EP1370627B1 - Verfahren zur herstellung von benzin mit niedrigem schwefelgehalt - Google Patents

Verfahren zur herstellung von benzin mit niedrigem schwefelgehalt Download PDF

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Publication number
EP1370627B1
EP1370627B1 EP02702449A EP02702449A EP1370627B1 EP 1370627 B1 EP1370627 B1 EP 1370627B1 EP 02702449 A EP02702449 A EP 02702449A EP 02702449 A EP02702449 A EP 02702449A EP 1370627 B1 EP1370627 B1 EP 1370627B1
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Prior art keywords
stage
gasoline
sulfur
fraction
light
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English (en)
French (fr)
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EP1370627A1 (de
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Quentin Debuisschert
Denis Uzio
Jean-Luc Nocca
Florent Picard
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
    • 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
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/08—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including acid treatment as the refining step in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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 invention relates to a method for producing low sulfur gasoline comprising hydrogenation, fractionation, a step of converting sulfur compounds and desulfurization.
  • This method makes it possible to upgrade a gasoline cutoff optionally further comprising hydrocarbons having two three or four carbon atoms, reducing the total sulfur content of said cut to very low levels compatible with current or future specifications.
  • This desulphurization is also carried out without a substantial reduction in fuel efficiency and minimizing the reduction of the octane number.
  • Hydrotreating (hydrodesulphurisation) of the feedstock sent to catalytic cracking leads to gasolines typically containing 100 ppm of sulfur.
  • the catalytic cracking feed hydrotreating units operate under severe temperature and pressure conditions, which implies a high hydrogen consumption and a high investment.
  • the entire charge must be desulfurized, resulting in the processing of very large load volumes.
  • the patent US-A-4,131,537 teaches the advantage of splitting the gasoline into several cuts, preferably three, depending on their boiling point, and of desulfurizing them under conditions which may be different and in the presence of a catalyst comprising at least one metal group VIB and / or group VIII. It is stated in this patent that the greatest benefit is obtained when the gasoline is split into three cuts, and when the intermediate boiling cut is treated under mild conditions.
  • the patent application EP-A-0 755 995 discloses a FCC gasoline desulfurization process comprising at least two steps.
  • the first is a catalytic hydrodesulfurization at a temperature between 200 and 350 ° C, with a desulphurization rate of between 60 and 90% and is carried out in the presence of a filler containing less than 0.1% by volume of sulfide. hydrogen (H2S).
  • the second, and optionally the following, are also catalytic hydrodesulfurization steps operated between 200 and 300 ° C and in the presence of a feed comprising less than 0.05% by volume of H2S.
  • the desulfurization rate is between 60 and 90% in this step. In this process, the concentration of H 2 S must be kept at a very low level.
  • the patent application EP-A-0 725 126 discloses a method for hydrodesulfurizing a cracking gasoline in which the gasoline is separated into a plurality of fractions comprising at least a first fraction rich in easily desulfurized compounds and a second fraction rich in difficult to desulphurize compounds. Before carrying out this separation, it is first necessary to determine the distribution of the sulfur compounds by means of analyzes. These analyzes are necessary to select the equipment and the separation conditions.
  • the gasolines to be treated generally have an initial point greater than 70 ° C, and again it is necessary to treat the light gasoline separately (fraction corresponding to the compounds of boiling point between C5 hydrocarbons having 5 carbon atoms and 70 ° C), for example by means of softening.
  • the patent US-A-5,318,690 proposes a process comprising fractionation of gasoline and sweetening of light gasoline, while heavy gasoline is desulphurized, then converted to zeolite ZSM-5 and desulphurized again under mild conditions.
  • This technique is based on a separation of the crude gasoline so as to obtain a light cut, preferably substantially free of sulfur compounds other than mercaptans. This makes it possible to treat said cut only by means of a softening which removes the mercaptans.
  • the olefins present in a relatively large amount in the heavy fraction are partly saturated during the hydrotreatment.
  • the patent advocates cracking zeolite ZSM-5 which produces olefins, but at the expense of yield.
  • these olefins can recombine with the H2S present in the medium to reform mercaptans. It is then necessary to perform additional softening or hydrodesulfurization.
  • the patent application WO 00/15319 discloses a process for simultaneously fractionating and treating a light naphtha.
  • the light cut contains mercaptans generally ranging from methyl mercaptan to hexyl mercaptan.
  • These sulfur compounds are removed from the light fraction only in the case where the fractionation column contains a hydrodesulfurization section at the top of the column. In the absence of this section, it is therefore not possible to eliminate the mercaptans which either end up in the desulfurized gasoline when the light fraction is recombined with the heavy desulphurized fraction, or can be eliminated with the whole of the light fraction, which causes a loss of the gasoline yield after desulphurization.
  • the patent US 6,083,379 describes a process for the desulphurization and improvement of the octane number of gasolines comprising a fractionation of the gasoline into at least two sections, the treatment of the light fraction in the presence of a zeolite, a fractionation of the light fraction thus treated, the mixture of heavy obtained during the two fractionation steps and the hydrodesulfurization of the mixture of these fractions.
  • the patent application WO 94/22980 describes a gasoline desulphurization process comprising a fractionation in two sections, the heavier cut is desulphurized in a hydrodesulphurization reactor and then treated in the presence of an acid catalyst which makes it possible to compensate for the loss of octane.
  • the lightest cut is also desulfurized by means of a non-hydrogenating extraction of mercaptans.
