EP1002853B1 - Verfahren zur Herstellung von Benzin mit niedrigem Schwefelgehalt - Google Patents

Verfahren zur Herstellung von Benzin mit niedrigem Schwefelgehalt Download PDF

Info

Publication number
EP1002853B1
EP1002853B1 EP99402792A EP99402792A EP1002853B1 EP 1002853 B1 EP1002853 B1 EP 1002853B1 EP 99402792 A EP99402792 A EP 99402792A EP 99402792 A EP99402792 A EP 99402792A EP 1002853 B1 EP1002853 B1 EP 1002853B1
Authority
EP
European Patent Office
Prior art keywords
gasoline
fraction
light
process according
catalyst
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.)
Expired - Lifetime
Application number
EP99402792A
Other languages
English (en)
French (fr)
Other versions
EP1002853A1 (de
Inventor
Blaise Didillon
Denis Uzio
Jean-Luc Nocca
Jean Cosyns
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Original Assignee
IFP Energies Nouvelles IFPEN
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by IFP Energies Nouvelles IFPEN filed Critical IFP Energies Nouvelles IFPEN
Publication of EP1002853A1 publication Critical patent/EP1002853A1/de
Application granted granted Critical
Publication of EP1002853B1 publication Critical patent/EP1002853B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
    • 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
    • C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps

