a non-hydrogenating desulfurization aiming to remove the sulfur compounds remaining in the form of mercaptans.
- It can be an extractive softening process using sodium or potassium soda or cresylate. Extractive processes are sufficient as long as the treated cut does not contain high molecular weight mercaptans.
- Softening can also be carried out by catalytic oxidation of the mercaptans to disulfides.
- This catalytic oxidation of the mercaptans to disulfides can be carried out simply by mixing the gasoline to be treated with an aqueous solution of an alkaline base, such as sodium hydroxide, in which a catalyst based on a metal chelate is added, in the presence of an oxidizing agent.
- an alkaline base such as sodium hydroxide
- a catalyst based on a metal chelate is added
- an oxidizing agent In the case where the mercaptans content of the gasoline is high, it is preferable to bring the section into contact with a fixed bed of supported catalyst, in the presence of an alkaline base and an oxidizing agent.
- the alkaline base is not incorporated into the catalyst.
- the reaction medium usually soda in aqueous solution; it is introduced into the reaction medium either continuously or intermittently, to maintain the alkalinity conditions and the aqueous phase necessary for the oxidation reaction.
- the oxidizing agent generally air, is advantageously mixed with the petrol cut to be softened.
- the metal chelate used as catalyst is generally a metal phthalocyanine, such as cobalt phthalocyanine for example.
- the reaction takes place at a pressure between 1 and 30 bar, at a temperature between 20 and 100 ° C, and preferably 20 and 80 ° C.
- the alkaline base can be incorporated into the catalyst by introducing an alkaline ion into a mixed oxide structure essentially consisting of combined aluminum and silicon oxides.
- aluminosilicates of alkali metals are used, characterized by an atomic Si / Al ratio of their structure less than or equal to 5 (that is to say a molar ratio SiO 2 / Al 2 O 3 less than or equal to 10), and which are intimately associated with activated carbon and a metal chelate and exhibit optimal catalytic performances in softening when the hydration rate of the catalyst is between 0.1 and 40% and preferably between 1 and 25% by weight thereof.
- alkaline aluminosilicates In addition to their superior catalytic performance, these alkaline aluminosilicates have the advantage of very low solubility in aqueous medium, which allows their prolonged use in the hydrated state to treat petroleum fractions to which a little water is regularly added, or optionally, alkaline solution.
- This softening step (preferably carried out in a fixed bed) of the light petrol fraction containing mercaptans can therefore be defined as comprising the passage, under oxidation conditions, of the petrol to be treated (stabilized) in contact with a porous catalyst.
- it comprises from 10 to 98%, preferably from 50 to 95% by weight, of at least one inorganic solid phase consisting of an alkaline aluminosilicate having an atomic ratio Si / Al less than or equal to 5, preferably less than or equal to 3, from 1 to 60% by weight of activated carbon, from 0.02 to 2% by weight of at least one metal chelate and from 0 to 20% by weight at least one mineral or organic binder.
- at least one inorganic solid phase consisting of an alkaline aluminosilicate having an atomic ratio Si / Al less than or equal to 5, preferably less than or equal to 3, from 1 to 60% by weight of activated carbon, from 0.02 to 2% by weight of at least one metal chelate and from 0 to 20% by weight at least one mineral or organic binder.
- This porous catalyst has a basicity determined according to standard ASTM 2896 greater than 20 milligrams of potassium hydroxide per gram and a total BET surface area greater than 10 m 2 / g, and contains within its porosity a permanent aqueous phase representing 0, 1 to 40%, preferably 1 to 25%, by weight of the dry catalyst.
- said alkaline aluminosilicate is obtained by reaction in the medium aqueous of at least one clay (kaolinite, halloysite, montmorillonite, etc ...) with at at least one compound (hydroxide, carbonate, acetate, nitrate, etc.) of at least one metal alkaline, in particular sodium, and potassium, this compound preferably being hydroxide, followed by heat treatment at a temperature between 90 and 600 ° C, preferably between 120 and 350 ° C.
- the clay can also be heat treated and ground before being brought into contact with the alkaline solution.
- Kaolinite and all of its thermal transformation products metalakaolin, reverse spinel phase, mullite can be used according to the invention.
- any chelate used for this purpose in the prior art in particular phthalocyanines, porphyrins or metal corrines, can be deposited on the support.
- phthalocyanines in particular phthalocyanines, porphyrins or metal corrines
- cobalt phthalocyanine and vanadium phthalocyanine are particularly preferred.
- Metallic phthalocyanine is preferably used in the form of a derivative of the latter, with particular preference for its commercially available sulfonates, such as, for example, cobalt phthalocyanine mono- or disulfonate and mixtures thereof. this.
- water can be added in adequate quantity to the cut petroleum, upstream of the catalyst continuously or discontinuously to maintain the degree of hydration within the desired range, i.e. the water content of the support is maintained between 0.1 and 40% by weight of the support, and preferably between 1 and 25%.
- the temperature of the feed is fixed at a sufficient value, less than 80 ° C., to dissolve the reaction water resulting from the transformation of the mercaptans into disulfides.
- the temperature of the load is thus chosen so as to maintain the water content of the support between 0.1 and 40% by weight of the support and, preferably, between 1 and 25% by weight of the latter. This range of predetermined values of water contents of the support will depend, of course, on the very nature of the catalytic support used during the softening reaction.
- this softening step can be eliminated when the light cut has been selectively hydrogenated to remove the dienes and that at the same time softening has been obtained.
- the softening yield may be such that the final step of softening with an oxidizing agent may no longer be necessary.
- This case is well verified with a palladium-based catalyst as described above.
- the presence of this treatment step with a palladium catalyst can also make it possible to modify the softening step, for example by increasing the hourly speed, hence increased productivity, or by reducing the quantity of catalyst, hence a reduced investment.
- a selective hydrogenation step of the dienes can be used which is not softening.
- Hydrodesulfurization of the heaviest fraction of FCC gasoline is conducted following the same process as that used for the light fraction.
- the catalyst contains also at least one metal from G VIII and / or from group VI, deposited on a support. Only the operating conditions are adjusted, in order to obtain the level of desulphurization desired, on this cut richer in sulfur.
- the temperature used is generally between 200 ° C and 420 ° C, preferably between 220 ° C and 400 ° C.
- the pressures operating procedures are generally between 20 and 80 bar and preferably between 30 and 50 bar.
- the effluent obtained is stripped to remove H2S and is sent to the pool essence.
- the invention also relates to an installation for implementing the method according to the invention.
- the softening zone is located after stripping and the installation also comprises a zone for the selective hydrogenation of the dienes situated between the fractionation column and the zone for mild hydrotreatment, said hydrogenation zone comprising a pipe for the introduction of the light cut and a pipe for the exit of the dedicated light cut.
- the installation also comprises a zone (15) for hydrotreating the heavy fraction, provided with a line (4) for the introduction of the heavy cut coming from the column (1), a line ( 16) for the outlet of the hydrotreated section and a pipe (17) bringing the hydrogen to the level of the charge or the zone, said zone being followed by a stripping column (18) provided with a pipe for the introduction of the hydrotreated section, a pipe (19) for the outlet of H 2 S and a pipe (20) for the outlet of the hydrotreated section.
- the cuts coming out through the pipes (20) and (13) can be sent to petrol storage via a pipe (21).
- the light cut of FCC essence is rich in olefins and contains almost all of the mercaptans.
- the heavier fraction, richer in sulfur, contains sulfur compounds essentially in the form of thiophenic derivatives.
- Table 2 below indicates the operating conditions used for the hydrotreatment of heavy gasoline, as well as the characteristics of the heavy gasoline thus desulfurized.
- the catalyst used is a CoMo supported alumina (HR 306C sold by the company Procatalyse). Characteristics of heavy petrol hydrodesulfurization.
- Table 3 shows the characteristics of light gasoline which is desulfurized and then softened.
- the temperature is 280 ° C
- the pressure is 20 bar
- the catalyst is LD 145 based on NiMo sold by the company Procatalyse followed by a CoMo catalyst (HR306 C sold by the company Procatalyse). Characteristics of the initial light essence, after gentle hydrotreatment then after softening.
- the softening is carried out on a catalyst comprising sodalite (alkaline aluminosilicate) and 20% of activated carbon, impregnated with an oxidizing agent such as sulfonated cobalt phthalocyamine (impregnation of PeCo: 60 kg (m 3 of cat) prepared as described in patent EP-A-638,628).
- an oxidizing agent such as sulfonated cobalt phthalocyamine (impregnation of PeCo: 60 kg (m 3 of cat) prepared as described in patent EP-A-638,628).
- the method and the installation according to the invention thus make it possible to obtain essences of FCC containing less than 50 ppm of sulfur, responding negatively to the "doctor test" and this with a loss in octane barrel index (RON + MON) / 2 of less than 8 points per compared to the same cut of raw FCC gasoline before treatment, and preferably less than or equal to 6 points.
Abstract
Description
La présente invention concerne un procédé et une installation pour la production d'essences de craquage catalytique à faible teneur en soufre.The present invention relates to a method and an installation for the production low sulfur catalytic cracking gasolines.
La production d'essence reformulée répondant aux nouvelles normes d'environnement
nécessite notamment que l'on diminue leur concentration en oléfines et/ou en
aromatiques (surtout le benzène) et en soufre (dont les mercaptans).
Les essences de craquage catalytique présentent des teneurs en oléfines élevées, et le
soufre présent dans le pool essence est imputable à près de 90 % à l'essence de FCC.The production of reformulated gasoline meeting new environmental standards requires in particular that their concentration of olefins and / or aromatics (especially benzene) and sulfur (including mercaptans) be reduced.
Catalytic cracked gasolines have high olefin contents, and the sulfur present in the gasoline pool is attributable to almost 90% of FCC gasoline.
L'hydrotraitement de la charge envoyée au craquage catalytique permet d'atteindre des essences contenant typiquement 100 ppm de soufre. Les unités d'hydrotraitement de charges FCC opèrent cependant dans des conditions sévères de température et de pression, ce qui suppose un effort d'investissement important.The hydrotreatment of the charge sent to catalytic cracking makes it possible to reach gasolines typically containing 100 ppm of sulfur. The hydrotreating units of FCC loads, however, operate under severe temperature and pressure, which implies a significant investment effort.