  • the patent US 5,968,346 discloses a method of hydroconversion of a hydrocarbon feedstock for removing impurities such as compounds comprising heteroatoms. This method comprises a first step of hydroconversion of the entire charge, followed by a separation of the liquid and the vapor present in the effluent of this first step and a contact of the gas with a liquid. The mixture of the two liquid fractions resulting from the contacting and the fractionation is then treated in a second hydroconversion stage in the presence of a catalyst.
  • the present invention relates to a process for the production of gasolines with a low sulfur content, which makes it possible to recover the whole of a sulfur-containing gasoline fraction, preferably a gasoline catalytic cracking or coking gasoline fraction (coking according to English terminology). , or pyrolysis, or visbreaking (visbreaking according to English terminology), and reduce sulfur levels in said gasoline cut at very low levels, without significant reduction in gasoline yield while minimizing the decrease in the index of octane due to the hydrogenation of olefins.
  • the feedstock of the process according to the invention may also optionally comprise, in addition to a gasoline cut, a C4 'cut comprising hydrocarbons containing two, three or four carbon atoms.
  • step f all of the heavy gasoline desulphurized from step f is mixed with the light gasoline from step c or d, without separation of the liquid and the gas contained in the heavy gasoline after desulphurization, optionally a simple stripping with an inert gas can be carried out to remove H2S from the totally desulfurized heavy gasoline.
  • a simple stripping with an inert gas can be carried out to remove H2S from the totally desulfurized heavy gasoline.
  • the recovery of light gasoline, desulphurised heavy gasoline, and possibly at least one intermediate gasoline is carried out separately. It is then unnecessary to perform step g.
  • the feedstock of the process according to the invention is a sulfur-containing gasoline cutter, preferably a gasoline cutter from a catalytic cracking unit, whose boiling point range typically extends from about the boiling points of hydrocarbons with 2 or 3 carbon atoms (C2 or C3) up to about 250 ° C, preferably from about the boiling points of the hydrocarbons with 2 or 3 carbon atoms (C2 or C3) up to about 220 ° C C, more preferably from about the boiling points of the 5-carbon hydrocarbons to about 220 ° C.
  • the end point of the gasoline cut depends on the refinery from which it comes and the constraints of the market, but generally remains within the limits indicated above.
  • a method for obtaining a gasoline preferably from a catalytic cracking unit, coking or deionization. visbreaking and having a limited sulfur content in which the gasoline is first subjected to a selective hydrogenation treatment diolefins, then optionally a step of processing the lighter sulfur compounds of gasoline which should after fractionation be in the light species so that they are essentially in the heavy fraction after the fractionation step of the process according to the invention.
  • the thus treated gasoline then undergoes a fractionation in at least two cuts.
  • At least one fraction resulting from the fractionation step may be treated in a step of conversion of the sulfur compounds chosen from the group consisting of thiophene, thiophene compounds and mercaptans.
  • Said step is preferably an alkylation or adsorption step.
  • the heavy gasoline is treated in a desulfurization section, preferably in the presence of a hydrodesulfurization catalyst or an absorbent.
  • No desulfurization of the light fraction is necessary in the process according to the invention, since most of the sulfur compounds initially present in the gasoline are found in the heavy fraction and optionally in the intermediate fraction or fractions after the steps of hydrogenation, transformation of light sulfur compounds (step b), fractionation (step c), and transformation of sulfur compounds including thiophene and mercaptans, in particular unconverted residual mercaptans and / or formed in steps a and b (step d); ).
  • This sequence makes it possible ultimately to obtain a desulphurized gasoline without significant reduction in the olefin content or octane number, even for high desulphurization rates, and this without it being necessary to treat light gasoline.
  • the fractionation point of the gasoline is preferably limited in order to avoid the presence of thiophene in light gasoline. Since the latter forms azeotropes with a certain number of hydrocarbons, only C5 olefins and a small part of the C6 olefins can be separated into the light gasoline. too much thiophene fraction in this section. In this case, it is advantageous to add to the process according to the invention a step d of transformation of thiophene and more generally of thiophene compounds, for example by means of an adsorption section or an alkylation reactor coupled to the fractionation section or integrated in said section according to a detailed mode in the following description.
  • step b and / or d in order to make it possible to recover a larger fraction of the olefins present in the light gasoline while limiting the sulfur content of this fraction without additional treatment, it is preferably proposed to treat the feed in step b and / or d in conditions and on catalysts which make it possible to convert the sulfur-containing compounds, preferably the light sulfur-containing compounds, into higher-boiling sulfur-containing compounds found after separation, optionally in at least an intermediate fraction or in heavy gasoline These intermediate and / or heavy cuts can then be desulfurized.
  • the sulfur content of catalytic cracked gasoline (FCC) gasoline cuts depends on the sulfur content of the FCC-treated feed, the presence or absence of FCC feed pretreatment, and the end point of the cut. .
  • the sulfur contents of the entirety of a petrol cut, in particular those coming 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, and in some cases they may even reach values of the order of 4000 to 5000 ppm by weight.
  • the method according to the invention is particularly applicable when high desulphurization rates of gasoline are required, ie when the desulphurized gas must contain at most 10% of the sulfur of the initial gasoline and possibly at most 5% or even more than 2% of the sulfur of the initial gasoline which corresponds to desulfurization rates greater than 90% or even greater than 95 or 98%.
  • a reactive column instead of the fractionation column, that is to say to place at least one of said reaction sections in the column of fractionation (internal column reaction section), preferably in a zone where the reagent concentration is maximum.