Definitions

  • the present invention relates to a process for the production of gasolines with a low sulfur content, which makes it possible to recover the totality of a petrol fraction containing sulfur, to reduce the total sulfur and mercaptan contents of said petrol fraction to very low levels. levels, with no significant decrease in fuel efficiency, and minimizing the decrease in octane number.
  • the production of reformulated species that meet the new environmental standards requires, in particular, that their concentration of olefins and / or aromatics (especially benzene) and sulfur (including mercaptans) be reduced.
  • the catalytic cracking gasolines have high olefin contents, and the sulfur present in the reformulated gasoline is attributable, to nearly 90%, to catalytic cracking gasoline (FCC). in a fluidized bed).
  • FCC catalytic cracking gasoline
  • the desulphurisation (hydrodesulphurisation) of gasolines and mainly of FCC species is therefore of obvious importance.
  • Hydrotreating (hydrodesulphurisation) of the feedstock sent to catalytic cracking leads to gasolines typically containing 100 ppm of sulfur.
  • the hydrocracking units of catalytic cracking feeds operate in severe conditions of temperature and pressure, which assumes a major investment effort.
  • the entire charge must be desulfurized, resulting in the processing of very large load volumes.
  • EP-A-0 725 126 discloses a method for hydrodesulphurizing a cracking gasoline in which the gasoline is separated into a plurality of fractions comprising at least a first fraction rich in compounds easy to desulphurize and a second fraction. rich in compounds difficult to desulphurize. Before carrying out this separation, it is necessary to first determine the distribution of the sulfur-containing products by means of analyzes. These analyzes are necessary to select the equipment and the separation conditions.
  • US-A-5,318,690 discloses a process with gasoline fractionation and softening of the light fraction, while the heavy fraction is desulfurized, then converted to ZSM-5 and desulfurized again under mild conditions. This technique is based on a separation of crude gasoline so as to obtain a light cut practically 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 heavy cut contains a relatively large amount of olefins which are partly saturated during hydrotreatment.
  • the patent advocates cracking zeolite ZSM-5 which produces olefins, but at the expense of yield.
  • these olefins can recombine with H 2 S present in the medium to reform mercaptans. It is then necessary to perform additional softening or hydrodesulfurization.
  • the present invention relates to a process for the production of gasolines with a low sulfur content, which makes it possible to recover the totality of a petrol fraction containing sulfur, to reduce the total sulfur and mercaptan contents of said petrol fraction to very low levels. levels, with no significant decrease in fuel efficiency, and minimizing the decrease in octane number.
  • the process according to the invention is a process for the production of gasoline with a low sulfur content from a petrol cut containing sulfur.
  • the method according to the invention comprises a separation of said essence into a light fraction and a heavy fraction, hydrodesulfurization of the light gasoline on a nickel-based catalyst, hydrodesulfurization of the heavy fraction on a catalyst comprising at least cobalt and / or at least one Group VIb metal, and the mixture of the desulphurized fractions.
  • 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 having 5 carbon atoms (C5) up 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.
  • the process according to the invention comprises a separation of the essence into two fractions: a light fraction (also hereinafter referred to as light cut or light gasoline), the end point of which is generally less than or equal to approximately 160 ° C., preferably lower at 140 ° C and more preferably below 120 ° C, a heavy fraction (also hereinafter referred to as heavy cut or heavy gasoline) which is constituted by the heavy fraction complementary to the light gasoline.
  • a light fraction also hereinafter referred to as light cut or light gasoline
  • heavy fraction also hereinafter referred to as heavy cut or heavy gasoline
  • the cutting point is chosen so as to maximize the olefin content in the light cut.
  • This content can be easily determined, for example by means of the determination of the bromine number, generally available on the site.
  • hydrodesulphurization also called hydrotreatment
  • hydrodesulphurization of the light gasoline is carried out on a nickel-based catalyst described in a patent application filed simultaneously, and the hydrodesulphurization of the heavy fraction on a conventional hydrotreatment (hydrodesulfurization) catalyst comprising a Group VIII metal and a Group VIb metal.
  • the light and heavy cuts thus desulfurized are then mixed.
  • the effluent obtained may optionally be stripped in order to remove the H 2 S produced during the hydrodesulfurization.
  • the gas to be desulphurized contains polyolefins (dienes), to perform a selective hydrogenation of the gasoline before fractionation.
  • the sulfur species contained in the feedstocks treated by the process of the invention may be mercaptans or heterocyclic compounds, such as, for example, thiophenes or alkylthiophenes, or heavier compounds, for example benzothiophene.
  • heterocyclic compounds unlike mercaptans, can not be removed by the extractive processes. These sulfur compounds are consequently eliminated by hydrotreatment, which leads to their decomposition into hydrocarbons and H 2 S.
  • sulfur compounds whose boiling points are below 160 ° C or even below 140 ° C and preferably below 120 ° C.
  • the sulfur content of catalytic cracked gasoline (FCC) gasoline cuts depends on the sulfur content of the FCC treated feed as well as the end point of the cut. Light fractions naturally have a lower sulfur content than heavier cuts.
  • the sulfur contents of the entirety of a petrol cut 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, they can even in certain cases reach values of the order of 4000 to 5000 ppm by weight.
