EP1369468B1 - Herstellungsverfahren von Kohlenwasserstoffen mit niedrigem Gehalt von Schwefel und von Stickstoff - Google Patents

Herstellungsverfahren von Kohlenwasserstoffen mit niedrigem Gehalt von Schwefel und von Stickstoff Download PDF

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Publication number
EP1369468B1
EP1369468B1 EP03291317.0A EP03291317A EP1369468B1 EP 1369468 B1 EP1369468 B1 EP 1369468B1 EP 03291317 A EP03291317 A EP 03291317A EP 1369468 B1 EP1369468 B1 EP 1369468B1
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Prior art keywords
feed
process according
catalyst
sulfur
ppm
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French (fr)
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EP1369468A1 (de
Inventor
Nathalie Marchal-George
Florent Picard
Denis Uzio
Quentin Debuissechert
Jean Luc Nocca
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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
    • 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
    • C10G67/06—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 a sorption process as the refining step in the absence of hydrogen

Definitions

  • the present invention relates to a process for producing low sulfur hydrocarbons.
  • This hydrocarbon fraction contains an olefin fraction generally greater than 5% by weight and most often greater than 10% by weight, a sulfur content greater than 100 ppm by weight and a nitrogen content greater than 20 ppm by weight.
  • the method makes it possible in particular to valorize all of a sulfur-containing gasoline cut by reducing the sulfur contents of said gasoline cut to very low levels, without reducing the gasoline yield, and by minimizing the reduction in the gasoline index. octane during said process.
  • the invention is particularly applicable when the gasoline to be treated is a cracked gasoline containing a sulfur content greater than 300 ppm by weight or even greater than 500 ppm, and a nitrogen content in general greater than 50 ppm by weight or greater at 100 ppm by weight and preferably above 150 ppm by weight, or even 200 ppm by weight or even more.
  • Future specifications for motor fuels include a significant reduction in the sulfur content of these fuels, including gasoline. This reduction is intended to limit, in particular the content of sulfur oxide and nitrogen in the automobile exhaust gas.
  • Current specifications for sulfur levels are in the order of 150 ppm by weight and will decrease in the coming years to reach levels below 10 ppm after a transition to 30 ppm by weight. The evolution of sulfur content specifications in fuels thus requires the development of new processes for the deep desulphurisation of gasolines.
  • the main sources of sulfur in gasoline bases are the so-called cracking gasoline, and mainly the gasoline fraction resulting from a process for the catalytic cracking of a residue from the atmospheric or vacuum distillation of a crude oil.
  • the gasoline fraction from catalytic cracking which represents on average 40% of gasoline bases, contributes more than 90% to the sulfur input in gasoline. Therefore, the production of low sulfur species requires a step of desulfurization of catalytic cracking gasolines. This desulfurization is conventionally carried out by one or more steps of contacting the sulfur compounds contained in said gasolines with a gas rich in hydrogen in a so-called hydrodesulfurization process.
  • the octane number of such species is very strongly related to their olefin content.
  • the preservation of the octane number of these species therefore requires limiting the conversion reactions of olefins into paraffins which are inherent to hydrodesulfurization processes.
  • the patent US 6,248,230 B1 discloses a method in which the natural polar compounds present in the gasoline fractions having boiling points between 110 and 560 ° C are partially removed by an adsorption process and optionally solvent extraction to improve the catalytic process according to obtaining gasolines with sulfur contents of less than 50 ppm.
  • the present invention for the same olefin saturation rate at the outlet of the reactor and for the same operating temperature of the hydrodesulfurization reactor, it will thus be possible to increase the activity of the catalyst by to a preliminary reduction of the nitrogenous compounds present in the essences.
  • the elimination of basic nitrogen compounds before hydrodesulphurization will limit the degree of saturation of olefins for a fixed sulfur content at the reactor outlet.
  • the present invention finds and particularly its application in the treatment of tree species with a high content of nitrogen compounds.
  • the present desulphurization process provides a solution for achieving high desulphurization rates while limiting the octane loss by hydrogenation of the olefins. This results in the production of a gasoline low in sulfur and high octane.
  • the present invention is a process for the desulfurization of a gasoline feedstock according to claim 1.
  • the denitrogenation treatment is carried out immediately before said contacting (hydrodesulfurization).