L'hydrotraitement des essences de craquage catalytique permet à la fois de réduire la teneur en soufre et en oléfines de la coupe. Cependant, ceci présente l'inconvénient majeur d'entraíner une perte très importante en octane baril de la coupe, en raison de la saturation de l'ensemble des oléfines.The hydrotreating of catalytic cracking gasolines both reduces the sulfur and olefin content in the cut. However, this has the disadvantage major to cause a very significant loss in octane barrel of the cup, due to the saturation of all olefins.
Il a été déjà proposé des procédés d'hydrotraitement des essences FCC. Par exemple, le brevet US-5,290,427 décrit un procédé consistant à fractionner l'essence, désulfurer les fractions et convertir la fraction essence sur une zéolithe ZSM-5.Hydrotreatment processes for FCC gasolines have already been proposed. For example, the US Pat. No. 5,290,427 describes a process consisting in fractionating petrol, desulfurizing the fractions and convert the gasoline fraction onto a ZSM-5 zeolite.
Le brevet US-5,318,690 propose un procédé avec un fractionnement de l'essence, un adoucissement de la fraction légère, tandis que la fraction lourde est hydrodésulfurée, puis convertie sur ZSM-5 et redésulfurée dans des conditions douces. Cette technique est basée sur une séparation de l'essence brute de façon à obtenir une coupe légère pratiquement dépourvue de composés soufrés autres que les mercaptans, de façon à traiter la coupe uniquement avec un adoucissement pour enlever les mercaptans. De ce fait, la coupe lourde contient une quantité relativement importante d'oléfines qui sont en partie saturées lors de l'hydrotraitement. Pour éviter cette perte d'indice d'octane, le brevet préconise un craquage sur ZSM-5 de façon à produire des oléfines, mais au détriment du rendement. De plus, ces oléfines peuvent se reconstituer en présence d'H2S pour former des mercaptans, ce qui a pour inconvénient d'appeler un adoucissement supplémentaire, ou une désulfuration. The patent US-5,318,690 proposes a process with a fractionation of gasoline, a softening of the light fraction, while the heavy fraction is hydrodesulfurized, then converted to ZSM-5 and redesulfurized under mild conditions. This technique is based on a separation of the raw petrol in order to obtain a light cut practically free of sulfur compounds other than mercaptans, so as to treat the cut only with softening to remove the mercaptans. From this fact, the heavy cut contains a relatively large amount of olefins which are in part saturated during hydrotreatment. To avoid this loss of octane number, the patent recommends cracking on ZSM-5 in order to produce olefins, but at detriment to performance. In addition, these olefins can be reconstituted in the presence of H2S to form mercaptans, which has the disadvantage of calling a additional softening, or desulfurization.
Un autre moyen couramment utilisé par le raffineur pour traiter ce problème du soufre dans les essences est de séparer la fraction à point d'ébullition d'au moins 180°C qui contient l'essentiel des composés soufrés autres que les mercaptans. Cette fraction est alors déclassée avec le LCO (light cycle oil) et n'est en général pas valorisée, ou elle est utilisée comme diluant de charge.Another way commonly used by the refiner to deal with this sulfur problem in gasolines is to separate the boiling point fraction of at least 180 ° C which contains most of the sulfur compounds other than mercaptans. This fraction is then downgraded with LCO (light cycle oil) and is generally not valued, or it is used as a charge diluent.
Le déposant a recherché un procédé de production d'essences à faible teneur en soufre à partir du craquage catalytique, qui permet de valoriser la totalité de la coupe essence, de réduire la teneur en soufre de la coupe essence à de très faibles niveaux, sans perte de rendement essence, et en minimisant la perte en octane.The applicant has sought a process for producing gasoline with a low sulfur content at from catalytic cracking, which makes it possible to recover the entire petrol cut, reduce the sulfur content of the petrol cut to very low levels, without loss of petrol yield, and minimizing octane loss.
Plus précisément dans le procédé selon l'invention, l'essence brute est fractionnée en au moins une coupe légère à point d'ébullition inférieur ou égal à 210°C contenant la majeure partie des oléfines et des mercaptans, et au moins une fraction lourde. La coupe légère est soumise à un hydrotraitement doux, en présence d'hydrogène, avec un catalyseur contenant au moins un métal du groupe VIII et/ou au moins un métal du groupe VI, à une température de 160-380°C, sous une pression de 5-50 bar, et l'effluent obtenu est strippé pour éliminer H2S. La fraction légère est soumise à un adoucissement qui est réalisé par au moins l'un des procédés suivants :
- traitement de la coupe légère avant l'hydrotraitement doux, en présence d'hydrogène avec un catalyseur contenant 0,1-1% de palladium déposé sur un support, à une température de 50-250°C, sous une pression de 4-50 bar;
- adoucissement extractif de l'effluent obtenu après hydrotraitement doux et strippage;
- adoucissement avec un agent oxydant, un catalyseur et une base alcaline incorporée ou non au catalyseur, de l'effluent obtenu après hydrotraitement doux et strippage.
- treatment of the light cut before the mild hydrotreatment, in the presence of hydrogen with a catalyst containing 0.1-1% of palladium deposited on a support, at a temperature of 50-250 ° C, under a pressure of 4-50 bar;
- extractive softening of the effluent obtained after gentle hydrotreatment and stripping;
- softening with an oxidizing agent, a catalyst and an alkaline base incorporated or not in the catalyst, of the effluent obtained after mild hydrotreatment and stripping.
La charge est une essence de craquage catalytique, dont la gamme de points d'ébullition
s'étend typiquement des C5 jusqu'à 220°C. Le point final de la coupe essence dépend
bien sûr de la raffinerie et des contraintes du marché, mais reste généralement dans les
limites indiquées ci-avant.
La teneur en soufre de ces coupes essences produites par craquage catalytique (FCC)
dépend de la teneur en soufre de la charge traitée au FCC, ainsi que du point final de la
coupe. Les fractions légères ont naturellement une teneur en soufre plus faible que les
coupes plus lourdes. Généralement, les teneurs en soufre de l'intégralité de la coupe
essence provenant du FCC sont supérieures à 100 ppm poids et la plupart du temps
supérieures à 500 ppm poids. Pour des essences ayant des points finaux supérieurs à
200°C, les teneurs en soufre sont souvent supérieures à 1000 ppm poids, pouvant même
dans certains cas atteindre des valeurs de l'ordre de 4000 à 5000 ppm poids.
Selon l'invention, l'essence brute provenant du craquage catalytique est fractionnée en
au moins une coupe légère et au moins une coupe lourde.
La coupe légère à un point d'ébullition final inférieur ou égal à 210°C, avantageusement
inférieur ou égal à 180°C, de préférence inférieur ou égal à 160°C et encore plus préféré
inférieur ou égal à 145°C.
La fraction légère de la coupe essence contient relativement peu de composés soufrés,
qui sont présents en majorité sous forme de mercaptans, tandis que les composés
soufrés des fractions plus lourdes sont présents sous forme de thiophènes substitués ou
non, ou de composés hétérocycliques tels le benzothiophène, qui, contrairement aux
mercaptans, ne peuvent pas être éliminés par les procédés extractifs. Ces composés
soufrés sont par conséquent éliminés par hydrotraitement. La coupe légère est
relativement riche en oléfines, et le soufre est essentiellement présent sous forme de
mercaptans, tandis que la coupe plus lourde est relativement pauvre en oléfines et est
caractérisée par des teneurs en soufre nettement plus élevées.
De façon plus générale, et contrairement à l'art antérieur le point de coupe est choisi de
façon à maximiser la teneur en oléfines dans la coupe légère.The filler is a catalytic cracking gasoline, the range of boiling points of which typically extends from C5 to 220 ° C. The end point of the gasoline cut depends of course on the refinery and market constraints, but generally remains within the limits indicated above.
The sulfur content of these gasoline cuts produced by catalytic cracking (FCC) depends on the sulfur content of the feed treated with FCC, as well as the end point of the cut. Light fractions naturally have a lower sulfur content than heavier cuts. Generally, the sulfur contents of the entire gasoline cut from the FCC are greater than 100 ppm by weight and most of the time greater than 500 ppm by weight. For gasolines having end points greater than 200 ° C., the sulfur contents are often greater than 1000 ppm by weight, possibly even in certain cases reaching values of the order of 4000 to 5000 ppm by weight.
According to the invention, the crude petrol obtained from catalytic cracking is fractionated into at least one light cut and at least one heavy cut.
Light cutting to a final boiling point less than or equal to 210 ° C, advantageously less than or equal to 180 ° C, preferably less than or equal to 160 ° C and even more preferably less than or equal to 145 ° C.
The light fraction of the gasoline fraction contains relatively few sulfur compounds, which are present mainly in the form of mercaptans, while the sulfur compounds of the heavier fractions are present in the form of substituted or unsubstituted thiophenes, or of heterocyclic compounds such as benzothiophene , which, unlike mercaptans, cannot be removed by extractive processes. These sulfur compounds are therefore removed by hydrotreatment. The light cut is relatively rich in olefins, and the sulfur is mainly present in the form of mercaptans, while the heavier cut is relatively poor in olefins and is characterized by significantly higher sulfur contents.
More generally, and unlike the prior art, the cutting point is chosen so as to maximize the olefin content in the light cut.
La coupe essence de craquage catalytique (FCC) est ainsi fractionnée en au moins deux fractions, qui sont ensuite soumises à des traitements de désulfuration différents. La fraction légère subit un traitement de désulfuration constitué par une hydrogénation douce, éventuellement précédée d'une hydrogénation sélective des dioléfines. Les conditions d'hydrogénation sont choisies douces pour minimiser la saturation des oléfines de haut indice d'octane. La désulfuration n'est donc pas complète mais elle permet d'éliminer pratiquement tous les composés soufrés autres que les mercaptans de façon à ce que restent dans la coupe essentiellement les mercaptans. Ils sont ensuite éliminés par adoucissement. Cette étape d'adoucissement peut être un adoucissement extractif, ou un adoucissement par oxydation catalytique des mercaptans en lit fixe.The gasoline catalytic cracking (FCC) cut is thus split into at least two fractions, which are then subjected to different desulfurization treatments. The light fraction undergoes a desulfurization treatment consisting of hydrogenation sweet, possibly preceded by a selective hydrogenation of the diolefins. The hydrogenation conditions are chosen mild to minimize saturation of high octane olefins. Desulfurization is therefore not complete, but it eliminates virtually all sulfur compounds other than mercaptans from so that the mercaptans essentially stay in the cut. They are then softened. This softening step can be a softening extractive, or softening by catalytic oxidation of mercaptans in a fixed bed.