  • the hydrogenation of the dienes is an optional but advantageous step which makes it possible to eliminate, before hydrodesulphurization, almost all the dienes present in the petrol fraction containing sulfur to be treated. It 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 or a support containing at least 50% alumina, will be used. .
  • 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 to 10 h -1 .
  • Another metal may be combined to form a bimetallic catalyst, such as, for example, molybdenum or tungsten.
  • 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 preferably with a fixed bed of catalyst.
  • the temperature is most generally between about 50 and about 250 ° C, and preferably between 80 and 200 ° C, and more preferably between 160 and 190 ° C.
  • the pressure is sufficient to maintain more than 80%, and preferably more than 95% by weight of the gasoline to be treated in the liquid phase in the reactor; it is most generally between 0.4 and 5 MPa and preferably greater than 1 MPa.
  • the pressure is advantageously between 1 and 4 MPa.
  • the space velocity is from about 1 to about 10 h -1 , preferably from 4 to 10 h -1 .
  • the light fraction of the catalytic cracking gasoline fraction can contain up to a few% by weight of diolefins.
  • 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 step of hydrogenation of the dienes takes place in a catalytic hydrogenation reactor which comprises a catalytic reaction zone traversed by the entire charge and the amount of hydrogen necessary to effect the desired reactions. .
  • This step consists of splitting the gasoline into two fractions, a light fraction, also called light gasoline, and a heavy fraction also called heavy gasoline.
  • the cutting point between these two species corresponds to the point final boiling point (also known as the end point) of light gasoline, and the initial boiling point (also known as the initial point) of heavy gasoline. It is at a temperature generally below 160 ° C in terms of boiling point, preferably below 140 ° C, and more preferably below 120 ° C.
  • the light gasoline thus has an end point (cutting point between the light fraction and the heavy fraction) generally greater than or equal to about 160 ° C, preferably greater than 140 ° C and more preferably greater than 120 ° C.
  • Heavy gasoline is the heavy fraction complementary to light gasoline. It has an initial point generally greater than or equal to approximately 160 ° C, preferably greater than 140 ° C and more preferably greater than 120 ° C.
  • This separation can be carried out using any techniques known to those skilled in the art, such as, for example, distillation or adsorption.
  • the end point of the light gasoline cut depends of course on the refinery, but remains within the limits indicated above.
  • the filler is preferably a light gasoline derived from the separation of a catalytic cracking gasoline.
  • Suitable catalysts are catalysts consisting of supported nickel.
  • the nickel content of the catalyst used according to the invention is generally between about 1 and about 80% by weight, preferably between 5 and 70% by weight and even more preferably between 10 and 50% by weight.
  • the catalyst is generally shaped, preferably in the form of beads, extrudates, pellets, or trilobes.
  • the nickel may be incorporated in the catalyst on the preformed support, it may also be mixed with the support before the shaping step.
  • Nickel is generally introduced in the form of a precursor salt, generally soluble in water, such as, for example, nickel nitrate. This mode of introduction is not specific to the invention. Any other mode of introduction known to those skilled in the art is suitable for the invention
  • the supports of the catalysts used in the process of the invention are generally porous solids chosen from refractory oxides, such as, for example, aluminas, silicas and silica-aluminas, magnesia, as well as titanium oxide and zinc oxide, the latter oxides may be used alone or in admixture with alumina or silica-alumina.
  • the supports are transition aluminas or silicas whose specific surface area is between 25 and 350 m 2 / g.
  • the supports chosen from natural compounds for example kieselguhr or kaolin may also be suitable as supports for the catalysts of the process according to the invention.
  • the catalyst After introducing the nickel and possibly forming the catalyst (when this step is carried out on a mixture already containing nickel), the catalyst is in a first activated step.
  • This activation may correspond to either an oxidation, then a reduction, or 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 nickel to metal. Generally, it consists of treating the catalyst under a flow of hydrogen at a temperature 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. This has the advantage of minimizing the risks of hydrogenation of unsaturated compounds such as olefins or aromatic compounds during the start-up phase.
  • the introduction of sulfur can occur between different activation steps. Preferably, no oxidation step is performed when the sulfur or a sulfur compound is 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. In the latter case, the catalyst is preferably reduced under the conditions described above, then sulphurized 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 of the invention.
  • the catalyst is then treated in hydrogen in order to convert at least a portion of the nickel into sulfide.
  • a procedure which is particularly suitable for the invention is that described in patents FR-B-2,708,596 and FR-B-2,708,597.
  • the sulfur content of the catalyst is generally between 0.5 and 25% by weight, preferably between 4 and 20% by weight.
  • the hydrodesulphurization of the light fraction of gasoline is intended, by using the catalyst described above, to convert the sulfur-containing compounds of the cut into H 2 S, so as to obtain an effluent, which after mixing with the Desulfurized heavy gasoline will meet the desired specifications in terms of sulfur compound content.
  • the light cut produced has the same distillation range and a slightly lower octane number, due to the partial but inevitable saturation of the olefins.
  • the operating conditions of the hydrotreatment reactor according to the present invention must be adjusted so as to reach the desired level of hydrodesulfurization, and in order to minimize the octane loss resulting from the saturation of the olefins.