  • step e is optionally f
  • said contacting is then performed at least and / or preferably with the heavy fraction from step c).
  • said contacting (hydrodesulfurization) is then carried out at least and / or preferably with the heavy fraction resulting from step c).
  • said contacting is for example carried out in at least two steps e) and f), whatever the embodiment envisaged.
  • said hydrodesulfurization catalyst comprises at least one element of group VIII of the periodic table and advantageously, said hydrodesulfurization catalyst comprises at least one element of group VIB of the periodic table.
  • said group VIII element of the classification is selected from the group consisting of nickel and cobalt and at least at least one group VIB element of the classification selected from the group consisting of molybdenum and tungsten.
  • the conditions of said contacting are as follows: a temperature of between 200 ° C. and 450 ° C., a pressure of between 1 and 3 MPa, a liquid hourly space velocity of between 1 h -1 and 10 h -1 and an H 2 ratio. / HC (hydrogen to hydrocarbon ratio expressed in liters per liter) of between 50 l / l and 500 l / l.
  • the present process is applied to gasoline from catalytic cracking or coking of a hydrocarbon heavy load or steam cracking.
  • the feedstock to be desulphurised is optionally pretreated in a series of reactors for selective hydrogenation of diolefins (step a) and for increasing the weight of light sulfur compounds (step b). .
  • the feedstock thus optionally pretreated is then distilled and fractionated into at least two cuts (step c): a light gasoline low in sulfur and rich in olefins and a heavy gasoline rich in sulfur and depleted in olefins.
  • the light fraction obtained from the preceding three stages generally contains less than 100 ppm of sulfur, preferably less than 50 ppm of sulfur, and very preferably less than 20 ppm of sulfur, and generally does not require any subsequent treatment. before incorporation as a gasoline base.
  • the heavy fraction resulting from the previous three stages, which concentrates most of the sulfur is treated according to the process that is the subject of the present invention. This preferred embodiment presents the advantage of further minimizing the octane loss because light olefins with 5 carbon atoms, easily hydrogenated, are not sent to the hydrodesulfurization section.
  • Step a) is optional and is primarily intended to remove diolefins present in gasoline. This step notably makes it possible to maximize the life of the catalysts used in the downstream stages. Steps b) and c) are also optional, but they allow, if they are carried out before step e), to minimize the octane loss throughout the process.
  • the denitrogenation step d) is carried out before contact with the hydrodesulphurization catalyst (steps e and / or f) or before at least one of steps a), b), and / or c), so that the nitrogen compound content does not exceed 20 ppm (expressed by weight).
  • the method according to the invention comprises at least two steps d) and e). Step d) corresponds to a step of at least partial elimination of the nitrogen contained in the essences, step e) corresponds to a step of hydrotreatment of the thus pretreated gasoline.
  • This optional pre-treatment stage of the gasoline to be desulfurized is intended to at least partially eliminate the diolefins present in the gasoline.
  • the hydrogenation of the dienes is an optional but advantageous step, which makes it possible to eliminate the great majority of the dienes present in the section to be treated before the hydrotreatment.
  • Diolefins are precursors of gums that polymerize in hydrotreating reactors and limit their life span.
  • This step generally takes place in the presence of a catalyst comprising at least one Group VIII metal, preferably selected from the group consisting of platinum, palladium and nickel, and a support.
  • a catalyst comprising at least one Group VIII metal, preferably selected from the group consisting of platinum, palladium and nickel, and a support.
  • a catalyst containing 1 to 20% by weight of nickel deposited on an inert support such as, for example, alumina, silica, silica-alumina, a nickel aluminate or a support containing at least 50% alumina.
  • This catalyst operates at a pressure of 0.4 to 5 MPa, at a temperature of 50 to 250 ° C, with a liquid hourly space velocity of 1 h -1 to 10 h -1 .
  • Another Group VIB metal may be combined to form a bimetallic catalyst, such as, for example, molybdenum or tungsten. This group VIB metal, if it is associated with the Group VIII metal, will be deposited at a level
  • the choice of operating conditions is particularly important.
  • the operation will generally be carried out under pressure in the presence of a quantity of hydrogen in small excess relative to the stoichiometric value necessary for hydrogenating the diolefins.