  • the reaction section will preferably be placed in a zone having the maximum concentration of these compounds. Since the light fraction of the gasoline does not require a desulfurization treatment, when a desulfurization section is internal to the fractionation column, the said reaction section will generally not be placed at the top of the column.
  • the reaction section internal to the column is chosen from the group consisting of the following reaction sections: hydrogenation (step a), transformation of light sulfur compounds (step b), transformation of sulfur compounds such as thiophene, thiophene compounds and optionally mercaptans (step d), desulfurization of the heavy fraction (step f).
  • the reaction section is placed in the middle of a fractionation column, so as to treat the compounds having intermediate boiling points, that is to say the compounds which can constitute a intermediate cut and which are recovered alone or with the heavy fraction at the bottom of the column, at the end of the fractionation step
  • the heavy fraction is then treated in an external reactor associated or not with the fractionation column.
  • Another variant of the process according to the invention consists both in using a reactive column comprising at least one reaction section and an external reactor coupled or not to said column.
  • Such variants are for example described in the patent application WO00 / 15319 .
  • the variants described above are only illustrations of the possible variants of the method according to the invention.
  • the method according to the invention can indeed be implemented by combining reaction sections (steps a, b, d, or f) or associated with the fractionation column of step c, or internally (s). to said column, either exteme (s) and uncoupled (s) to said column in that the effluent of said reaction section (s) (s) is not recycled to the fractionation column.
  • One of the advantages of the process according to the invention lies in the fact that it is not necessary to desulphurize the light fraction of the gasoline resulting from the fractionation.
  • the transformation of the sulfur and thiophene compounds makes it possible to considerably reduce the content of sulfur compounds in the light cut and optionally at least one intermediate cut, and generally to recover most of these compounds in the heavy fraction, and optionally in the intermediate fraction or fractions.
  • Steps b and d are distinguished inter alia by the fact that the conversion of the thiophene compounds is generally less than 60% by weight, or even less than 40% by weight in step b, whereas the conversion or adsorption of said compounds is more often greater than 80% by weight, preferably greater than 90% by weight, very preferably greater than 95% by weight in step d.
  • step b essentially increases the weight of light mercaptans.
  • This operation is carried out while maintaining most of the olefins in the light fraction, possibly in at least one intermediate fraction that does not require extensive desulfurization.
  • the content of sulfur compounds of the light fraction thus obtained is generally less than 50 ppm, preferably less than 20 ppm, more preferably less than 10 ppm and very preferably less than 5 ppm.
  • Another advantage lies in the fact that the residual content of sulfur compounds of the gasoline desulphurized by means of the process according to the invention is particularly low, and that the octane number of the gasoline is maintained at a high level.
  • step a hydrogenation of diolefins
  • Hydrogenation of dienes is a step which eliminates, before hydrodesulphurization, almost all the dienes present in the gasoline cutter containing sulfur to be treated. It preferably takes place in the first step (step a) of the process according to the invention, generally in the presence of a catalyst comprising at least one metal of group VIII, preferably chosen from the group consisting of platinum, palladium and nickel , and a support.
  • a catalyst comprising at least one metal of group VIII, preferably chosen from the group consisting of platinum, palladium and nickel
  • a support a catalyst based on nickel or palladium deposited on an inert support, such as, for example, alumina, silica or a support containing at least 50% alumina, will be used.
  • the pressure employed is sufficient to maintain more than 60%, preferably 80%, and more preferably 95% by weight of the gasoline to be treated in the liquid phase in the reactor; it is most generally between about 0.4 and about 5 MPa and preferably greater than 1 MPa, more preferably between 1 and 4 MPa.
  • the hourly space velocity of the liquid to be treated is between about 1 and about 20 h -1 (volume of filler per volume of catalyst per hour), preferably between 2 and 10 h -1 , very preferably between 3 and 8 h -1 .
  • the temperature is most generally between about 50 and about 250 ° C, and preferably between 80 and 220 ° C, and more preferably between 100 and 200 ° C, to ensure sufficient conversion of the diolefins.
  • the ratio of hydrogen on charge expressed in liters is generally between 1 and 50 liters per liter, preferably between 3 and 30 liters per liter, more preferably between 8 and 25 liters per liter.
  • the choice of operating conditions is particularly important. It will operate most generally under pressure and in the presence of a quantity of hydrogen in small excess relative to the stoichiometric value necessary to hydrogenate the diolefins.
  • the hydrogen and the feedstock to be treated are injected in ascending or descending streams into a reactor preferably comprising a fixed bed of catalyst.
  • Another metal may be associated with the main metal to form a bimetallic catalyst, such as, for example, molybdenum or tungsten.
  • the catalytic cracked gasoline may contain up to a few weight percent of diolefins. After hydrogenation, the diolefin content is generally reduced to less than 3000 ppm, or even less than 2500 ppm and more preferably less than 1500 ppm. In some cases, it can be obtained less than 500 ppm. The diene content after selective hydrogenation can even if necessary be reduced to less than 250 ppm.
  • the hydrogenation stage of the dienes 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 effect the desired reactions.
  • This step consists of transforming the light compounds of sulfur. That is to say the compounds that after the separation step b would be in the light gasoline, heavier sulfur compounds driven in heavy gasoline.
  • the light compounds transformed have a boiling point lower than that of thiophene.
  • This transformation is preferably carried out on a catalyst comprising at least one element of group VIII (groups 8, 9 and 10 of the new, periodic classification), or comprising a resin.
  • group VIII groups 8, 9 and 10 of the new, periodic classification
  • the choice of catalyst is made in particular to promote the reaction between light mercaptans and olefins, which leads to heavier mercaptans.