  • the catalyst used in the process according to the invention generally makes it possible to convert at most 70% of the olefins, preferably at most 60-65% of the olefins, and more preferably less than 20% of the olefins (the diolefins being totally or almost totally hydrogenated). ). With the catalyst of the process according to the invention, it is thus possible to achieve high levels of hydrodesulphurization while limiting the loss of olefins and therefore the reduction of the octane number.
  • the hydrodesulfurization of the light fraction is carried out in the presence of hydrogen, with the nickel-based catalyst having a temperature of between about 160 ° C and about 420 ° C, at low to moderate pressure, generally between about 0.5 and about 8 MPa.
  • the space velocity of the liquid is between about 0.5 and about 10 h -1 (expressed as volume of liquid per volume of catalyst per hour), preferably between 1 and 8 h -1 .
  • the H 2 / HC ratio is adjusted according to the desired hydrodesulphurization rates in the range of from about 100 to about 600 liters per liter.
  • the temperature is between 200 ° C and 400 ° C, and very preferably between 290 ° C and 350 ° C.
  • the pressure is between 1 and 3 MPa.
  • the fraction corresponding to heavy gasoline is subjected to conventional hydrotreatment (hydrodesulphurization) carried out on a conventional hydrotreating catalyst in order to convert the sulfur-containing compounds of the cut into H 2 S, and so as to obtain an effluent, after mixing with the light desulfurized gasoline, which meets the desired specifications in terms of content of sulfur compounds.
  • hydrotreatment hydrodesulphurization
  • the heavy fraction thus desulphurized has the same distillation range and a slightly lower octane number than before hydrotreatment, because of the total saturation of the olefins. This loss of octane is limited because the heavy fraction (heavy gasoline) has an olefin content generally less than 20% by weight and preferably less than 10% by weight.
  • the operating conditions of the hydrotreating reactor according to the present invention must be adjusted to await the desired level of desulfurization. At least 90% of the sulfur compounds present in heavy gasoline are generally converted to H 2 S.
  • the heavy fraction is hydrotreated in the presence of hydrogen with a catalyst consisting of cobalt and at least one Group VIb metal supported at a temperature of from about 160 ° C to about 420 ° C under generally from about 0.5 to about 8 MPa.
  • the space velocity of the liquid is between about 0.5 and about 10 h -1 (expressed as volume of liquid per volume of catalyst per hour), preferably between 1 and 6 h -1 .
  • the H 2 / HC ratio is adjusted according to the desired desulfurization rates in the range of 100 to 600 liters per liter and preferably 300 to 600 liters per liter.
  • the temperature is between 200 ° C and 300 ° C.
  • the pressure is between 2 and 4 MPa.
  • At least one conventional hydrodesulphurization catalyst comprising cobalt and at least one metal from group VIb (Group 6 metals).
  • group VIb Group 6 metals
  • the metal of group Vlb 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.
  • Each of the two fractions is then subjected to hydrodesulfurization, under the conditions described above, in order to eliminate almost completely the sulfur of the heavy fraction and to eliminate a part of the sulfur present in the light fraction, preferably limiting to to reach the sulfur content necessary for the product obtained by mixing the two hydrodesulphurized sections has a sulfur content corresponding to the desired specifications.
  • reaction zones where the hydrodesulphurization reactions of the light and heavy gasoline fractions are carried out outside the distillation zone, but to use reaction zones as feedstock.
  • hydrodesulphurizing the liquid fractions taken from trays in the distillation zone with recycling of the desulphurized effluents to said distillation zone, at one or more levels above or below, preferably in the vicinity, of the sampling levels.
  • Example 1 hydrodesulphurization of unfractionated gasoline.
  • HR306C® catalyst marketed by the company Procatalyse
  • 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.
  • Example 2 hydrodesulphurization of fractionated gasoline.
  • the heavy fraction of the gasoline is subjected to hydrodesulfurization on a conventional hydrotreating catalyst in an isothermal tubular reactor.
  • 25 ml of HR306C® catalyst, marketed by the company Procatalyse, are placed in the 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 light fraction of the gasoline is subjected to hydrotreatment on a supported nickel catalyst in an isothermal tubular reactor.
  • the catalyst is prepared as follows.
  • the catalyst is prepared from a transition alumina of 140 m 2 / g in the form of beads 2 mm in diameter.
  • the pore volume is 1 ml / g of support.
  • 1 kilogram of support is impregnated with 1 liter of nickel nitrate solution.
  • the catalyst is then dried at 120 ° C and calcined under a stream of air at 400 ° C for one hour.
  • the nickel content of the catalyst is 20% by weight.
  • the catalyst (100 ml) is then sulphurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C. in contact with a filler containing 4% sulfur as dimethyl disulphide in n-heptane.
  • the hydrodesulfurization of the light gasoline is then carried out.
  • the temperature is 280 ° C
  • the charge rate is 200 ml / hour.
  • the H 2 / charge ratio expressed in liters of hydrogen per liter of filler is 400, the operating pressure is 2.7 MPa.
  • Example 3 hydrodesulphurization of fractionated gasoline using a cobalt-molybdenum catalyst.
  • the heavy fraction of the gasoline is subjected to hydrodesulfurization on a conventional hydrotreating catalyst in an isothermal tubular reactor.
  • 25 ml of HR306C® catalyst, marketed by the company Procatalyse, are placed in the 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 light fraction of the gasoline is subjected to hydrodesulfurization on the HR306C® catalyst in an isothermal tubular 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.
  • Table 7 Hydrodesulfurization of light gasoline over HR 306CP catalyst Light petrol Lightly desulphurated gasoline S total (ppm) 1600 700 S ex mercaptans (ppm) 0 250 Olefins (% vol.) 46 36 Initial point (° C) 80 80 End point (° C) 110 110