  • the hydrogen and the feedstock to be treated are injected in ascending or descending streams into a reactor of preferably fixed catalyst bed.
  • the temperature is most generally between 50 and 300 ° C, and preferably between 80 and 250 ° C, and preferably between 120 and 210 ° C.
  • the pressure is most generally 0.4 to 5 MPa and preferably greater than 1 MPa.
  • An advantageous pressure is between 1 to 4 MPa inclusive.
  • the space velocity is, in these conditions of the order of 1 to 12 h -1 , preferably of the order of 4 to 10 h -1 .
  • the light fraction of the catalytic cracking gasoline fraction can contain up to a few% 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 diene content after selective hydrogenation can even be reduced to less than 250 ppm.
  • the step of hydrogenation of the dienes takes place in a catalytic hydrogenation reactor which comprises a catalytic reaction zone traversed preferentially by the totality of the charge and by the quantity of hydrogen necessary to carry out the desired reactions.
  • Some nitrogen compounds are also processed during this step. This is the case, for example, weakly nitrile nitriles which, by hydrogenation, are converted into amines which have a higher basicity.
  • This optional step consists of converting light saturated sulfur compounds, ie compounds whose boiling point is lower than that of thiophene, into saturated sulfur compounds whose boiling point is greater than that of thiophene.
  • These light sulfur compounds are typically mercaptans of 1 to 5 carbon atoms, CS 2 and sulfides comprising 2 to 4 carbon atoms.
  • 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) on a support of alumina, silica or silica-alumina or nickel aluminate type.
  • the choice of the catalyst is carried out in particular so as to promote the reaction between the light mercaptans and the olefins, which leads to mercaptans or sulfides with higher boiling points than thiophene.
  • This optional step may be carried out at the same time as step a), in the same reaction bed and with the same catalyst.
  • 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 mercaptans are converted.
  • the temperatures are generally between 100 and 300 ° C and preferably between 150 and 250 ° C.
  • the H 2 / feed ratio is adjusted between 1 and 20 liters per liter, preferably between 3 and 15 liters per liter.
  • the space velocity is generally between 1 and 10 h -1 , preferably between 2 and 6 h -1 and the pressure between 0.5 and 5 MPa, preferably between 1 and 3 MPa.
  • Nitrogen compounds present in gasoline are also partly weighed down during this stage.
  • the nitrogen compounds present in the PI fraction (initial point) -60 ° C. were converted into heavier nitrogen compounds with a boiling point greater than 60 ° C.
  • Step b) thus makes it possible to separate a part of the nitrogenous compounds from the fraction PI-60 ° C.
  • This separation is preferably carried out by means of a conventional distillation column.
  • 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.
  • the light gasoline obtained after the separation generally contains at least all of the five-carbon olefins, preferably the five-carbon compounds and at least 20 percent of the six-carbon olefins.
  • this light fraction obtained after steps a) and b) has a low sulfur content, ie it is not generally necessary to treat the light cut before using it as fuel.
  • the nitrogen compounds present in the essences belong mainly to the following families: nitriles, amines, pyroles, pyridines and anilines. These compounds are generally present in the range of from 20 to 400 ppm in gasolines. These compounds are for the most part basic, they are eliminated by separation in an acid medium.
  • the nitrogen removal step in the gasolines therefore consists in washing the gasoline with an aqueous solution containing an acidic compound.
  • the acids used are phosphoric acid, sulfuric acid, hydrochloric acid or formic acid. Any type of acid soluble in water and whose acidity is sufficient to protonate nitrogen can be used for this operation. This operation is performed by contacting the gasoline to be treated with the acid, for example, in a washing column. The washing conditions are optimized so that the recovered gasoline contains less than 20 ppm.
  • An advantageous embodiment of the invention consists in carrying out step a) before step d). Indeed, certain nitrogen compounds such as nitriles are converted during step a) to form the corresponding amines.
  • the reaction observed is as follows: CH3-CH2-CN + 2 H 2 ⁇ CH 3 CH 2 CH 2 -NH 2
  • Amines being more basic than nitriles, their extraction during step d) will be facilitated.
  • the hydrodesulfurization step (step e) consists in passing the gasoline to be treated in the presence of hydrogen, on a hydrodesulfurization catalyst, at a temperature of between 200 ° C. and 350 ° C., preferably between 250 ° C. C and 320 ° C and at a pressure of between 1 and 3 MPa, preferably between 1.5 and 2.5 MPa.