  • This step may possibly be carried out at the same time as step a.
  • it may be particularly advantageous to operate, during the hydrogenation of the diolefins, under conditions such that at least a portion of the compounds in the form of mercaptan are converted. Thus some reduction of the mercaptan content is obtained.
  • Another possibility is to use a catalyst based on nickel identical to or different from the catalyst of step a, such as, for example, the catalyst recommended in the process of the patent. US-A-3,691,066 , which makes it possible to transform mercaptans (butyl mercaptan) into heavier sulfur compounds (sulphides).
  • Another possibility for carrying out this step is to hydrogenate thiophene at least partially to thiophane whose boiling point is greater than that of thiophene (boiling point 121 ° C.).
  • This step can be carried out on a catalyst based on nickel, platinum or palladium. In this case the temperatures are generally between 100 and 300 ° C and preferably between 150 and 250 ° C.
  • the H2 / filler ratio is adjusted to between 1 and 20 liters per liter, preferably between 3 and 15 liters per liter, so as to favor, if possible, the desired hydrogenation of the thiophene compounds and to minimize the hydrogenation of the olefins present in the feedstock.
  • the space velocity is generally between 1 and 10 h -1 , preferably between 2 and 4 h -1 and the pressure between 0.5 and 5 MPa, preferably between 1 and 3 MPa.
  • This separation is preferably carried out by means of a conventional distillation column also known as a splitter.
  • This fractionation column must make it possible to separate a light fraction of the gasoline containing a small sulfur fraction and a heavy fraction preferably containing most of the sulfur initially present in the initial gasoline.
  • This column generally operates at a pressure of between 0.1 and 2 MPa and preferably between 0.2 and 1 MPa.
  • the number of theoretical plates of this separation column is generally between 10 and 100 and preferably between 20 and 60.
  • the reflux ratio expressed as the ratio of the liquid flow rate in the column divided by the distillate flow rate expressed in kg. / h, is generally less than unity and preferably less than 0.8.
  • the light gasoline obtained after the separation generally contains at least all the C5 olefins, preferably the C5 compounds and at least 20% of the C6 olefins. Generally, this light fraction has a low sulfur content, ie it is not generally necessary to treat the light cut before using it as fuel.
  • the light cut L is preferably injected into a liquid gas separation tank in order to separate the unconsumed hydrogen and the H 2 S, formed during step a and / or b, from olefins generally having from 5 to 7 carbon atoms. carbon.
  • Heavy cut H2 whose boiling temperatures are generally greater than about 160 ° C or about 120 ° C is fed to f) desulphurization step.
  • the sections 12 may again be fractionated into an intermediate section 13 and a heavy section H3, especially when step d is an alkylation step of the thiophene compounds.
  • the H3 cut thus obtained may optionally be mixed with the H2 cut, preferably before desulfurization.
  • Step d is a step of transformation of the sulfur compounds selected from the group consisting of thiophene, thiophene compounds and mercaptans present in the light cut and / or in at least one intermediate fraction.
  • This step consists of passing the light fraction and / or possibly at least one intermediate fraction resulting from the fractionation (step c) over a catalyst having an acid function which makes it possible to carry out the addition of the sulfur compounds in the form of mercaptans to the olefins and the alkylation reaction of thiophene and thiophene derivatives with these same olefins.
  • the operating conditions are adjusted to achieve the desired conversion with conversion rates of thiophene and / or thiophenics and / or light mercaptans, preferably mercaptans having from 1 to 6 carbon atoms, greater than 80% by weight, preferably greater than 90% by weight, very preferably greater than 95% by weight.
  • Other compounds such as COS or CS2 may optionally also be adsorbed or converted.
  • the gasoline may be additive of a compound known to inhibit the oligomerizing activity of acid catalysts such as alcohols, ethers or water.
  • the light cut or intermediate cut obtained in step c is treated in a section for converting by alkylation the compounds selected from the group consisting of thiophene, thiophene compounds and mercaptans.
  • the thiophenic compounds contained in the 60 ° C.-160 ° C. section will react with conversion levels of greater than 80% by weight, preferably greater than 90% by weight, with the olefins to form thiophene alkyls according to the following reaction for thiophene. :
  • benzene may also be removed by alkylation with the olefins.
  • These compounds of higher molecular weight are mainly characterized by higher boiling temperatures than they had before alkylation.
  • the theoretical boiling temperature which is 80 ° C., is displaced towards 250 ° C. for the thiophene alkyls, and this reaction therefore generally leads to a heavier gasoline, especially in the case where the gasoline fraction and / or the starting gasoline are light.
  • This alkylation step is carried out in the presence of an acid catalyst.
  • This catalyst may be indifferently a resin, a zeolite, a clay, any functionalized silica or any silico-aluminate having acidity, or any grafted support of acidic functional groups.
  • the ratio of the charge volume injected onto the catalyst volume is between 0.1 and 10 titer / liter / hour and preferably between 0.5 and 4 titer / liter / hour.
  • this alkylation step is carried out in the presence of at least one acidic catalyst selected from the group consisting of silicoaluminates, titanosilicates, mixed titanium alumina, clays, resins, mixed oxides obtained by grafting with least an organosoluble or water-soluble organometallic compound (selected from the group consisting of alkys and / or alkoxy metals of at least one element such as titanium, zirconium silicon, germanium, tin, tantalum, niobium, etc.) on at least one oxide such as alumina (gamma, delta, eta, alone or as a mixture), silica, silica aluminas, titanium silicas, zirconia silicas or any other solid having any acidity.