L'hydrogénation des diènes est une étape optionnelle mais avantageuse qui permet
d'éliminer pratiquement la totalité des diènes présents dans la fraction légère avant
l'hydrotraitement doux. Elle se déroule généralement en présence d'un catalyseur
comprenant au moins un métal du groupe VIII (et de préférence Pt, Pd ou Ni) et un
support, à une température de 50-250°C sous une pression de 4-50 bar. Cette étape ne
provoque pas forcément l'adoucissement. Il est particulièrement avantageux d'opérer
dans des conditions telles qu'un adoucissement, au moins partiel, de l'essence soit
obtenu, c'est-à-dire avec la réduction de la teneur en mercaptans.
Pour ce faire, on emploiera avantageusement un catalyseur comprenant 0,1 à 1% de
palladium déposé sur un support opérant sous une pression de 4-25 bar, à une
température de 50-250 °C, avec une vitesse spatiale horaire du liquide (LHSV) de 1 à
10 h-1.The hydrogenation of the dienes is an optional but advantageous step which makes it possible to eliminate practically all of the dienes present in the light fraction before the mild hydrotreatment. It generally takes place in the presence of a catalyst comprising at least one metal from group VIII (and preferably Pt, Pd or Ni) and a support, at a temperature of 50-250 ° C under a pressure of 4-50 bar. This step does not necessarily cause softening. It is particularly advantageous to operate under conditions such that at least partial softening of the gasoline is obtained, that is to say with the reduction of the mercaptan content.
To do this, it is advantageous to use a catalyst comprising 0.1 to 1% of palladium deposited on a support operating under a pressure of 4-25 bar, at a temperature of 50-250 ° C., with an hourly space velocity of the liquid ( LHSV) from 1 to 10 h -1 .
Le catalyseur comporte du palladium (0,1 à 1 % poids, et de préférence 0,2-0,5 % poids) déposé sur un support inerte tel que l'alumine, la silice, la silice-alumine, ou un support contenant au moins 50 % d'alumine.The catalyst comprises palladium (0.1 to 1% by weight, and preferably 0.2-0.5% weight) deposited on an inert support such as alumina, silica, silica-alumina, or a support containing at least 50% alumina.
Un autre métal peut être associé pour former un catalyseur bimétallique, tel que le nickel (1-20 % poids, et de préférence 5-15 % poids) ou 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 nickel (1-20% by weight, and preferably 5-15% by weight) or 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 choix des conditions opératoires est particulièrement important. On opèrera le plus généralement sous pression en présence d'une quantité d'hydrogène en faible excès par rapport à la valeur stoechiométrique nécessaire pour hydrogéner les dioléfines. L'hydrogène et la charge à traiter sont injectés en courants ascendants ou descendants dans un réacteur de préférence à lit fixe de catalyseur. La température est comprise le plus généralement entre 50 et 200 °C, et de préférence entre 80 et 200°C, et de préférence entre 150 et 170 °C.The choice of operating conditions is particularly important. We will operate the most generally under pressure in the presence of a small amount of hydrogen by compared to the stoichiometric value necessary to hydrogenate the 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 included on more generally between 50 and 200 ° C, and preferably between 80 and 200 ° C, and preferably between 150 and 170 ° C.
La pression est suffisante pour maintenir plus de 80% poids, et de préférence plus de 95% poids, de l'essence à traiter en phase liquide dans le réacteur à savoir le plus généralement entre 4 et 50 bar et de préférence au-dessus de 10 bar. Une pression avantageuse est comprise entre 10-30 bar, et de préférence entre 12-25 bar.The pressure is sufficient to maintain more than 80% by weight, and preferably more than 95% by weight, of the gasoline to be treated in the liquid phase in the reactor, namely the most generally between 4 and 50 bar and preferably above 10 bar. A pressure advantageous is between 10-30 bar, and preferably between 12-25 bar.
La vitesse spatiale est dans ces conditions établie entre 1-10 h-1, de préférence entre 4-10h-1.The space speed is in these conditions established between 1-10 h -1 , preferably between 4-10 h-1.
La fraction légère de la coupe essence de craquage catalytique peut contenir de l'ordre
de 1% poids de dioléfines. Après hydrogénation, la teneur en dioléfines est réduite à
moins de 3 000 ppm, voire moins de 2 500 ppm et mieux moins de 1 500 ppm. Dans
certains cas il peut être obtenu moins de 500 ppm. La teneur en diènes après
hydrogénation sélective peut même être réduite à moins de 250 ppm.
Selon une réalisation de l'invention, l'étape d'hydrogénation se déroule dans un réacteur
catalytique d'hydrogénation qui comprend une zone réactionnelle catalytique traversée
par la totalité de la charge et la quantité d'hydrogène nécessaire pour effectuer les
réactions désirées.The light fraction of the catalytic cracking gasoline fraction may contain around 1% by weight of diolefins. After hydrogenation, the diolefin content is reduced to less than 3000 ppm, or even less than 2500 ppm and better still less than 1500 ppm. In some cases it can be obtained less than 500 ppm. The content of dienes after selective hydrogenation can even be reduced to less than 250 ppm.
According to one embodiment of the invention, the hydrogenation step takes place in a catalytic hydrogenation reactor which comprises a catalytic reaction zone traversed by the entire charge and the quantity of hydrogen necessary to carry out the desired reactions.
Selon une réalisation préférée de l'invention, l'étape d'hydrogénation se déroule dans un
réacteur catalytique d'hydrogénation qui est agencé de manière particulière, à savoir au
moins deux zones catalytiques, la première étant traversée par la charge liquide (et une
quantité d'hydrogène inférieure à la stoechiométrie nécessaire pour convertir toutes les
dioléfines en mono-oléfines), la seconde 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 restantes en mono-oléfines et pour isomériser au
moins en partie les oléfines primaires et secondaires en oléfines tertiaires) par exemple
injectée par une tubulure latérale et dispersée à l'aide d'un diffuseur approprié.
La proportion de la première zone (en volume) est tout au plus égale à 75 % de la
somme des 2 zones et de préférence de 15 à 30 %.
Un autre mode de réalisation avantageux comprend une hydrogénation des diènes sur
un catalyseur différent du Pd, un hydrotraitement doux et un adoucissement oxydant
final.According to a preferred embodiment of the invention, the hydrogenation stage takes place in a catalytic hydrogenation reactor which is arranged in a particular manner, namely at least two catalytic zones, the first being crossed by the liquid charge (and a amount of hydrogen lower than the stoichiometry necessary to convert all the diolefins into mono-olefins), the second receiving the liquid charge coming from the first zone (as well as the rest of the hydrogen i.e. an amount of sufficient hydrogen to convert the remaining diolefins into mono-olefins and to at least partially isomerize the primary and secondary olefins into tertiary olefins) for example injected through a side tube and dispersed using an appropriate diffuser.
The proportion of the first zone (by volume) is at most equal to 75% of the sum of the 2 zones and preferably from 15 to 30%.
Another advantageous embodiment comprises a hydrogenation of the dienes on a catalyst different from Pd, a mild hydrotreatment and a final oxidative softening.
L'hydrodésulfuration douce de la fraction légère de la coupe essence de FCC a pour but
, en utilisant un catalyseur d'hydrotraitement conventionnel dans des conditions douces
de température et de pression, de convertir en H2S les composés soufrés de la coupe
autres ques les mercaptans, de façon à obtenir un effluent ne contenant comme
composés soufrés que les mercaptans. La coupe ainsi produite possède le même
intervalle de distillation, et un indice d'octane un peu plus faible du fait de la saturation
partielle inévitable des oléfines.
Les conditions du réacteur d'hydrotraitement doivent être ajustées pour atteindre le
niveau de désulfuration désiré, et surtout pour minimiser la perte en octane résultant de
la saturation des oléfines. On convertit généralement au plus 90 % des oléfines (les
dioléfines étant totalement ou pratiquement totalement hydrogénées), et de préférence
sont converties au plus 80-85 % des oléfines.
La température de l'étape d'hydrotraitement doux est généralement comprise entre
160°C et 380°C, de préférence entre 180°C et 360°C, et plus préférentiellement entre
180°C et 320°C. Des pressions faibles à modérées sont généralement suffisantes,
comprises entre 5 et 50 bar, de préférence entre 10 et 45 bar, et plus préférentiellement
entre 10 et 30 bar. La vitesse spatiale LHSV est comprise entre 0.5 et 10 h-1, de
préférence entre 1 et 6 h-1.
Le(s) catalyseur(s) utilisé(s) dans le réacteur d'hydrotraitement doux est un catalyseur
conventionnel d'hydrodésulfuration, comprenant au moins un métal du groupe VI et/ou
au moins un métal du groupe VIII, sur un support approprié. Le métal du groupe VI est
généralement du molybdène ou du tungstène, et le métal du groupe VIII est
généralement du nickel ou du cobalt. Des combinaisons telles que Ni-Mo ou Co-Mo
sont typiques.Le support du catalyseur est habituellement un solide poreux tel qu'une
alumine, une silice-alumine ou d'autres solides poreux tels que la magnésie, la silice ou
TiO2, seuls ou en mélange avec l'alumine ou la silice-alumine.The purpose of the mild hydrodesulfurization of the light fraction of the FCC gasoline fraction is, using a conventional hydrotreatment catalyst under mild conditions of temperature and pressure, to convert the sulfur compounds of the fraction other than H 2 S mercaptans, so as to obtain an effluent containing as sulfur compounds only mercaptans. The resulting cut has the same distillation range, and a slightly lower octane number due to the inevitable partial saturation of the olefins.
The conditions of the hydrotreatment reactor must be adjusted to reach the desired level of desulphurization, and above all to minimize the loss of octane resulting from the saturation of the olefins. Generally, at most 90% of the olefins are converted (the diolefins being totally or practically completely hydrogenated), and preferably at most 80-85% of the olefins are converted.
The temperature of the mild hydrotreatment stage is generally between 160 ° C and 380 ° C, preferably between 180 ° C and 360 ° C, and more preferably between 180 ° C and 320 ° C. Low to moderate pressures are generally sufficient, between 5 and 50 bar, preferably between 10 and 45 bar, and more preferably between 10 and 30 bar. The LHSV space speed is between 0.5 and 10 h -1, preferably between 1 and 6 h -1.
The catalyst (s) used in the mild hydrotreatment reactor is a conventional hydrodesulfurization catalyst, comprising at least one group VI metal and / or at least one group VIII metal, on a suitable support . The group VI metal is generally molybdenum or tungsten, and the group VIII metal is generally nickel or cobalt. Combinations such as Ni-Mo or Co-Mo are typical. The catalyst support is usually a porous solid such as alumina, silica-alumina or other porous solids such as magnesia, silica or TiO2, alone or as a mixture with alumina or silica-alumina.