  • the liquid space velocity is generally between 1 h -1 and 10 h -1 , preferably between 2 h -1 and 5 h -1
  • the H 2 / H 2 ratio is between 50 liters / liter (1 / l) and 500 l / l, preferably between 100 l / l and 450 l / l, and more preferably between 150 l / l and 400 l / l.
  • the ratio H 2 / HC is the ratio between the hydrogen flow rate under 1 atmosphere and 0 ° C and the hydrocarbon flow rate. Under these conditions, the reaction takes place in the gas phase. The operating conditions during this step are therefore adjusted according to the characteristics of the feedstock to be treated to achieve a desired desulfurization rate.
  • the effluents resulting from this hydrodesulfurization step are partially desulfurized gasoline, residual hydrogen and H 2 S produced by decomposition of the sulfur compounds.
  • the catalysts used in step e) comprise at least one group VIII element and / or at least one group VIB element on a suitable support.
  • 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 group VIII element, when present, is preferably cobalt, and the group VIB element, when present, is usually molybdenum or tungsten.
  • 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 molybdenum density expressed in% by weight of MoO 3 per unit area, is greater than 0.07 and preferably greater than 0.07. at 0.10.
  • the catalyst according to the invention preferably has a specific surface area of less than 200 m 2 / g, more preferably less than 180m 2 / g, and very preferably less than 150 m 2 / g.
  • the catalyst is preferably used at least in part in its sulfurized form.
  • 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.
  • Sulfurization consists of 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 hydrodesulfurization step e) may be followed by an additional step to improve the final desulfurization rate. This step is necessarily performed after step e) and can be carried out with or without intermediate removal of H 2 S.
  • Step f) comprises at least one step of decomposition of saturated sulfur compounds from step e). These sulfur compounds are converted to H 2 S on a catalyst and under conditions such that the olefins are very little hydrogenated.
  • the degree of hydrogenation (saturation) of the olefins in this step is generally less than 20%, and preferably less than 10%.
  • This hydrodesulfurization step (step f) generally consists in passing the gasoline to be treated in the presence of hydrogen, on a hydrodesulfurization catalyst, at a temperature of between 250 ° C. and 450 ° C., preferably between 300 ° C. C and 360 ° C and at a pressure of between 1 and 3 MPa, preferably between 1.5 and 2.5 MPa.
  • the liquid space velocity is generally between 1 h -1 and 10 h -1 , preferably between 1 h -1 and 5 h -1
  • the H 2 / H 2 ratio is between 50 liters / liter (l / l) and 500 l / l, preferably between 100 l / l and 450 l / l, and more preferably between 150 l / l and 400 l / l.
  • the reaction takes place in the gas phase.
  • the operating conditions during this step are therefore adjusted according to the characteristics of the feedstock to be treated to achieve a desired desulfurization rate.
  • the catalyst used in step e) comprises at least one group VIII element selected from the group consisting of nickel, cobalt, iron, molybdenum and tungsten.
  • the metal content of group VIII expressed as oxide is generally between 1 and 60% by weight, preferably between 1 and 40% by weight.
  • 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 between 25 and 350 m 2 / g.
  • the catalyst is preferably used at least in part in its sulfurized form.
  • 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.
  • Sulfurization consists of 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.
  • Example 1 The interest and advantages of the present invention are demonstrated by the comparison of Example 1 according to the prior art, and of Example 2, according to the invention.
  • Example 1 relates to a desulfurization process without preliminary elimination of nitrogen.
  • a hydrodesulphurization catalyst A is obtained by impregnation of a transition alumina in the form of beads having a specific surface area of 130 m 2 / g and a pore volume of 1.04 m 2 / g, by an 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 sample is 3% CoO and 10% MoO 3 .
  • Catalyst A 100 ml of Catalyst A are placed in a fixed-bed tubular hydrodesulfurization reactor.
  • the catalyst is first sulphurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C., in contact with a feedstock consisting of 2% of sulfur in the form of dimethyl disulphide in n-heptane.