  • a particular embodiment of the invention may consist in using a physical mixture of at least two of the above catalysts in proportions varying from 95/5 to 5/95, preferably from 85/15 to 15185 and very preferably from 70/30 to 30/70 ".
  • the temperature for this step is generally between 10 and 350 ° C depending on the type of catalyst or the strength of the acidity.
  • the temperature is between 50 and 150 ° C., preferably between 50 and 120 ° C.
  • the olefin molar ratio on thiophene compounds is between 0.1 and 1000 mol / mol, preferably between 0.5 and 500 mol / mol.
  • the operating pressure of this step is generally between 0.1 and 3 MPa and preferably such that the filler is in liquid form under the conditions of temperature and pressure, ie at a pressure greater than 0.5 MPa.
  • the effluent from step d, of transformation of the sulfur compounds, preferably alkylation or adsorption may optionally be mixed at least in part with a heavy cut from the fractionation in step c.
  • the effluent from step d of transformation of the sulfur compounds can also optionally be sent to a new fractionation unit to be separated into two fractions, an untreated or optionally desulfurized intermediate fraction without being mixed, and a heavy fraction which is preferably mixed with the heavy fraction from step d before being desulphurized in step f,
  • Step d may advantageously be carried out on the light fraction resulting from step c. Indeed, the alkylation of the light mercaptans present in this fraction then facilitates the desired removal of the sulfur compounds, but also makes it possible to reduce the vapor pressure (RVP or Reid Vapor Pressure index according to the Anglosaxon terminology) of the final desulphurized gasoline. .
  • RVP Reid Vapor Pressure index according to the Anglosaxon terminology
  • All of the effluent D1 from said alkylation unit (step d) or the D3 cut resulting from the fractionation after alkylation may be preferably mixed at least in part with a heavy cut (for example the H2 cut) and sent to the desulfurization section of step f.
  • a heavy cut for example the H2 cut
  • step f Desulfurization of the heavy fraction
  • This step may for example be a hydrodesulphurization step carried out by passing the heavy gasoline, in the presence of hydrogen, over a catalyst comprising at least one element of group VIII and / or at least one element of group VIb at least portion in sulphide form, at a temperature between about 210 ° C and about 350 ° C, preferably between 220 ° C and 320 ° C, at a pressure generally between about 1 and about 4 MPa, preferably between 1.5 and 3 MPa.
  • the space velocity of the liquid is between about 1 and about 20 h -1 (expressed as volume of liquid per volume of catalyst per hour), preferably between 1 and 10 h -1 , very preferably between 3 and 8 h -1.
  • the ratio H 2 / HC is between 100 to 600 liters per liter and preferably between 300 and 600 liters per liter.
  • the content of Group VIII metal expressed as oxide is generally between 0.5 and 15% by weight, preferably between 1 and 10% by weight.
  • the metal content of group VIb is generally between 1.5 and 60% by weight, preferably between 3 and 50% by weight.
  • the element of group VIII, when present, is preferably cobalt
  • the element of group VIb, when present is usually molybdenum or tungsten. Combinations such as cobalt-molybdenum are preferred.
  • the catalyst support is usually a porous solid, such as for example an alumina, a silica-alumina or other porous solids, such as, for example, magnesia, silica or titanium oxide, alone or in mixture with alumina or silica-alumina.
  • the catalyst according to the invention preferably has a specific surface area of less than 190 m 2 / g, more preferably less than 180 m 2 / g, and very preferably less than 150 m 2 / g.
  • the catalyst After introduction of the element or elements and possibly shaping of the catalyst (when this step is performed on a mixture already containing the base elements), the catalyst is in a first activated step.
  • This activation can correspond to either an oxidation then a reduction, a direct reduction, or a calcination only.
  • the calcination step is generally carried out at temperatures of from about 100 to about 600 ° C and preferably from 200 to 450 ° C under an air flow rate.
  • the reduction step is performed under conditions to convert at least a portion of the oxidized forms of the base metal to metal. Generally, it consists in treating the catalyst under a flow of hydrogen at a temperature preferably of at least 300 ° C.
  • the reduction can also be achieved in part by means of chemical reducers.
  • the catalyst is preferably used at least in part in its sulfurized form.
  • the introduction of sulfur may occur before or after any activation step, that is, calcination or reduction.
  • no catalyst oxidation step is performed when the sulfur or a sulfur compound has been introduced on the catalyst.
  • the sulfur or a sulfur compound can be introduced ex situ, that is to say outside the reactor where the process according to the invention is carried out, or in situ, that is to say in the reactor used for process according to the invention.
  • the catalyst is preferably reduced under the conditions described above, then sulfided by passing a feed containing at least one sulfur compound, which once decomposed leads to the fixation of sulfur on the catalyst.
  • This charge may be gaseous or liquid, for example hydrogen containing H 2 S, or a liquid containing at least one sulfur compound.
  • the sulfur compound is added to the ex situ catalyst .
  • a sulfur compound may be introduced onto the catalyst in the presence of possibly another compound.
  • the catalyst is then dried and then transferred to the reactor for carrying out the process according to the invention.
  • the catalyst is then treated in hydrogen to convert at least a portion of the main metal sulfide.
  • a procedure which is particularly suitable for the invention is that described in the patents FR-B-2 708 596 and FR-B-2,708,597 .
  • the desulfurization of heavy gasoline can also be carried out by means of an absorber comprising an absorbent mass, for example based on zinc oxide.