Landscapes

  • Chemical & Material Sciences (AREA)
  • 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)
  • Catalysts (AREA)

Claims (8)

  1. Verfahren zur Herstellung von Benzin mit niedrigem Schwefelgehalt, bei dem das Verfahren umfasst:
    - Separation von Benzin, das Schwefel in einer leichten Fraktion und einer schweren Fraktion enthält, wobei der Trennpunkt so ausgewählt ist, dass die leichte Fraktion den größten Teil der Olefine des Zulaufs einschließt und die schwere Fraktion einen Olefingehalt unter 20 Gew.-% aufweist,
    - Hydrodesulfurierung der leichten Fraktion auf einem Katalysator, der aus einem Nickelträger besteht,
    - Hydrodesulfurierung der schweren Fraktion auf einem Katalysator, der aus einem Cobaltträger und mindestens einem Metallträger der Gruppe VIb besteht, und
    - Vermischen der entschwefelten Fraktionen.
  2. Verfahren nach Anspruch 1, in dem das Benzin, das Schwefel enthält, aus einem katalytischen Krackverfahren hervorgegangen ist.
  3. Verfahren nach Anspruch 1 oder 2, in dem das Metall der Gruppe VIb Molybden oder Tungsten ist.
  4. Verfahren nach einer der vorstehenden Ansprüche, in dem, vor der Separation, eine Hydrogenierung der Diene durchgeführt wird, die in dem Benzinanteil vorhanden sind, der Schwefel enthält.
  5. Verfahren nach einem der vorstehenden Ansprüche, in dem der Trennpunkt zwischen der leichten Fraktion und der schweren Fraktion bei einer Temperatur unterhalb von 160 °C liegt.
  6. Verfahren nach einem der vorstehenden Ansprüche, in dem die Hydrodesulfurierung der leichten Fraktion und die Hydrodesulfurierung der schweren Fraktion in Gegenwart von Wasserstoff bei einer Temperatur zwischen 160 °C und 420 °C, unter einem Druck zwischen etwa 0,5 und etwa 8 MPa, mit einer Raumgeschwindigkeit der Flüssigkeit zwischen etwa 0,5 und etwa 10 h-1 und einem Verhältnis H2/HC zwischen etwa 100 und etwa 600 Litern je Liter durchgeführt werden.
  7. Verfahren nach einem der vorstehenden Ansprüche, in dem die Separation in einer Destillationssäule durchgeführt wird, und in dem die Zuläufe der Hydrodesulfurierungsreaktoren auf zwei verschiedenen Ebenen der Säule entnommen werden und die abfließenden Medien aus den Reaktoren in die Säule zurückgeschickt werden.
  8. Verfahren nach einem der vorstehenden Ansprüche, in dem die Separation in einer Destillationssäule ausgeführt wird und in dem die Hydrodesulfurierungskatalysatoren im Innern dieser Säule platziert sind.
EP99402792A 1998-11-18 1999-11-09 Verfahren zur Herstellung von Benzin mit niedrigem Schwefelgehalt Expired - Lifetime EP1002853B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9814480A FR2785908B1 (fr) 1998-11-18 1998-11-18 Procede de production d'essences a faible teneur en soufre
FR9814480 1998-11-18

Publications (2)

Publication Number Publication Date
EP1002853A1 EP1002853A1 (de) 2000-05-24
EP1002853B1 true EP1002853B1 (de) 2006-06-14

Family

ID=9532861

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99402792A Expired - Lifetime EP1002853B1 (de) 1998-11-18 1999-11-09 Verfahren zur Herstellung von Benzin mit niedrigem Schwefelgehalt

Country Status (8)

Country Link
US (1) US6334948B1 (de)
EP (1) EP1002853B1 (de)
JP (1) JP4547745B2 (de)
KR (1) KR100626623B1 (de)
CN (1) CN1158378C (de)
DE (1) DE69931876T2 (de)
ES (1) ES2267238T3 (de)
FR (1) FR2785908B1 (de)