La fraction la plus légère de la coupe essence est ensuite soumise à une désulfuration
non-hydrogénante visant à éliminer les composés soufrés restant sous forme de
mercaptans.
Il peut s'agir d'un procédé d'adoucissement extractif utilisant de la soude ou du crésylate
de sodium ou de potassium. Les procédés extractifs sont suffisants tant que la coupe
traitée ne contient pas de mercaptans de haut poids moléculaire.
L'adoucissement peut également être réalisée par oxydation catalytique des mercaptans
en disulfures. Cette oxydation catalytique des mercaptans en disulfures peut être
réalisée simplement en mélangeant l'essence à traiter à une solution aqueuse d'une base
alcaline, telle la soude, dans laquelle on ajoute un catalyseur à base d'un chélate
métallique, en présence d'un agent oxydant.
Dans le cas où la teneur en mercaptans de l'essence est importante, il est préférable de
réaliser la mise au contact de la coupe avec un lit fixe de catalyseur supporté, en
présence d'une base alcaline et d'un agent oxydant. Dans une première variante, la base
alcaline n'est pas incorporée au catalyseur. Il s'agit habituellement de la soude en
solution aqueuse; elle est introduite dans le milieu réactionnel soit en continu, soit par
intermittence, pour maintenir les conditions d'alcalinité et la phase aqueuse nécessaires
à la réaction d'oxydation. L'agent oxydant, généralement de l'air, est avantageusement
mélangé à la coupe essence à adoucir. Le chélate métallique utilisé comme catalyseur
est généralement une phtalocyanine métallique, telle la phtalocyanine de cobalt par
exemple. La réaction a lieu à une pression comprise entre 1 et 30 bar, à une température
comprise entre 20 et 100°C, et de préférence 20 et 80°C. Il convient de renouveler la
solution sodique qui s'épuise, d'une part en raison des impuretés provenant de la charge,
d'autre part en raison de la variation de la concentration de la base, qui diminue du fait
de l'apport d'eau par la charge et de la transformation des mercaptans en disulfures.
Dans une seconde variante préférée, la base alcaline peut être incorporée au sein du
catalyseur en introduisant un ion alcalin dans une structure oxyde mixte constituée
essentiellement d'oxydes d'aluminium et de silicium combinés.
Avantageusement, on emploie des aluminosilicates de métaux alcalins, plus
particulièrement de sodium et de potassium, caractérisés par un rapport atomique Si/Al
de leur structure inférieur ou égal à 5 (c'est à dire un rapport molaire SiO2/Al2O3
inférieur ou égal à 10), et qui sont associés intimement à du charbon actif et à un
chélate métallique et présentent des performances catalytiques optimales en
adoucissement lorsque le taux d'hydratation du catalyseur est compris entre 0,1 et 40%
et de préférence entre 1 et 25% en poids de celui-ci. Outre leurs performances
catalytiques supérieures, ces aluminosilicates alcalins présentent l'avantage d'une très
faible solubilité en milieu aqueux, ce qui permet leur utilisation prolongée à l'état
hydraté pour traiter des coupes pétrolières auxquelles on ajoute régulièrement un peu
d'eau ou, éventuellement, de solution alcaline.
Cette étape d'adoucissement (de préférence réalisée en lit fixe) de la fraction essence
légère contenant des mercaptans peut donc être définie comme comprenant le passage,
dans des conditions d'oxydation, de l'essence à traiter (stabilisée) au contact d'un
catalyseur poreux. De préférence, selon le brevet EP-A-638.628, il comprend de 10 à
98%, de préférence de 50 à 95% en poids, d'au moins une phase solide minérale
constituée d'un aluminosilicate alcalin ayant un rapport atomique Si/Al inférieur ou égal
à 5, de préférence inférieur ou égal à 3, de 1 à 60% en poids de charbon actif, de 0,02 à
2% en poids d'au moins un chélate métallique et de 0 à 20% en poids d'au moins un
liant minéral ou organique. Ce catalyseur poreux présente une basicité déterminée selon
la norme ASTM 2896 supérieure à 20 milligrammes de potasse par gramme et une
surface totale BET supérieure à 10 m2/g, et contient à l'intérieur de sa porosité une
phase aqueuse permanente représentant de 0,1 à 40%, de préférence de 1 à 25%, en
poids du catalyseur sec.The lighter fraction of the gasoline fraction is then subjected to a non-hydrogenating desulfurization aiming to remove the sulfur compounds remaining in the form of mercaptans.
It can be an extractive softening process using sodium or potassium soda or cresylate. Extractive processes are sufficient as long as the treated cut does not contain high molecular weight mercaptans.
Softening can also be carried out by catalytic oxidation of the mercaptans to disulfides. This catalytic oxidation of the mercaptans to disulfides can be carried out simply by mixing the gasoline to be treated with an aqueous solution of an alkaline base, such as sodium hydroxide, in which a catalyst based on a metal chelate is added, in the presence of an oxidizing agent.
In the case where the mercaptans content of the gasoline is high, it is preferable to bring the section into contact with a fixed bed of supported catalyst, in the presence of an alkaline base and an oxidizing agent. In a first variant, the alkaline base is not incorporated into the catalyst. It is usually soda in aqueous solution; it is introduced into the reaction medium either continuously or intermittently, to maintain the alkalinity conditions and the aqueous phase necessary for the oxidation reaction. The oxidizing agent, generally air, is advantageously mixed with the petrol cut to be softened. The metal chelate used as catalyst is generally a metal phthalocyanine, such as cobalt phthalocyanine for example. The reaction takes place at a pressure between 1 and 30 bar, at a temperature between 20 and 100 ° C, and preferably 20 and 80 ° C. It is advisable to renew the sodium solution which runs out, on the one hand because of the impurities coming from the load, on the other hand because of the variation of the concentration of the base, which decreases due to the contribution of by charging and transforming mercaptans into disulfides.
In a second preferred variant, the alkaline base can be incorporated into the catalyst by introducing an alkaline ion into a mixed oxide structure essentially consisting of combined aluminum and silicon oxides.
Advantageously, aluminosilicates of alkali metals, more particularly of sodium and potassium, are used, characterized by an atomic Si / Al ratio of their structure less than or equal to 5 (that is to say a molar ratio SiO 2 / Al 2 O 3 less than or equal to 10), and which are intimately associated with activated carbon and a metal chelate and exhibit optimal catalytic performances in softening when the hydration rate of the catalyst is between 0.1 and 40% and preferably between 1 and 25% by weight thereof. In addition to their superior catalytic performance, these alkaline aluminosilicates have the advantage of very low solubility in aqueous medium, which allows their prolonged use in the hydrated state to treat petroleum fractions to which a little water is regularly added, or optionally, alkaline solution.
This softening step (preferably carried out in a fixed bed) of the light petrol fraction containing mercaptans can therefore be defined as comprising the passage, under oxidation conditions, of the petrol to be treated (stabilized) in contact with a porous catalyst. Preferably, according to patent EP-A-638,628, it comprises from 10 to 98%, preferably from 50 to 95% by weight, of at least one inorganic solid phase consisting of an alkaline aluminosilicate having an atomic ratio Si / Al less than or equal to 5, preferably less than or equal to 3, from 1 to 60% by weight of activated carbon, from 0.02 to 2% by weight of at least one metal chelate and from 0 to 20% by weight at least one mineral or organic binder. This porous catalyst has a basicity determined according to standard ASTM 2896 greater than 20 milligrams of potassium hydroxide per gram and a total BET surface area greater than 10 m 2 / g, and contains within its porosity a permanent aqueous phase representing 0, 1 to 40%, preferably 1 to 25%, by weight of the dry catalyst.
Parmi les phases minérales basiques du type aluminosilicates (principalement de sodium et/ou de potassium) qui conviennent particulièrement bien, on peut citer un grand nombre de phases:
- lorsque l'alcalin est majoritairement le potassium :
- la kaliophilite : K2O, Al2O3, SiO2(1,8 < < 2,4).
- le feldspathoïde appelé leucite : K2O, Al2O3, SiO2 (3,5 < < 4,5).
- les zéolithes du type :
- philipsite : (K, Na)O, Al2O3, SiO2 (3,0 < < 5,0).
- érionite ou offrétite : (K, Na, Mg, Ca)O, Al2O3, SiO2 (4 < < 8).
- mazzite ou zéolithe Oméga : (K, Na, Mg, Ca)O, Al2O3, SiO2 (4 < < 8).
- zéolithe L : (K, Na)O, Al2O3, SiO2 (5 < < 8).
- lorsque l'alcalin est le sodium :
- les aluminosilicates de sodium amorphes dont l'organisation cristalline ne peut être détectée par diffraction X et dont le rapport atomique Si/Al est inférieur ou égal à 5, et de préférence inférieur ou égal à 3.
- la sodalite Na2O, A12O3, SiO2 (1,8 < < 2,4). La sodalite peut contenir différents ions ou sels alcalins dans sa structure, comme par exemple Cl-, Br-, ClO3-, BrO3-, IO3-, NO3-, OH-, CO3--, SO3--, CrO4--, MoO4--, PO4---, etc... , sous forme de sels acalins, principalement de sodium. Ces différentes variétés conviennent pour la présente invention. Les variétés préférées pour la présente invention sont celles contenant l'ion OH- sous forme de NaOH et l'ion S-- sous forme de Na2S.
- la néphéline Na2O, Al2O3, SiO2 (1,8 < < 2,4).
- les tectosilicates du type analcime, natrolite, mesolite, thomsonite, clinoptilolite, stilbite, zéolithe Na-P1, dachiardite, chabasite, gmelinite, cancrinite, la faujasite comprenant les zéolithes synthétiques X et Y, la zéolithe A.
- when the alkali is mainly potassium:
- kaliophilite: K 2 O, Al 2 O 3 , SiO 2 (1.8 <<2.4).
- the feldspathoid called leucite: K2O, Al2O3, SiO2 (3.5 <<4.5).
- zeolites of the type:
- philipsite: (K, Na) O, Al2O3, SiO2 (3.0 <<5.0).
- erionite or offretite: (K, Na, Mg, Ca) O, Al2O3, SiO2 (4 <<8).
- Omega mazzite or zeolite: (K, Na, Mg, Ca) O, Al2O3, SiO2 (4 <<8).