  • Said desulfurization can also be carried out by means of a combination between a hydrodesulfurization section and an absorber; preferably located after the hydrodesulfurization section.
  • the desulfurization section preferably comprises only one absorber and / or one reactor.
  • Said reactor contains only one type (in terms of chemical formulation) of hydrodesulfurization catalyst, possibly arranged in several separate beds.
  • said catalyst is cobalt-based, most preferably it is a catalyst comprising cobalt and molybdenum or tungsten.
  • the catalyst employed in this section is sulfided.
  • the optional treatment section of at least one intermediate section can comprise several reactors possibly associated with one or more absorbers.
  • Said section may comprise two reactors in series, possibly with a separation of the gas containing H2S and the liquid between the two reactors.
  • two different catalysts arranged in at least two beds inside said reactors, optionally with an intermediate addition of hydrogen (also called quench according to English terminology).
  • said catalysts are sulphurized.
  • FIG. 1 illustrates some preferred variants of the method according to the invention.
  • the charge is admitted via line 1 and mixed with hydrogen arriving via line 2.
  • the mixture 3 is introduced into the reactor 4 containing a catalyst for selective hydrogenation of diolefins (step a).
  • the effluent from this reactor is introduced into a reactor 7, optionally after the addition of hydrogen via line 6.
  • the reactor 7 contains a catalyst which makes it possible to weigh up light sulfur compounds, such as light mercaptans, by reaction with olefins (step b).
  • Efftuent 8 from the reactor 7 is introduced into a fractionation column (9) to achieve a separation of the gasoline in at least 2 sections: a light cut which is untreated, and a heavy cut 13 which is desulfurized in a reactor 20 containing a hydrodesulphurization catalyst, after mixing with hydrogen taken up by line 19.
  • the heavy desulfurized fraction 21 is mixed with the light fraction to yield the desulfurized gasoline 22.
  • the fractionation column 9 makes it possible to separate the effluent 8 from the reactor 7 in 4 sections: an untreated light section 10, a first intermediate section 11 introduced into a reactor 11 alkylation 14 which allows the alkylation of thiophene, thiophenic compounds and optionally mercaptans and whose effluent is returned to the fractionation column 9 via line 15, a second intermediate fraction 12 treated in the presence of hydrogen brought via line 16 in a reactor containing a hydrodesulphurization catalyst, and a heavy cut 13 which is also desulphurized in the presence of hydrogen taken via line 19 in a reactor 20 containing a hydrodesulfurization catalyst.
  • the desulphurized heavy fraction 21, and the desulfurized intermediate fraction 18 are mixed with the light fraction to yield the desulfurized gasoline 22.
  • the process according to the invention is a process for producing gasoline with a low sulfur content, comprising at least the following steps: at least one selective hydrogenation of the diolefins present in the initial gasoline (step a) at least one step of transforming the light sulfur compounds present in the gasoline (step b), at least one fractionation (step c) of the gasoline obtained in step a or b into at least fractions a light fraction a fraction intermediate and a heavy fraction a step (step d) of transformation of the thiophene compounds and mercaptans present in at least one cut obtained in step c, a desulphurization treatment in one step (step f) of at least a portion of the heavy fraction resulting from the fractionation in step c.
  • steps a and b are carried out simultaneously in the same reactor.
  • steps b and / or d make it possible to increase the molecular weight of the sulfur compounds, in order to separate them mainly in the heavy fraction of step c.
  • the heavy gasoline is desulfurized in step f in the presence of a hydrodesulphurization catalyst or an absorbent, and more preferably the heavy gasoline desulfurized in step f is stripped by means of an inert gas.
  • the process according to the invention may also comprise a step g of mixing the light fraction resulting from step c or d and optionally at least one fraction intermediate resulting from stage c or d with the heavy desulfurized fraction resulting from stage f.
  • the process according to the invention comprises at least one internal column-forming editorial section selected from the group consisting of the following reaction sections: hydrogenation (step a), transformation of light sulfur compounds (step b), transformation sulfur compounds selected from the group consisting of thiophene, thiophene compounds and mercaptans (step d), and desulfurization of the heavy fraction (step f).
  • At least one reaction section of the process according to the invention is coupled to the column and selected from the group consisting of the following reaction sections: hydrogenation (step a), transformation of light sulfur compounds (step b), transformation of the sulfur compounds selected from the group consisting of thiophene, thiophene compounds and mercaptans (step d), and desulfurization of the heavy fraction (step-f).
  • the effluent from step d of transformation of the sulfur compounds may optionally be mixed at least in part with a heavy cut from the fractionation in step c.
  • Said effluent may also be sent to a new fractionation unit to be separated into two fractions, an untreated or optionally desulfurized intermediate fraction without being mixed, and a heavy fraction which is preferably mixed with the heavy fraction resulting from step c before being desulphurized in step f.
  • a catalytic cracking gasoline whose characteristics are shown in Table 1 is separated into two fractions (step c), a light fraction whose cutting point corresponds to a temperature of 63 ° C and a heavy fraction.
  • the light fraction represents 25% by weight of the starting gasoline and contains 88% of the compounds olefins having 5 carbon atoms which were present in the starting gasoline and 23% of the olefins having 6 carbon atoms.
  • the light fraction has a content of sulfur, mercaptan and diolefin such that it is no longer necessary to carry out additional treatment of this fraction before using it.
  • the heavy fraction is subjected to hydrodesulfurization on a catalyst in isothermal tubular reactor.