Families Citing this family (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6649043B1 (en) 1996-08-23 2003-11-18 Exxonmobil Research And Engineering Company Regeneration of hydrogen sulfide sorbents
FR2797639B1 (fr) * 1999-08-19 2001-09-21 Inst Francais Du Petrole Procede de production d'essences a faible teneur en soufre
US6596157B2 (en) * 2000-04-04 2003-07-22 Exxonmobil Research And Engineering Company Staged hydrotreating method for naphtha desulfurization
FR2811328B1 (fr) * 2000-07-06 2002-08-23 Inst Francais Du Petrole Procede comprenant deux etapes d'hydrodesulfuration d'essence et une elimination intermediaire de l'h2s forme au cours de la premiere etape
US6610197B2 (en) * 2000-11-02 2003-08-26 Exxonmobil Research And Engineering Company Low-sulfur fuel and process of making
KR100559965B1 (ko) * 2000-11-17 2006-03-13 닛끼 가부시끼가이샤 경유유분의 탈황방법, 탈황경유 및 경유유분의 탈황장치
US7090767B2 (en) * 2002-05-02 2006-08-15 Equistar Chemicals, Lp Hydrodesulfurization of gasoline fractions
JP2006500202A (ja) * 2002-09-23 2006-01-05 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ 触媒粒子及びその脱硫への使用法
JP2006512434A (ja) * 2002-12-30 2006-04-13 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ 洗剤の製造方法
CN1312257C (zh) * 2003-01-30 2007-04-25 中国石油化工股份有限公司 一种降低汽油中烯烃、硫含量的方法
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
FR2857975B1 (fr) * 2003-07-25 2008-01-11 Inst Francais Du Petrole Procede de disulfuration des essences
CN1313576C (zh) * 2003-09-15 2007-05-02 中国石油化工股份有限公司 一种劣质汽油加氢处理方法
CN1313575C (zh) * 2003-09-15 2007-05-02 中国石油化工股份有限公司 一种劣质汽油加氢改质方法
US7341657B2 (en) 2003-12-22 2008-03-11 China Petroleum & Chemical Corporation Process for reducing sulfur and olefin contents in gasoline
EP1702045A4 (de) * 2003-12-23 2011-08-17 China Petroleum & Chemical Verfahren zur verringerung des schwefel- und olefingehalts in benzin
CN100478425C (zh) * 2004-07-29 2009-04-15 中国石油化工股份有限公司 一种柴油馏分的改质方法
FR2900157B1 (fr) 2006-04-24 2010-09-24 Inst Francais Du Petrole Procede de desulfuration d'essences olefiniques comprenant au moins deux etapes distinctes d'hydrodesulfuration
CN101089130B (zh) * 2006-06-16 2010-10-27 中国石油化工股份有限公司 一种生产低硫汽油的方法
CN101191079B (zh) * 2006-11-21 2011-03-23 中国石油化工股份有限公司上海石油化工研究院 用于全馏分裂解汽油选择性加氢的方法
US7842181B2 (en) * 2006-12-06 2010-11-30 Saudi Arabian Oil Company Composition and process for the removal of sulfur from middle distillate fuels
CN101307255B (zh) * 2007-05-18 2011-12-21 中国石油化工股份有限公司 一种劣质汽油馏分生产低硫汽油的方法
JP5431656B2 (ja) * 2007-06-06 2014-03-05 出光興産株式会社 脱硫重質分解ガソリンの製造方法
US7780847B2 (en) * 2007-10-01 2010-08-24 Saudi Arabian Oil Company Method of producing low sulfur, high octane gasoline
CN101429444B (zh) * 2007-11-09 2012-11-14 丁冉峰 一种催化烃重组制备高质量汽油的系统及其方法
CA2705034C (en) * 2007-11-09 2016-10-11 Ranfeng Ding System and process for producing high quality gasoline by catalytic hydrocarbon recombination
CN101429448B (zh) * 2007-11-09 2012-11-14 丁冉峰 一种催化烃重组制备高质量汽油的系统及其方法
CN101429442B (zh) * 2007-11-09 2013-02-06 丁冉峰 一种催化烃重组制备高质量汽油的设备及其方法
CN101429447B (zh) * 2007-11-09 2012-11-14 丁冉峰 一种催化烃重组制备高质量汽油的系统及其方法
US8142646B2 (en) * 2007-11-30 2012-03-27 Saudi Arabian Oil Company Process to produce low sulfur catalytically cracked gasoline without saturation of olefinic compounds
US20090145808A1 (en) * 2007-11-30 2009-06-11 Saudi Arabian Oil Company Catalyst to attain low sulfur diesel
WO2009105749A2 (en) 2008-02-21 2009-08-27 Saudi Arabian Oil Company Catalyst to attain low sulfur gasoline