  • the treated feedstock is a catalytic cracking gasoline boiling point of 50 ° C and end point of 225 ° C. Its sulfur content is 1450 ppm by weight and its bromine number (IBr) is 69 g / 100 g.
  • This gasoline has a nitrogen content of 180 ppm of nitrogen including 165 ppm of basic nitrogen (basic nitrogen is understood to mean nitrogen included in compounds comprising a nitrogen group having a basic character). The total nitrogen is assayed by the ASTM4629 method, and the basic nitrogen is assayed by the ASTM4739 method.
  • This feedstock is treated on catalyst A at a pressure of 2 MPa, a H 2 / HC ratio of 300 l / l and a WH of 2 h -1 .
  • Table 1 shows the influence of temperature on the desulfurization and saturation rates of olefins.
  • Table 1 Temperature (° C) Sulfur content of desulphurized gasoline (ppm by weight) Desulfurization rate (HDS -%) IBr of desulphurized gasoline (g / 100 g) Saturation rate of olefins (HDO -%) 280 292 79.9 49.2 28.7 290 165 88.6 45.6 33.9 300 108 92.6 38.97 43.6
  • the sulfur content of the effluent is thus greater than 100 ppm for an olefin saturation of nearly 44%.
  • Example 2 is carried out according to the invention, that is to say that the basic nitrogen compounds are mainly removed during an acidic washing step, before the desulfurization step.
  • the treated feedstock is the same as that of Example 1.
  • This feed contains 180 ppm of nitrogen including 165 ppm of basic nitrogen.
  • 50 kg of this gasoline is mixed, in a batch reactor (or batch according to the English term), to 100 kg of a sulfuric acid solution concentrated to 10% by weight in distilled water. The mixture is stirred for 15 minutes and then left to decant. The aqueous phase which is found in the lower part of the reactor is withdrawn. The remaining gasoline is washed with 50 kg of distilled water. After decantation, the water is separated from the gasoline.
  • the gasoline thus produced has a nitrogen content of 12 ppm including 0 ppm of basic nitrogen.
  • Example 1 The reactor used in Example 1 is loaded with fresh catalyst and sulfide according to the same procedure as Example 1.
  • This feedstock is treated on catalyst A at a pressure of 2 MPa, a H 2 / HC ratio of 300 l / l and a WH of 2 h -1 .
  • the operating conditions applied for Example 2 are identical to the operating conditions of Example 1.
  • Table 2 shows the influence of temperature on the olefin desulphurization and saturation rates.
  • Table 2 Temperature (° C) Sulfur content of desulphurized gasoline (ppm by weight) Desulfurization rate (HDS -%) IBr of desulphurized gasoline (g / 100 g) Saturation rate of olefins (HDO -%) 280 160 89.0 48.2 30.1 290 97 93.3 43.1 37.5 300 59 95.9 37.4 45.8
  • the desulfurization rate achieved by the process according to the invention is higher than that of Example 1.
  • the saturation levels of the olefins are comparable.
  • a desulfurization process carried out according to the invention makes it possible to increase the selectivity of the catalyst used: the losses in olefins and thus in octane number (measured at constant desulfurization rate) are lower when the At least part of the gasoline is freed of nitrogen compounds before desulphurization than when it is treated directly.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (10)

  1. Verfahren zur Entschwefelung einer Benzincharge durch einen Hydroentschwefelungskatalysator, bei dem die Charge vom katalytischen Cracken oder von der Verkokung einer schweren Kohlenwasserstoffcharge oder einem Dampfcracken stammt und mindestens 150 Gewichts-ppm an Schwefelverbindungen umfasst, bei dem die Charge einer vorherigen Entstickungsbehandlung unterzogen wird, die in einem Waschen des Benzins mit einer wässrigen Lösung, die eine saure Verbindung enthält, besteht, wobei diese Entstickungsbehandlung unter solchen Bedingungen durchgeführt wird, dass der Gehalt an Stickstoffverbindungen, die in der Charge zum Zeitpunkt der Kontaktierung mit dem Hydroentschwefelungskatalysator vorhanden ist, 20 Gewichts-ppm nicht überschreitet, und bei dem die Kontaktnahme mit dem Hydroentschwefelungskatalysator bei einer Temperatur zwischen 200 °C und 450 °C unter einem Druck zwischen 1 und 3 MPa, bei einer Raumgeschwindigkeit der Flüssigkeit pro Stunde zwischen 1 h-1 und 10 h-1 und mit einem Verhältnis H2/HC zwischen 50 1/1 und 500 1/1 erfolgt.