  • the catalyst is obtained by impregnation "without excess solution" of a transition alumina, in the form of beads, with a specific surface area of 130 m 2 / g and a pore volume of 0.9 ml / g, with a solution aqueous solution containing molybdenum and cobalt in the form of ammonium heptamolybdate and cobalt nitrate.
  • the catalyst is then dried and calcined under air at 500 ° C.
  • the cobalt and molybdenum content of this catalyst sample A is 3% CoO and 14% MoO3.
  • the catalyst is previously sulphurized by treatment for 4 hours at a pressure of 3.4 MPa at 350 ° C., in contact with a feedstock containing 2% by weight of S in the form of dimethylsulphide diluted in n-heptane.
  • the temperature of the reaction zone is 280 ° C.
  • the characteristics of the effluents obtained are presented in Table 2.
  • the desulphurized heavy gasoline is then mixed with the light gasoline whose composition is given in Table 1.
  • the gasoline thus constituted contains 185 ppm of sulfur including 100 ppm of mercaptans. Such gasoline will therefore require additional treatment before use.
  • the gasoline whose characteristics are described in Example 1 is subjected to a hydrogenation treatment of diolefins (step a) under conditions such that the sulfur-containing light compounds present in the feed are partly converted into heavier compounds (step b performed simultaneously in step a).
  • This treatment is carried out in a continuous reactor operating in updraft.
  • the catalyst is an HR945 catalyst marketed by the company Procatalyse.
  • the reaction is carried out at 160 ° C. under a total pressure of 13 bar, with a space velocity of 6 h -1 .
  • the H2 / feed ratio expressed in liters of hydrogen per liter of feed and 10.
  • step c the essence is separated into two fractions (step c) under the conditions described in Example 1.
  • the characteristics of the two fractions obtained are specified in Table 4.
  • Table 4 Characteristics of light and heavy cuts after fractionation (step c) Catalytic cracking gasoline light fraction heavy fraction total essence PI-63 63-220 ° C IND REFRACTION at 20 ° C 1.44 1.38 1.45 VOLUMIC MASS 15/4 0.78 0.67 0.79 IBr (g / 100g) 75.5 158 48 MAV (mg / g) 0.2 0.0 0.3 TOTAL NITROGEN (mg / l) 40 2.7 50 RON 92.2 92.8 92.0 MY 79.9 82.9 78.9 SULFUR NON MERCAPTANS (mg / Kg) 1561 31 2071 MERCAPTANS (mg / kg) 6 2 7 TOTAL SULFUR (mg / Kg) 1567 33 2078
  • the light fraction contains a content of sulfur, mercaptan and diolefin such that it is no longer necessary to carry out additional treatment of this fraction before using it.
  • the heavy fraction is subjected to hydrodesulfurization on the catalyst A of Example 1 in an isothermal tubular reactor.
  • the catalyst is previously sulphurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C., in contact with a feedstock containing 2% by weight of S in the form of dimethylsulphide diluted in n-heptane.
  • the temperature of the reaction zone is 280 ° C.
  • the characteristics of the effluents obtained are presented in Table 5.
  • the desulphurized heavy gasoline is then mixed with the untreated light gasoline whose composition is given in Table 4.
  • the desulphurized gasoline thus constituted contains 147 ppm of sulfur including 68 ppm of mercaptans.

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Claims (9)

  1. Verfahren zur Herstellung von Benzin mit niedrigem Schwefelgehalt, welches mindestens die folgenden Schritte umfasst:
    - mindestens eine selektive Hydrierung der Diolefine, die im Ausgangsbenzin vorliegen (Schritt a),
    - mindestens einen Schritt der Umwandlung der leichten Schwefelverbindungen, die in dem Benzin vorliegen (Schritt b), um das Molekulargewicht der Schwefelverbindungen zu erhöhen, wobei die Umwandlung an einem Katalysator erfolgt, der mindestens ein Element der Gruppe VIII umfasst,
    - mindestens eine Fraktionierung (Schritt c) des Benzins, das in Schritt b erhalten wurde, in mindestens eine Leichtfraktion, mindestens eine Mittelfraktion und eine Schwerfraktion,
    - einen Schritt (Schritt d) der Umwandlung der Schwefelverbindungen, welcher darin besteht, mindestens eine Mittelfraktion, die aus der Fraktionierung (Schritt c) stammt, über einen Katalysator zu leiten, der eine funktionelle Säuregruppe aufweist, welche es ermöglicht, eine Addition der Schwefelverbindungen in Form von Mercaptanen an die Olefine sowie eine Reaktion der Alkylierung des Thiophens und der Thiophenderivate durch ebendiese Olefine durchzuführen,
    - eine einschrittige Behandlung (Schritt f) zur Entschwefelung mindestens eines Teil der Schwerfraktion, die aus der Fraktionierung in Schritt c stammt,
    und bei welchem der Stoffstrom, der aus dem Schritt d zur Umwandlung der Schwefelverbindungen stammt, in eine neue Fraktionierungseinheit eingeleitet wird, um in zwei Fraktionen getrennt zu werden, nämlich eine unbehandelte Mittelfraktion und eine Schwerfraktion, die mit der Schwerfraktion vermischt wird, welche aus dem Schritt c stammt, bevor sie in Schritt f entschwefelt wird.
  2. Verfahren nach Anspruch 1, wobei die Leichtfraktion in einem Schritt zur Umwandlung der Schwefelverbindungen gemäß Schritt d behandelt wird,
  3. Verfahren nach einem der Ansprüche 1 oder 2, wobei die Schritte a und b gleichzeitig in demselben Reaktor durchgeführt werden.