CN101993725B (zh) * 2009-08-27 2013-06-26 中国石油化工股份有限公司 一种生产低硫汽油的方法
CN102051223B (zh) * 2009-10-27 2013-08-28 中国石油化工股份有限公司 一种催化裂化汽油加氢工艺方法
US20130056391A1 (en) 2010-03-17 2013-03-07 Indian Oil Corporation Limited Catalytical hydrodesulfurization of kerosene in two steps on cobalt-molybdenum catalyst and intermediate stripping
CN102284300B (zh) * 2010-06-21 2013-04-24 中国石油天然气股份有限公司 一种劣质柴油加氢处理催化剂及制备方法
US9005432B2 (en) 2010-06-29 2015-04-14 Saudi Arabian Oil Company Removal of sulfur compounds from petroleum stream
WO2012066572A2 (en) 2010-11-19 2012-05-24 Indian Oil Corporation Ltd. Process for deep desulfurization of cracked gasoline with minimum octane loss
US8535518B2 (en) 2011-01-19 2013-09-17 Saudi Arabian Oil Company Petroleum upgrading and desulfurizing process
CN103059966B (zh) * 2011-10-21 2015-04-15 中国石油化工股份有限公司 一种生产低硫汽油的方法
CN103059945B (zh) * 2011-10-21 2015-09-30 中国石油化工股份有限公司 一种催化汽油加氢脱硫方法
CN103242904B (zh) * 2012-02-06 2015-09-30 中国石油化工股份有限公司 一种加氢精制联合工艺方法
FR2993569B1 (fr) 2012-07-17 2015-12-04 IFP Energies Nouvelles Procede de desulfuration d'une essence
FR2993570B1 (fr) 2012-07-17 2015-12-04 IFP Energies Nouvelles Procede de production d'une essence legere basse teneur en soufre
FR2997415B1 (fr) 2012-10-29 2015-10-02 IFP Energies Nouvelles Procede de production d'une essence a basse teneur en soufre
FR3000964B1 (fr) 2013-01-14 2016-01-01 IFP Energies Nouvelles Procede de production d'une essence basse teneur en soufre
US10308883B2 (en) 2015-10-07 2019-06-04 Axens Process for desulfurizing cracked naphtha
US10752847B2 (en) 2017-03-08 2020-08-25 Saudi Arabian Oil Company Integrated hydrothermal process to upgrade heavy oil
US10703999B2 (en) 2017-03-14 2020-07-07 Saudi Arabian Oil Company Integrated supercritical water and steam cracking process
US10526552B1 (en) 2018-10-12 2020-01-07 Saudi Arabian Oil Company Upgrading of heavy oil for steam cracking process
CN117339605B (zh) * 2022-06-27 2025-11-18 中国石油化工股份有限公司 一种硫化型变换催化剂及其制备方法
CN117920329A (zh) * 2022-10-25 2024-04-26 中国石油化工股份有限公司 一种低温硫醇硫醚化催化剂及其制备方法和低温硫醇硫醚化的方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2512570A (en) * 1948-07-20 1950-06-20 Shell Dev Desulfurization of hydrocarbon oils
US2904501A (en) * 1955-03-01 1959-09-15 Exxon Research Engineering Co Hydroforming catalytic pentenes
US3133013A (en) * 1961-01-23 1964-05-12 Universal Oil Prod Co Hydrorefining of coke-forming hydrocarbon distillates
US4131537A (en) * 1977-10-04 1978-12-26 Exxon Research & Engineering Co. Naphtha hydrofining process
FR2476118B1 (fr) * 1980-02-19 1987-03-20 Inst Francais Du Petrole Procede de desulfuration d'un effluent de craquage catalytique ou de craquage a la vapeur
US4990242A (en) * 1989-06-14 1991-02-05 Exxon Research And Engineering Company Enhanced sulfur removal from fuels
US5360532A (en) * 1991-08-15 1994-11-01 Mobil Oil Corporation Gasoline upgrading process
SA95160068B1 (ar) * 1994-12-13 2006-05-28 كيميكال ريسيرتش اند ليسنسنج كومباني عملية لإزالة المركبتانات mercaptans وكبرتيد هيدروجين hydrogen sulfide من تيارات هيدروكربون hydrocarbon
JP3443474B2 (ja) * 1995-02-03 2003-09-02 新日本石油株式会社 接触分解ガソリンの脱硫処理方法
FR2743080B1 (fr) * 1995-12-27 1998-02-06 Inst Francais Du Petrole Procede de reduction selective de la teneur en benzene et en composes insatures legers d'une coupe d'hydrocarbures
JP3729621B2 (ja) * 1997-09-24 2005-12-21 新日本石油株式会社 接触分解ガソリンの水素化脱硫方法及びガソリン
JP3868128B2 (ja) * 1998-10-05 2007-01-17 新日本石油株式会社 軽油の水素化脱硫装置及び方法