- zeolite L: (K, Na) O, Al2O3, SiO2 (5 <<8).
- when the alkali is sodium:
- amorphous sodium aluminosilicates whose crystal organization cannot be detected by X-ray diffraction and whose Si / Al atomic ratio is less than or equal to 5, and preferably less than or equal to 3.
- sodalite Na2O, A12O3, SiO2 (1.8 <<2.4). Sodalite can contain different ions or alkaline salts in its structure, such as for example Cl-, Br-, ClO3-, BrO3-, IO3-, NO3-, OH-, CO3--, SO3--, CrO4--, MoO4 -, PO4 ---, etc ..., in the form of alkaline salts, mainly sodium. These different varieties are suitable for the present invention. The preferred varieties for the present invention are those containing the OH- ion in the form of NaOH and the S-- ion in the form of Na2S.
- nepheline Na2O, Al2O3, SiO2 (1.8 <<2.4).
- tectosilicates of the analcime, natrolite, mesolite, thomsonite, clinoptilolite, stilbite, Na-P1 zeolite, dachiardite, chabasite, gmelinite, cancrinite type, faujasite comprising the synthetic zeolites X and Y, zeolite A.
D'une façon préférée, ledit aluminosilicate alcalin est obtenu par réaction en milieu aqueux d'au moins un argile (kaolinite, halloysite, montmorillonite, etc...) avec au moins un composé (hydroxyde, carbonate, acétate, nitrate, etc...) d'au moins un métal alcalin, notamment le sodium, et le potassium, ce composé étant de préférence l'hydroxyde, suivie d'un traitement thermique à une température entre 90 et 600°C, de préférence entre 120 et 350°C.Preferably, said alkaline aluminosilicate is obtained by reaction in the medium aqueous of at least one clay (kaolinite, halloysite, montmorillonite, etc ...) with at at least one compound (hydroxide, carbonate, acetate, nitrate, etc.) of at least one metal alkaline, in particular sodium, and potassium, this compound preferably being hydroxide, followed by heat treatment at a temperature between 90 and 600 ° C, preferably between 120 and 350 ° C.
L'argile peut aussi être traitée thermiquement et broyée avant d'être mis au contact de la solution alcaline. Ainsi, la kaolinite et tous ses produits de transformation thermique (métakaolin, phase spinelle inverse, mullite) peuvent être utilisés selon le procédé de l'invention. The clay can also be heat treated and ground before being brought into contact with the alkaline solution. Kaolinite and all of its thermal transformation products (metakaolin, reverse spinel phase, mullite) can be used according to the the invention.
Lorsque l'argile considérée est le kaolin, la kaolinite et/ou le métakaolin constituent les
réactifs chimiques de base préférés.
Comme chélate métallique, on pourra déposer sur le support tout chélate utilisé dans ce
but dans la technique antérieure, en particulier les phtalocyanines, les porphyrines ou
les corrines métalliques. On préfère particulièrement la phtalocyanine de cobalt et la
phtalocyanine de vanadium. On utilise, de préférence, la phtalocyanine métallique sous
forme d'un dérivé de cette dernière, avec une préférence particulière pour ses sulfonates
disponibles dans le commerce, comme par exemple le mono- ou le disulfonate de
phtalocyanine de cobalt et des mélanges de ceux-ci.When the clay considered is kaolin, kaolinite and / or metakaolin constitute the preferred basic chemical reagents.
As metal chelate, any chelate used for this purpose in the prior art, in particular phthalocyanines, porphyrins or metal corrines, can be deposited on the support. Particularly preferred is cobalt phthalocyanine and vanadium phthalocyanine. Metallic phthalocyanine is preferably used in the form of a derivative of the latter, with particular preference for its commercially available sulfonates, such as, for example, cobalt phthalocyanine mono- or disulfonate and mixtures thereof. this.
Les conditions réactionnelles mises en oeuvre pour réaliser cette seconde variante de l'étape d'adoucissement se caractérisent par l'absence de base aqueuse, une température et une vitesse spatiale horaire plus élevées. Les conditions adoptées sont généralement les suivantes :
- Température: 20 à 100°C, de préférence 20 à 80°C.
- Pression: 105 à 30.105 Pascal.
- Quantité d'agent oxydant air: 1 à 3 kg/kg de mercaptans.
- Vitesse spatiale horaire en VVH (volume de charge par volume de catalyseur et par heure): 1 à 10h-1 dans le cadre du procédé de l'invention.
- Temperature: 20 to 100 ° C, preferably 20 to 80 ° C.
- Pressure: 10 5 to 30.10 5 Pascal.
- Quantity of air oxidizing agent: 1 to 3 kg / kg of mercaptans.
- Hourly space velocity in VVH (volume of charge per volume of catalyst and per hour): 1 to 10 h -1 in the context of the process of the invention.
La teneur en eau du catalyseur à base alcaline utilisé dans l'étape d'adoucissement
oxydant de la présente invention peut varier en cours d'opération dans deux directions
opposées:
Dans le premier cas, de l'eau peut être ajoutée, en quantité adéquate, à la coupe pétrolière, en amont du catalyseur de manière continue ou discontinue pour maintenir le degré d'hydratation à l'intérieur de l'intervalle désiré, c'est-à-dire que la teneur en eau du support est maintenue entre 0,1 et 40% pds du support, et de préférence entre 1 et 25%.In the first case, water can be added in adequate quantity to the cut petroleum, upstream of the catalyst continuously or discontinuously to maintain the degree of hydration within the desired range, i.e. the water content of the support is maintained between 0.1 and 40% by weight of the support, and preferably between 1 and 25%.
Dans le second cas, il suffit que la température de la charge soit fixée à une valeur
suffisante, inférieure à 80°C, pour solubiliser l'eau de réaction résultant de la
transformation des mercaptans en disulfures. La température de la charge est ainsi
choisie de manière à maintenir la teneur en eau du support entre 0,1 et 40% en poids du
support et, de préférence, entre 1 et 25% en poids de celui-ci.
Cet intervalle de valeurs prédeterminées de teneurs en eau du support dépendra, bien
entendu, de la nature même du support catalytique utilisé lors de la réaction
d'adoucissement. En effet, le demandeur a constaté, conformément au brevet
FR-2.651.791, que si de nombreux supports catalytiques sont susceptibles d'être utilisés
sans soude (ou sans base) aqueuse, leur activité ne se manifestera que lorsque leur
teneur en eau (également appelée taux d'hydratation du support) est maintenue dans un
intervalle de valeurs relativement étroit, variable suivant les supports, mais
apparemment lié à la teneur du support en silicate et à la structure de ses pores.In the second case, it suffices that the temperature of the feed is fixed at a sufficient value, less than 80 ° C., to dissolve the reaction water resulting from the transformation of the mercaptans into disulfides. The temperature of the load is thus chosen so as to maintain the water content of the support between 0.1 and 40% by weight of the support and, preferably, between 1 and 25% by weight of the latter.
This range of predetermined values of water contents of the support will depend, of course, on the very nature of the catalytic support used during the softening reaction. Indeed, the applicant has found, in accordance with patent FR-2,651,791, that if numerous catalytic supports are capable of being used without aqueous sodium hydroxide (or without base), their activity will only manifest themselves when their water content ( also called the hydration level of the support) is maintained in a relatively narrow range of values, variable depending on the supports, but apparently linked to the content of the silicate support and to the structure of its pores.
Le déposant a pu constater que, de façon particulièrement avantageuse, cette étape
d'adoucissement peut être éliminée lorsque la coupe légère a été hydrogénée
sélectivement pour éliminer les diènes et que dans le même temps un adoucissement a
été obtenu. Le rendement en adoucissement peut être tel que l'étape finale
d'adoucissement par un agent oxydant peut n'être plus nécessaire. Ce cas se vérifie bien
avec un catalyseur à base de palladium tel que décrit précédemment.
La présence de cette étape de traitement avec un catalyseur au palladium peut permettre
également de modifier l'étape d'adoucissement, par exemple en augmentant la vitesse
horaire, d'où une productivité accrue, ou en réduisant la quantité de catalyseur, d'où un
investissement réduit.
Lorsque l'étape finale d'adoucissement est employée, on peut utiliser une étape
d'hydrogénation sélective des diènes qui ne soit pas adoucissante.The applicant has observed that, particularly advantageously, this softening step can be eliminated when the light cut has been selectively hydrogenated to remove the dienes and that at the same time softening has been obtained. The softening yield may be such that the final step of softening with an oxidizing agent may no longer be necessary. This case is well verified with a palladium-based catalyst as described above.
The presence of this treatment step with a palladium catalyst can also make it possible to modify the softening step, for example by increasing the hourly speed, hence increased productivity, or by reducing the quantity of catalyst, hence a reduced investment.
When the final softening step is used, a selective hydrogenation step of the dienes can be used which is not softening.
L'hydrodésulfuration de la fraction la plus lourde de l'essence de FCC est conduite suivant le même procédé que celui utilisé pour la fraction légère. Le catalyseur contient également au moins un métal du G VIII et/ou du groupe VI, déposé sur un support. Seules les conditions opératoires sont ajustées, afin d'obtenir le niveau de désulfuration désiré, sur cette coupe plus riche en soufre. La température utilisée est généralement comprise entre 200°C et 420°C, de préférence entre 220°C et 400°C. Les pressions opératoires utilisées sont généralement comprises entre 20 et 80 bar et de préférence entre 30 et 50 bar.L'effluent obtenu est strippé pour éliminer H2S et est envoyé au pool essence.Hydrodesulfurization of the heaviest fraction of FCC gasoline is conducted following the same process as that used for the light fraction. The catalyst contains also at least one metal from G VIII and / or from group VI, deposited on a support. Only the operating conditions are adjusted, in order to obtain the level of desulphurization desired, on this cut richer in sulfur. The temperature used is generally between 200 ° C and 420 ° C, preferably between 220 ° C and 400 ° C. The pressures operating procedures are generally between 20 and 80 bar and preferably between 30 and 50 bar. The effluent obtained is stripped to remove H2S and is sent to the pool essence.
L'invention concerne également.une installation pour mettre en oeuvre le procédé selon l'invention.The invention also relates to an installation for implementing the method according to the invention.