  4. Verfahren nach einem der Ansprüche 1 oder 2, wobei es der Schritt b ermöglicht, das Molekulargewicht der Schwefelverbindungen zu erhöhen.
  5. Verfahren nach einem der Ansprüche 1 bis 4, wobei das Schwerbenzin in Schritt f in Gegenwart eines Katalysators für die hydrierende Entschwefelung oder eines Absorptionsmittels entschwefelt wird.
  6. Verfahren nach einem beliebigen der Ansprüche 1 bis 5, wobei das Schwerbenzin, das in Schritt f entschwefelt wird, mittels eines Inertgases gestrippt wird.
  7. Verfahren nach einem der Ansprüche 1 bis 6, das darüber hinaus einen Schritt g umfasst, bei welchem die Leichtfraktion, die aus Schritt c oder d stammt, und möglicherweise eine Mittelfraktion, die aus Schritt c oder d stammt, mit der entschwefelten Schwerfraktion, die aus Schritt f stammt, vermischt werden.
  8. Verfahren nach einem der Ansprüche 1 bis 7, wobei sich mindestens ein Reaktionsbereich im Inneren der Kolonne befindet und aus der Gruppe ausgewählt ist, die aus den folgenden Reaktionsbereichen ausgewählt ist: Hydrierung (Schritt a), Umwandlung der leichten Schwefelverbindungen (Schritt b), Umwandlung der Schwefelverbindungen, die aus der Gruppe ausgewählt sind, welche aus Thiophen, den Thiophenverbindungen und den Mercaptanen besteht (Schritt d), und Entschwefelung der Schwerfraktion (Schritt f).
  9. Verfahren nach einem der Ansprüche 1 bis 8, wobei mindestens ein Reaktionsbereich mit der Kolonne gekoppelt ist und aus der Gruppe ausgewählt ist, die aus den folgenden Reaktionsbereichen ausgewählt ist: Hydrierung (Schritt a), Umwandlung der leichten Schwefelverbindungen (Schritt b), Umwandlung der Schwefelverbindungen, die aus der Gruppe ausgewählt sind, welche aus Thiophen, den Thiophenverbindungen und den Mercaptanen besteht (Schritt d), und Entschwefelung der Schwerfraktion (Schritt f).
EP02702449A 2001-03-12 2002-01-29 Verfahren zur herstellung von benzin mit niedrigem schwefelgehalt Expired - Lifetime EP1370627B1 (de)

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FR0103358A FR2821850B1 (fr) 2001-03-12 2001-03-12 Procede de production d'essence a faible teneur en soufre comprenant une hydrogenation, un fractionnement, une etape de transformation des composes soufres et une desulfuration
FR0103358 2001-03-12
PCT/FR2002/000349 WO2002072738A1 (fr) 2001-03-12 2002-01-29 Procede de production d'essence a faible teneur en soufre

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CN108659884A (zh) * 2017-03-28 2018-10-16 中国石油化工股份有限公司 汽油脱硫的方法

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US7122114B2 (en) * 2003-07-14 2006-10-17 Christopher Dean Desulfurization of a naphtha gasoline stream derived from a fluid catalytic cracking unit
FR2857975B1 (fr) 2003-07-25 2008-01-11 Inst Francais Du Petrole Procede de disulfuration des essences
FR2908781B1 (fr) * 2006-11-16 2012-10-19 Inst Francais Du Petrole Procede de desulfuration profonde des essences de craquage avec une faible perte en indice d'octane
CN101307254B (zh) * 2007-05-18 2011-06-22 中国石油化工股份有限公司 劣质汽油生产清洁汽油的方法
US8246811B2 (en) 2009-05-26 2012-08-21 IFP Energies Nouvelles Process for the production of a hydrocarbon fraction with a high octane number and a low sulfur content
US10308883B2 (en) * 2015-10-07 2019-06-04 Axens Process for desulfurizing cracked naphtha
FR3057578B1 (fr) 2016-10-19 2018-11-16 IFP Energies Nouvelles Procede d'hydrodesulfuration d'une essence olefinique.

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US5360532A (en) * 1991-08-15 1994-11-01 Mobil Oil Corporation Gasoline upgrading process
JP3387700B2 (ja) * 1995-07-26 2003-03-17 新日本石油株式会社 接触分解ガソリンの脱硫方法
FR2797639B1 (fr) * 1999-08-19 2001-09-21 Inst Francais Du Petrole Procede de production d'essences a faible teneur en soufre
FR2807061B1 (fr) * 2000-03-29 2002-05-31 Inst Francais Du Petrole Procede de desulfuration d'essence comprenant une desulfuration des fractions lourde et intermediaire issues d'un fractionnement en au moins trois coupes

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CN108659884A (zh) * 2017-03-28 2018-10-16 中国石油化工股份有限公司 汽油脱硫的方法
CN108659884B (zh) * 2017-03-28 2020-10-27 中国石油化工股份有限公司 汽油脱硫的方法

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KR100813775B1 (ko) 2008-03-13
JP4186157B2 (ja) 2008-11-26
ES2360432T3 (es) 2011-06-03
WO2002072738A1 (fr) 2002-09-19
ES2371061T3 (es) 2011-12-27
BR0208042A (pt) 2004-02-25
JP2004523628A (ja) 2004-08-05
KR20030080085A (ko) 2003-10-10
BR0208042B1 (pt) 2012-08-07
FR2821850B1 (fr) 2007-04-27
EP1370627A1 (de) 2003-12-17
CA2440180C (fr) 2009-12-22

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