Also Published As

Publication number Publication date
EP1002853A1 (de) 2000-05-24
JP2000160169A (ja) 2000-06-13
US6334948B1 (en) 2002-01-01
FR2785908A1 (fr) 2000-05-19
FR2785908B1 (fr) 2005-12-16
KR100626623B1 (ko) 2006-09-25
ES2267238T3 (es) 2007-03-01
DE69931876T2 (de) 2006-10-05
JP4547745B2 (ja) 2010-09-22
CN1158378C (zh) 2004-07-21
CN1253993A (zh) 2000-05-24
DE69931876D1 (de) 2006-07-27
KR20000035520A (ko) 2000-06-26

Similar Documents

Publication Publication Date Title
EP2169032B1 (de) Katalysator zur teilweise oder ganz Zersetzung oder Hydrierung von ungesättigten schwefelhaltigen Verbindungen
EP1174485B1 (de) Zweistufiges Benzin Entschwefelungsverfahren mit zwischenzeitlicher Entfernung von H2S
FR2785908A1 (fr) Procede de production d'essences a faible teneur en soufre
EP1138749B1 (de) Benzin Entschwefelungsverfahren mit Entschwefelung von Schwer- und Mittelfraktionen von einen Fraktionierung in mindestens drei Schnitten
EP1923452B1 (de) Verfahren zur Tiefenentschwefelung von Krack-Benzinstoffen mit einem geringen Oktanzahlverlust
CA2299152C (fr) Procede de production d'essences a faible teneur en soufre
FR2837831A1 (fr) Procede de production d'hydrocarbures a faible teneur en soufre et en mercaptans
EP2816094A1 (de) Herstellungsverfahren einer Essenz mit niedrigem Schwefel- und Mercaptangehalt
FR2993570A1 (fr) Procede de production d'une essence legere basse teneur en soufre
EP1369466B1 (de) Hydroentschwefelungsverfahren für Schwefel und Olefine enthaltende Schnitten in Anwesenheit eines Träger-Katalysators welcher Metalle von den Gruppen VIII und VIB enthält
EP1370627B1 (de) Verfahren zur herstellung von benzin mit niedrigem schwefelgehalt
EP3228683B1 (de) Aufbereitungsverfahren einer essenz
WO2014108612A1 (fr) Procede de production d'une essence basse teneur en soufre
CA2440189C (fr) Procede de production d'une essence desulfuree a partir d'une coupe essence contenant de l'essence de craquage
FR2785833A1 (fr) Catalyseur comprenant du nickel et son utilisation dans un procede d'hydrodesulfuration de charges hydrocarbonees
EP1370629B1 (de) Verfahren zur herstellung von benzin mit niedrigem schwefelgehalt
WO2015165664A1 (fr) Procédé de production d'une essence a basse teneur en soufre et en mercaptans
WO2025087707A1 (fr) Procede de traitement d'une essence de pyrolyse

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 ES IT NL

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20001124

AKX Designation fees paid

Free format text: DE ES IT NL

17Q First examination report despatched

Effective date: 20030807

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 ES IT NL

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20060614

REF Corresponds to:

Ref document number: 69931876

Country of ref document: DE

Date of ref document: 20060727

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2267238

Country of ref document: ES

Kind code of ref document: T3

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: 20070315

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 69931876

Country of ref document: DE

Owner name: IFP ENERGIES NOUVELLES, FR

Free format text: FORMER OWNER: INSTITUT FRANCAIS DU PETROLE, RUEIL MALMAISON, FR

Effective date: 20110331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20141112

Year of fee payment: 16

Ref country code: DE

Payment date: 20141126

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20141124

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20141121

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69931876

Country of ref document: DE

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: 20151109

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20151201

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: 20151201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160601

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20170303

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20151110