Elle comprend:
- une colonne (1) de fractionnement munie d'une conduite (2) pour l'introduction de l'essence brute provenant du craquage catalytique et comportant au moins 2 conduites, l'une (3) dans la partie haute de la colonne pour la sortie de la coupe légère, et une autre (4) dans la partie basse de la colonne pour la sortie de la coupe lourde ;
- une zone (5) d'hydrotraitement en présence d'hydrogène comportant un lit catalytique, une conduite (6) pour l'entrée de la coupe d'essence légère à traiter, ladite conduite étant reliée soit à la colonne (1) de fractionnement, soit à la zone de traitement (7) sur catalyseur au palladium, ladite zone d'hydrotraitement comportant également une conduite (8) pour la sortie de l'effluent hydrotraité,
- une zone (9) de strippage comportant une conduite pour l'introduction de l'essence légère hydrotraitée, une conduite (10) pour l'évacuation de H2S et une conduite (11) pour la sortie de l'essence légère strippée,
- une zone (12) d'adoucissement située après la zone de strippage comportant une conduite pour l'introduction de l'essence légère strippée et une conduite (14) pour amener l'agent oxydant au niveau de ladite zone ;
- une zone (7) de traitement située avant la zone d'hydrotraitement et comportant une conduite (3) pour l'introduction de la coupe d'essence légère issue de la colonne de fractionnement, une conduite pour la sortie de la coupe d'essence légère traitée, ladite zone comportant également au moins un lit d'un catalyseur à 0,1-1% de palladium déposé sur un support, et ladite installation comportant en outre une conduite (13) pour la sortie de l'essence légère strippée et adoucie hors de l'installation, et reliée soit à la zone (9) soit à la zone (12) lorsqu'elle existe.
- a fractionation column (1) provided with a pipe (2) for the introduction of the crude petrol coming from catalytic cracking and comprising at least 2 pipes, one (3) in the upper part of the column for the exit from the light cup, and another (4) in the lower part of the column for the exit from the heavy cup;
- a hydrotreating zone (5) in the presence of hydrogen comprising a catalytic bed, a pipe (6) for the entry of the light gasoline fraction to be treated, said pipe being connected either to the fractionation column (1) either in the treatment zone (7) on a palladium catalyst, said hydrotreatment zone also comprising a line (8) for the outlet of the hydrotreated effluent,
- a stripping zone (9) comprising a line for the introduction of hydrotreated light gasoline, a line (10) for the removal of H2S and a line (11) for the exit of light stripped gasoline,
- a softening zone (12) situated after the stripping zone comprising a line for the introduction of light stripped gasoline and a line (14) for bringing the oxidizing agent to the level of said zone;
- a treatment zone (7) located before the hydrotreatment zone and comprising a line (3) for the introduction of the light gasoline cut from the fractionation column, a line for the output of the gasoline cut light treated, said zone also comprising at least one bed of a catalyst containing 0.1-1% of palladium deposited on a support, and said installation further comprising a pipe (13) for the outlet of light stripped petrol and softened outside the installation, and connected either to zone (9) or to zone (12) when it exists.
Selon une variante, la zone d'adoucissement est située après le strippage et l'installation
comporte en outre une zone d'hydrogénation sélective des diènes située entre la colonne
de fractionnement et la zone d'hydrotraitement doux, ladite zone d'hydrogénation
comportant une conduite pour l'introduction de la coupe légère et une conduite pour la
sortie de la coupe légère dédiénisée.
Dans un mode préféré, l'installation comporte également une zone (15)
d'hydrotraitement de la fraction lourde, munie d'une conduite (4) pour l'introduction de
la coupe lourde provenant de la colonne (1) , une conduite (16) pour la sortie de la
coupe hydrotraitée et une conduite (17) amenant l'hydrogène au niveau de la charge ou
de la zone, ladite zone étant suivie d'une colonne (18) de strippage munie d'une
conduite pour l'introduction de la coupe hydrotraitée, d'une conduite (19) pour la sortie
de H2S et d'une conduite (20) pour la sortie de la coupe hydrotraitée. Les coupes sortant
par les canalisations (20) et (13) peuvent être envoyées au stockage essence par une
canalisation (21).According to a variant, the softening zone is located after stripping and the installation also comprises a zone for the selective hydrogenation of the dienes situated between the fractionation column and the zone for mild hydrotreatment, said hydrogenation zone comprising a pipe for the introduction of the light cut and a pipe for the exit of the dedicated light cut.
In a preferred embodiment, the installation also comprises a zone (15) for hydrotreating the heavy fraction, provided with a line (4) for the introduction of the heavy cut coming from the column (1), a line ( 16) for the outlet of the hydrotreated section and a pipe (17) bringing the hydrogen to the level of the charge or the zone, said zone being followed by a stripping column (18) provided with a pipe for the introduction of the hydrotreated section, a pipe (19) for the outlet of H 2 S and a pipe (20) for the outlet of the hydrotreated section. The cuts coming out through the pipes (20) and (13) can be sent to petrol storage via a pipe (21).
Les chiffres se rapportent aux figures 1 et 2. Sur la figure 1, l'installation pour le traitement de la coupe légère est représenté avec en pointillé les zones d'adoucissements. On comprendra que les trois modes de réalisations suivants peuvent être utilisés :
- premier mode, avec la zone (7) d'adoucissant mais sans la zone (12);
- deuxième mode, avec la zone (12) mais sans la zone (7);
- et troisième mode, avec les zones (12) et (7).
- first mode, with the softener zone (7) but without the zone (12);
- second mode, with the zone (12) but without the zone (7);
- and third mode, with zones (12) and (7).
Sur la figure 2, on a ajouté le traitement de la coupe lourde.
On n'a pas représenté les conduites pour amener l'hydrogène, qui alourdiraient les
schémas, mais il est bien évident qu'en présence de la zone (7) ou d'une zone
d'hydrogénation des diènes, il y a une conduite pour amener l'hydrogène au niveau de la
coupe légère ou dans le réacteur directement. En l'absence de telles zones, la conduite
débouche directement dans la zone d'hydrotraitement ou dans la coupe légère.In Figure 2, the processing of the heavy cut was added.
The lines for bringing the hydrogen have not been shown, which would make the diagrams heavier, but it is obvious that in the presence of zone (7) or of a dienes hydrogenation zone, there is a line to bring the hydrogen to the light section or directly into the reactor. In the absence of such zones, the pipe leads directly into the hydrotreating zone or into the light cut.
L'exemple ci-après illustre le procédé, dans le cas où la coupe essence brute est
fractionnée en une coupe légère C5 moins del80°C, et une fraction plus lourde 180-220°C.
Le tableau 1 indique les caractéristiques de ces différentes coupes.
La coupe légère de l'essence de FCC est riche en oléfines et contient la quasi-totalité des
mercaptans. La fraction plus lourde, plus riche en soufre, contient des composés soufrés
essentiellement sous forme de dérivés thiophéniques.
Le tableau 2 ci-après indique les conditions opératoires utilisées pour l'hydrotraitement
de l'essence lourde, ainsi que les caractéristiques de l'essence lourde ainsi désulfurée.
Le catalyseur utilisé est un CoMo supporté alumine (HR 306C vendu par la société
Procatalyse).
Caractéristiques de l'essence lourde désulfurée
Table 2 below indicates the operating conditions used for the hydrotreatment of heavy gasoline, as well as the characteristics of the heavy gasoline thus desulfurized.
The catalyst used is a CoMo supported alumina (HR 306C sold by the company Procatalyse).
Characteristics of desulfurized heavy petrol
Le tableau 3 ci-après indique les caractéristiques de l'essence légère désulfurée puis
adoucie. Lors de l'étape d'hydrotraitement doux, la température est de 280°C, la
pression est de 20 bar, LHV de 8h-1 et le catalyseur est le LD 145 à base de NiMo
vendu par la société Procatalyse suivi d'un catalyseur CoMo (HR306 C vendu par la
société Procatalyse).
L'adoucissement est effectué sur un catalyseur comportant de la sodalite (aluminosilicate alcalin) et 20% de charbon actif, imprégné avec un agent oxydant tel la phtalocyamine de cobalt sulfonnée (imprégnation de PeCo : 60 kg (m3 de cata) préparé tel que decrit dans le brevet EP-A-638.628).The softening is carried out on a catalyst comprising sodalite (alkaline aluminosilicate) and 20% of activated carbon, impregnated with an oxidizing agent such as sulfonated cobalt phthalocyamine (impregnation of PeCo: 60 kg (m 3 of cat) prepared as described in patent EP-A-638,628).
Le procédé et l'installation selon l'invention permettent ainsi d'obtenir des essences de FCC contenant moins de 50 ppm de soufre, répondant négativement au "doctor test" et ce avec une perte en indice d'octane baril (RON + MON)/2 inférieure à 8 points par rapport à la même coupe d'essence brute de FCC avant traitement, et de préférence inférieure ou égale à 6 points.The method and the installation according to the invention thus make it possible to obtain essences of FCC containing less than 50 ppm of sulfur, responding negatively to the "doctor test" and this with a loss in octane barrel index (RON + MON) / 2 of less than 8 points per compared to the same cut of raw FCC gasoline before treatment, and preferably less than or equal to 6 points.