  2. Verfahren nach Anspruch 1, bei dem die vorherige Entstickungsbehandlung unmittelbar vor der Kontaktierung erfolgt.
  3. Verfahren nach Anspruch 1, bei dem mindestens ein Schritt, der in folgender Gruppe ausgewählt ist:
    a) selektive Hydrierung der in der Charge enthaltenen Diene,
    b) Umwandlung der in der Charge enthaltenen leichten Schwefelverbindungen,
    c) Trennung der Charge in mindestens zwei Fraktionen, darunter:
    - eine leichte Fraktion, die einen kleinen Teil der Schwefelverbindungen enthält,
    - eine schwere Fraktion, die den Großteil der Schwefelverbindungen enthält,
    zwischen der Entstickungsbehandlung (Schritt d) und der Kontaktierung mit dem Hydroentschwefelungskatalysator (Schritte e und eventuell f) durchgeführt wird.
  4. Verfahren nach Anspruch 3, bei dem die Kontaktierung mindestens mit der aus Schritt c) stammenden schweren Fraktion erfolgt.
  5. Verfahren nach Anspruch 2, bei dem mindestens ein Schritt, der in folgender Gruppe ausgewählt ist:
    a) selektive Hydrierung der in der Charge enthaltenen Diene,
    b) Umwandlung der in der Charge enthaltenen leichten Schwefelverbindungen,
    c) Trennung der Charge in mindestens zwei Fraktionen, darunter:
    - eine leichte Fraktion, die einen kleinen Teil der Schwefelverbindungen enthält,
    - eine schwere Fraktion, die den Großteil der Schwefelverbindungen enthält,
    vor der Entstickungsbehandlung (Schritt d) durchgeführt wird.
  6. Verfahren nach Anspruch 5, bei dem die Kontaktierung mit dem Hydroentschwefelungskatalysator mindestens mit der aus Schritt c) stammenden schweren Fraktion erfolgt.
  7. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Kontaktierung in mindestens zwei Schritten e) und f) erfolgt.
  8. Verfahren nach einem der vorhergehenden Ansprüche, bei dem der Hydroentschwefelungskatalysator mindestens ein Element der Gruppe VIII des Periodensystems umfasst.
  9. Verfahren nach einem der vorhergehenden Ansprüche, bei dem der Hydroentschwefelungskatalysator mindestens ein Element der Gruppe VIB des Periodensystems umfasst.
  10. Verfahren nach Anspruch 8 oder 9, bei dem der Katalysator mindestens ein Element der Gruppe VIII des Periodensystems umfasst, ausgewählt aus der Gruppe, die von Nickel und Kobalt gebildet ist, und mindestens ein Element der Gruppe VIB des Periodensystems umfasst, ausgewählt aus der Gruppe, die von Molybdän und Wolfram gebildet ist.
EP03291317.0A 2002-06-07 2003-06-02 Herstellungsverfahren von Kohlenwasserstoffen mit niedrigem Gehalt von Schwefel und von Stickstoff Expired - Lifetime EP1369468B1 (de)

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Application Number Priority Date Filing Date Title
FR0207054A FR2840620B1 (fr) 2002-06-07 2002-06-07 Procede de production d'hydrocarbures a faible teneur en soufre et en azote
FR0207054 2002-06-07

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EP1369468A1 EP1369468A1 (de) 2003-12-10
EP1369468B1 true EP1369468B1 (de) 2017-10-04

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US (1) US20040035752A1 (de)
EP (1) EP1369468B1 (de)
JP (1) JP4834285B2 (de)
CN (1) CN100343369C (de)
BR (1) BR0301675A (de)
FR (1) FR2840620B1 (de)

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JP4834285B2 (ja) 2011-12-14
EP1369468A1 (de) 2003-12-10
JP2004010897A (ja) 2004-01-15
CN1475550A (zh) 2004-02-18
FR2840620B1 (fr) 2004-07-30
BR0301675A (pt) 2004-08-24
FR2840620A1 (fr) 2003-12-12
CN100343369C (zh) 2007-10-17

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