Claims (12)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9611691A FR2753717B1 (en) | 1996-09-24 | 1996-09-24 | PROCESS AND PLANT FOR THE PRODUCTION OF LOW SULFUR CATALYTIC CRACKING ESSENCES |
FR9611691 | 1996-09-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0832958A1 true EP0832958A1 (en) | 1998-04-01 |
EP0832958B1 EP0832958B1 (en) | 2005-08-17 |
Family
ID=9496062
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97402088A Expired - Lifetime EP0832958B1 (en) | 1996-09-24 | 1997-09-08 | Process and apparatus for the production of low sulphur catalytically cracked gasolines |
Country Status (6)
Country | Link |
---|---|
US (2) | US6007704A (en) |
EP (1) | EP0832958B1 (en) |
JP (1) | JP4006483B2 (en) |
KR (1) | KR100456209B1 (en) |
DE (1) | DE69733985T2 (en) |
FR (1) | FR2753717B1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1077247A1 (en) * | 1999-08-19 | 2001-02-21 | Institut Francais Du Petrole | Process for the production of low sulphur gasolines |
EP1138749A1 (en) * | 2000-03-29 | 2001-10-04 | Institut Francais Du Petrole | Gasoline desulphurisation process comprising the desulphurisation of heavy and intermediate fractions from a fractionation into at least three cuts |
EP1247857A2 (en) * | 2001-04-03 | 2002-10-09 | Chevron U.S.A. Inc. | Mild hydrotreating/extraction process for low sulfurfuel for use in fuel cells |
CN102443433A (en) * | 2010-10-15 | 2012-05-09 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
CN102465031A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Hydrotreating method for heavy hydrocarbon raw materials |
CN110643380A (en) * | 2019-08-22 | 2020-01-03 | 中科合成油工程股份有限公司 | Method for converting coal pyrolysis product into gasoline, diesel oil and hydrogen |
Families Citing this family (40)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19626126C2 (en) * | 1996-06-28 | 1998-04-16 | Fraunhofer Ges Forschung | Method for forming a spatial chip arrangement and spatial chip arrangement |
US6649043B1 (en) | 1996-08-23 | 2003-11-18 | Exxonmobil Research And Engineering Company | Regeneration of hydrogen sulfide sorbents |
BR9911753A (en) * | 1998-06-30 | 2001-04-03 | Eastman Chem Co | Base-modified clay, process for preparing it, catalyst composition, and process for preparing a monoester glycol |
US6692635B2 (en) * | 1999-02-24 | 2004-02-17 | Institut Francais Du Petrole | Process for the production of gasolines with low sulfur contents |
US6602405B2 (en) * | 2000-01-21 | 2003-08-05 | Bp Corporation North America Inc. | Sulfur removal process |
US6599417B2 (en) * | 2000-01-21 | 2003-07-29 | Bp Corporation North America Inc. | Sulfur removal process |
US6596157B2 (en) * | 2000-04-04 | 2003-07-22 | Exxonmobil Research And Engineering Company | Staged hydrotreating method for naphtha desulfurization |
CA2407066A1 (en) * | 2000-04-18 | 2001-10-25 | Exxonmobil Research And Engineering Company | Selective hydroprocessing and mercaptan removal |
US6656877B2 (en) | 2000-05-30 | 2003-12-02 | Conocophillips Company | Desulfurization and sorbents for same |
US6946068B2 (en) * | 2000-06-09 | 2005-09-20 | Catalytic Distillation Technologies | Process for desulfurization of cracked naphtha |
FR2811328B1 (en) * | 2000-07-06 | 2002-08-23 | Inst Francais Du Petrole | PROCESS INCLUDING TWO STAGES OF GASOLINE HYDRODESULFURATION AND AN INTERMEDIATE REMOVAL OF THE H2S FORMED DURING THE FIRST STAGE |
JP4991083B2 (en) * | 2000-09-22 | 2012-08-01 | バスフ・カタリスツ・エルエルシー | Structurally enhanced cracking catalyst |
US6610197B2 (en) * | 2000-11-02 | 2003-08-26 | Exxonmobil Research And Engineering Company | Low-sulfur fuel and process of making |
US20020148754A1 (en) * | 2001-02-08 | 2002-10-17 | Gong William H. | Integrated preparation of blending components for refinery transportation fuels |
US6860999B2 (en) * | 2001-06-19 | 2005-03-01 | Exxonmobil Research And Engineering Company | Liquid hydrocarbon treatment method |
FR2834515B1 (en) | 2002-01-10 | 2006-03-10 | Atofina | VAPOCRAQUAGE OF MODIFIED NAPHTA |
US8158843B2 (en) * | 2002-02-12 | 2012-04-17 | The Penn State Research Foundation | Deep desulfurization of hydrocarbon fuels |
EP1514917A4 (en) * | 2002-05-22 | 2007-05-23 | Japan Energy Corp | Adsorption desulfurization agent for desulfurizing petroleum fraction and desulfurization method using the same |
TW200513320A (en) * | 2003-06-16 | 2005-04-16 | Shell Int Research | A process and catalyst for the selective hydrogenation of diolefins contained in an olefin containing stream and for the removal of arsenic therefrom and a method of making such catalyst |
FR2857973B1 (en) * | 2003-07-25 | 2008-02-22 | Inst Francais Du Petrole | METHOD FOR DESULFURING ESSENCES BY ADSORPTION |
KR101114742B1 (en) * | 2003-11-07 | 2012-02-29 | 제이엑스 닛코닛세키에너지주식회사 | Lead-free gasoline composition and method for production thereof |
US8084383B2 (en) * | 2004-03-16 | 2011-12-27 | W.R. Grace & Co.-Conn. | Gasoline sulfur reduction catalyst for fluid catalytic cracking process |
US7752659B2 (en) * | 2005-02-14 | 2010-07-06 | Lenovo (Singapore) Pte. Ltd. | Packet filtering in a NIC to control antidote loading |
WO2006120898A1 (en) * | 2005-05-06 | 2006-11-16 | Japan Energy Corporation | Process for producing low-sulfur cracked-gasoline base and lead-free gasoline composition |
JP5280624B2 (en) * | 2005-12-01 | 2013-09-04 | Jx日鉱日石エネルギー株式会社 | Unleaded gasoline composition |
JP5280623B2 (en) * | 2005-12-01 | 2013-09-04 | Jx日鉱日石エネルギー株式会社 | Unleaded gasoline composition |
JP5280625B2 (en) * | 2005-12-01 | 2013-09-04 | Jx日鉱日石エネルギー株式会社 | Unleaded gasoline composition |
FR2900157B1 (en) * | 2006-04-24 | 2010-09-24 | Inst Francais Du Petrole | PROCESS FOR THE DESULFURATION OF OLEFINIC ESSENCES COMPRISING AT LEAST TWO DISTINCT HYDRODESULFURATION STAGES |
FR2908781B1 (en) * | 2006-11-16 | 2012-10-19 | Inst Francais Du Petrole | PROCESS FOR DEEP DEFLAVING CRACKING SPECIES WITH LOW LOSS OF OCTANE INDEX |
US8524043B2 (en) * | 2007-11-09 | 2013-09-03 | Ranfeng Ding | System for producing high quality gasoline by catalytic hydrocarbon recombination |
WO2009094934A1 (en) * | 2008-01-29 | 2009-08-06 | Beijing Grand Golden-Bright Engineering & Technologies Co., Ltd | A system and a process for producing high quality gasoline |
JP5706126B2 (en) * | 2010-10-07 | 2015-04-22 | 出光興産株式会社 | Adsorbent regeneration method |
WO2012066572A2 (en) | 2010-11-19 | 2012-05-24 | Indian Oil Corporation Ltd. | Process for deep desulfurization of cracked gasoline with minimum octane loss |
CN102041086A (en) * | 2011-01-17 | 2011-05-04 | 江苏佳誉信实业有限公司 | Selective hydrodesulfurization method for high-sulfur high-olefin catalytic gasoline |
CN103087771B (en) * | 2011-11-07 | 2015-06-03 | 中国石油化工股份有限公司 | Hydrogenation method for deeply desulfurizing gasoline |
CN107236571B (en) * | 2016-03-29 | 2019-01-08 | 中国石油化工股份有限公司 | A method of producing catalytically cracked stock |
CN107880934A (en) * | 2017-11-02 | 2018-04-06 | 中石化炼化工程(集团)股份有限公司 | The method and high-knock rating gasoline or high-knock rating gasoline blend component that catalytic cracking diesel oil utilizes |
CN107903943A (en) * | 2017-11-02 | 2018-04-13 | 中石化炼化工程(集团)股份有限公司 | The method and high-knock rating gasoline or high-knock rating gasoline blend component that catalytic cracking diesel oil utilizes |
CN109097104B (en) * | 2018-09-11 | 2019-11-08 | 福州大学 | A kind of FCC gasoline method for modifying |
SG11202104102SA (en) | 2018-11-07 | 2021-05-28 | Exxonmobil Chemical Patents Inc | Process for c5+ hydrocarbon conversion |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB967879A (en) * | 1961-07-06 | 1964-08-26 | Engelhard Ind Inc | Improvements in or relating to the hydrogenation of olefins in the presence of aromatic hydrocarbons |
DE1470487A1 (en) * | 1961-11-24 | 1968-12-19 | British Petroleum Co | Process for the desulfurization of hydrocarbonaceous materials |
DE1645689A1 (en) * | 1968-03-19 | 1971-07-01 | Air Prod & Chem | Process for the treatment of an unsaturated hydrocarbon distillate |
FR2104631A1 (en) * | 1967-04-28 | 1972-04-21 | Universal Oil Prod Co | |
GB1565754A (en) * | 1978-03-08 | 1980-04-23 | British Petroleum Co | Selective hydrogenation |
US5064525A (en) * | 1991-02-19 | 1991-11-12 | Uop | Combined hydrogenolysis plus oxidation process for sweetening a sour hydrocarbon fraction |
US5290427A (en) * | 1991-08-15 | 1994-03-01 | Mobil Oil Corporation | Gasoline upgrading process |
US5318690A (en) * | 1991-08-15 | 1994-06-07 | Mobil Oil Corporation | Gasoline upgrading process |
EP0685552A1 (en) * | 1994-06-01 | 1995-12-06 | Institut Francais Du Petrole | Process and installation for the selective hydrogenation of catalytic cracking gasoline |
EP0708167A1 (en) * | 1994-10-22 | 1996-04-24 | Krupp Koppers GmbH | Process for the production of a precursor product containing aromatic hydrocarbons for the recuperation of aromatics from raw coking benzene |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2025255A (en) * | 1934-02-07 | 1935-12-24 | Shell Dev | Method of treating cracked oil distillates |
US2270667A (en) * | 1940-05-20 | 1942-01-20 | Shell Dev | Process for extraction |
US2983669A (en) * | 1958-12-30 | 1961-05-09 | Houdry Process Corp | Hydrodesulfurization of selected gasoline fractions |
US3161586A (en) * | 1962-12-21 | 1964-12-15 | Universal Oil Prod Co | Hydrorefining of coke-forming hydrocarbon distillates |
US3424673A (en) * | 1966-03-07 | 1969-01-28 | Sun Oil Co | Process for hydrodesulfurizing the lower boiling fraction of a cracked gas oil blend |
US3457163A (en) * | 1967-06-16 | 1969-07-22 | Universal Oil Prod Co | Method for selective hydrogenation of diolefins with separation of gum formers prior to the reaction zone |
US3902991A (en) * | 1973-04-27 | 1975-09-02 | Chevron Res | Hydrodesulfurization process for the production of low-sulfur hydrocarbon mixture |
US3847800A (en) * | 1973-08-06 | 1974-11-12 | Kvb Eng Inc | Method for removing sulfur and nitrogen in petroleum oils |
US3957625A (en) * | 1975-02-07 | 1976-05-18 | Mobil Oil Corporation | Method for reducing the sulfur level of gasoline product |
US4113603A (en) * | 1977-10-19 | 1978-09-12 | The Lummus Company | Two-stage hydrotreating of pyrolysis gasoline to remove mercaptan sulfur and dienes |
FR2410038A1 (en) * | 1977-11-29 | 1979-06-22 | Inst Francais Du Petrole | SELECTIVE HYDROGENATION PROCESS OF GASOLINES CONTAINING BOTH GUM-GENERATING COMPOUNDS AND UNDESIRABLE SULFUR COMPOUNDS |
FR2473542B1 (en) * | 1980-01-12 | 1986-04-11 | Jgc Corp | PROCESS FOR SULFURIZING AND REFINING HYDROCARBON FRACTIONS CONTAINING LARGE QUANTITIES OF AROMATIC CONSTITUENTS |
FR2523149A1 (en) * | 1982-03-15 | 1983-09-16 | Catalyse Soc Prod Francais | NEW CATALYST SUPPORTING PALLADIUM-OR, ITS PREPARATION AND USE IN SELECTIVE HYDROGENATION REACTIONS OF DIOLEFINIC AND / OR ACETYLENE HYDROCARBONS |
US4897175A (en) * | 1988-08-29 | 1990-01-30 | Uop | Process for improving the color and color stability of a hydrocarbon fraction |
US4908122A (en) * | 1989-05-08 | 1990-03-13 | Uop | Process for sweetening a sour hydrocarbon fraction |
US4990242A (en) * | 1989-06-14 | 1991-02-05 | Exxon Research And Engineering Company | Enhanced sulfur removal from fuels |
US5503734A (en) * | 1991-08-15 | 1996-04-02 | Mobil Oil Corporation | Hydrocarbon upgrading process |
FR2689517B1 (en) * | 1992-04-02 | 1995-07-28 | Inst Francais Du Petrole | PROCESS FOR SELECTIVE HYDROGENATION OF HYDROCARBONS. |
JP3443474B2 (en) * | 1995-02-03 | 2003-09-02 | 新日本石油株式会社 | Desulfurization treatment method for catalytic cracking gasoline |
JP3450940B2 (en) * | 1995-06-08 | 2003-09-29 | 新日本石油株式会社 | Desulfurization method of catalytic cracking gasoline |
-
1996
- 1996-09-24 FR FR9611691A patent/FR2753717B1/en not_active Expired - Lifetime
-
1997
- 1997-09-08 DE DE69733985T patent/DE69733985T2/en not_active Expired - Lifetime
- 1997-09-08 EP EP97402088A patent/EP0832958B1/en not_active Expired - Lifetime
- 1997-09-22 KR KR1019970047976A patent/KR100456209B1/en not_active IP Right Cessation
- 1997-09-23 US US08/936,101 patent/US6007704A/en not_active Expired - Lifetime
- 1997-09-24 JP JP25872297A patent/JP4006483B2/en not_active Expired - Fee Related
-
1999
- 1999-11-05 US US09/434,282 patent/US6838060B1/en not_active Expired - Fee Related
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB967879A (en) * | 1961-07-06 | 1964-08-26 | Engelhard Ind Inc | Improvements in or relating to the hydrogenation of olefins in the presence of aromatic hydrocarbons |
DE1470487A1 (en) * | 1961-11-24 | 1968-12-19 | British Petroleum Co | Process for the desulfurization of hydrocarbonaceous materials |
FR2104631A1 (en) * | 1967-04-28 | 1972-04-21 | Universal Oil Prod Co | |
DE1645689A1 (en) * | 1968-03-19 | 1971-07-01 | Air Prod & Chem | Process for the treatment of an unsaturated hydrocarbon distillate |
GB1565754A (en) * | 1978-03-08 | 1980-04-23 | British Petroleum Co | Selective hydrogenation |
US5064525A (en) * | 1991-02-19 | 1991-11-12 | Uop | Combined hydrogenolysis plus oxidation process for sweetening a sour hydrocarbon fraction |
US5290427A (en) * | 1991-08-15 | 1994-03-01 | Mobil Oil Corporation | Gasoline upgrading process |
US5318690A (en) * | 1991-08-15 | 1994-06-07 | Mobil Oil Corporation | Gasoline upgrading process |
EP0685552A1 (en) * | 1994-06-01 | 1995-12-06 | Institut Francais Du Petrole | Process and installation for the selective hydrogenation of catalytic cracking gasoline |
EP0708167A1 (en) * | 1994-10-22 | 1996-04-24 | Krupp Koppers GmbH | Process for the production of a precursor product containing aromatic hydrocarbons for the recuperation of aromatics from raw coking benzene |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1077247A1 (en) * | 1999-08-19 | 2001-02-21 | Institut Francais Du Petrole | Process for the production of low sulphur gasolines |
FR2797639A1 (en) * | 1999-08-19 | 2001-02-23 | Inst Francais Du Petrole | PROCESS FOR PRODUCING LOW SULFUR ESSENCE |
EP2169032A1 (en) | 1999-08-19 | 2010-03-31 | Institut Français du Pétrole | Catalyst capable of at least partially decomposing or hydrogenating unsaturated sulfur compounds |
US6896795B2 (en) | 1999-08-19 | 2005-05-24 | Institut Francais Du Petrole | Process for the production of gasolines with low sulfur contents |
US6830678B2 (en) | 2000-03-29 | 2004-12-14 | Institut Francais Dupetrole | Process of desulphurizing gasoline comprising desulphurization of the heavy and intermediate fractions resulting from fractionation into at least three cuts |
FR2807061A1 (en) * | 2000-03-29 | 2001-10-05 | Inst Francais Du Petrole | FUEL DESULFURIZATION PROCESS COMPRISING DESULFURIZATION OF HEAVY AND INTERMEDIATE FRACTIONS FROM A FRACTIONATION IN AT LEAST THREE CUT |
EP1138749A1 (en) * | 2000-03-29 | 2001-10-04 | Institut Francais Du Petrole | Gasoline desulphurisation process comprising the desulphurisation of heavy and intermediate fractions from a fractionation into at least three cuts |
EP1247857A3 (en) * | 2001-04-03 | 2003-03-19 | Chevron U.S.A. Inc. | Mild hydrotreating/extraction process for low sulfurfuel for use in fuel cells |
EP1247857A2 (en) * | 2001-04-03 | 2002-10-09 | Chevron U.S.A. Inc. | Mild hydrotreating/extraction process for low sulfurfuel for use in fuel cells |
CN102443433A (en) * | 2010-10-15 | 2012-05-09 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
CN102443433B (en) * | 2010-10-15 | 2014-07-30 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline |
CN102465031A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Hydrotreating method for heavy hydrocarbon raw materials |
CN102465031B (en) * | 2010-11-04 | 2014-07-23 | 中国石油化工股份有限公司 | Hydrotreating method for heavy hydrocarbon raw materials |
CN110643380A (en) * | 2019-08-22 | 2020-01-03 | 中科合成油工程股份有限公司 | Method for converting coal pyrolysis product into gasoline, diesel oil and hydrogen |
Also Published As
Publication number | Publication date |
---|---|
DE69733985T2 (en) | 2006-01-26 |
JP4006483B2 (en) | 2007-11-14 |
KR100456209B1 (en) | 2005-01-27 |
DE69733985D1 (en) | 2005-09-22 |
FR2753717B1 (en) | 1998-10-30 |
US6838060B1 (en) | 2005-01-04 |
KR19980024831A (en) | 1998-07-06 |
FR2753717A1 (en) | 1998-03-27 |
US6007704A (en) | 1999-12-28 |
EP0832958B1 (en) | 2005-08-17 |
JPH10102070A (en) | 1998-04-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0832958B1 (en) | Process and apparatus for the production of low sulphur catalytically cracked gasolines | |
EP1002853B1 (en) | Process for the production of low sulfur gasolines | |
EP1138749B1 (en) | Gasoline desulphurisation process comprising the desulphurisation of heavy and intermediate fractions from a fractionation into at least three cuts | |
EP2169032B1 (en) | Catalyst capable of at least partially decomposing or hydrogenating unsaturated sulfur compounds | |
EP1174485B1 (en) | Process comprising two gasoline hydrodesulphurisation steps with intermediary elimination of H2S | |
EP2256179B1 (en) | Method for producing a hydrocarbon cut with a high octane level and low sulphur content | |
KR100493874B1 (en) | Process for highly shape selective dewaxing which retards catalyst aging | |
EP1931751B1 (en) | Gasoline desulfurization method comprising adsorption desulfurization of the light fraction and hydrodesulfurization of the heavy fraction | |
EP1849850A1 (en) | Method of desulphurating olefin gasolines comprising at least two distinct hydrodesulphuration steps | |
CA2299152C (en) | Process for the production of low-sulfur fuels | |
RU2186831C2 (en) | Hydrodesulfurization method and method for improving quality of hydrocarbon stock | |
EP1370627B1 (en) | Method for producing petrol having a low sulphur content | |
EP0831140B1 (en) | Process for the purification of catalytically cracked gasolines | |
CA2440189C (en) | Method for producing desulphurised petrol from a petroleum fraction containing cracked petrol | |
EP1370629B1 (en) | Method for producing low-sulphur petrol | |
FR2785833A1 (en) | Nickel based catalyst and its use in the dehydrosulfuration of hydrocarbonaceous charges | |
FR2625748A1 (en) | USE OF A CATALYST CONTAINING A ZEOLITHE OF THE ERIONITE FAMILY IN A CRACKING METHOD COMPRISING AT LEAST ONE REGENERATION AREA |
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): DE FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19981001 |
|
AKX | Designation fees paid |
Free format text: DE FR GB IT NL |
|
RBV | Designated contracting states (corrected) |
Designated state(s): DE FR GB IT NL |
|
17Q | First examination report despatched |
Effective date: 20021202 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB IT NL |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REF | Corresponds to: |
Ref document number: 69733985 Country of ref document: DE Date of ref document: 20050922 Kind code of ref document: P |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20050912 |
|
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 |
Effective date: 20060518 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: CD |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 69733985 Country of ref document: DE Owner name: IFP ENERGIES NOUVELLES, FR Free format text: FORMER OWNER: INSTITUT FRANCAIS DU PETROLE, RUEIL-MALMAISON, HAUTS-DE-SEINE, FR Effective date: 20110331 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20150924 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20150915 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20151001 Year of fee payment: 19 Ref country code: IT Payment date: 20150930 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20150921 Year of fee payment: 19 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 69733985 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MM Effective date: 20161001 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20160908 |
|
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: 20161001 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20170531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160930 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160908 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170401 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160908 |