EP2886629A1 - Verfahren zur Hydroentschwefelung von Kohlenwasserstoffanteilen - Google Patents

Verfahren zur Hydroentschwefelung von Kohlenwasserstoffanteilen Download PDF

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Publication number
EP2886629A1
EP2886629A1 EP14306951.6A EP14306951A EP2886629A1 EP 2886629 A1 EP2886629 A1 EP 2886629A1 EP 14306951 A EP14306951 A EP 14306951A EP 2886629 A1 EP2886629 A1 EP 2886629A1
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EP
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Prior art keywords
mixture
hydrocarbon
cut
boiling point
hydrodesulfurization
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English (en)
French (fr)
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EP2886629B1 (de
Inventor
Julien Gornay
Philibert Leflaive
Olivier TOUZALIN
Annick Pucci
Delphine Largeteau
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • 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
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
    • 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
    • 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
    • C10G2400/04—Diesel oil
    • 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
    • C10G2400/06—Gasoil

Definitions

  • the present invention relates to a process for the concomitant production of at least two hydrocarbon cuts with low sulfur contents.
  • the process allows to desulphurize jointly (in a mixture) a gasoline fraction containing olefins and a heavier cut than the gasoline cut so as to subsequently produce a desulfurized gasoline cut with a limited octane loss and a heavy cut also desulfurized.
  • the present invention is particularly interesting for producing at least two desulphurized cups which are likely to be sent respectively to the gasoline pool and the diesel pool, kerosene and / or fuel oil.
  • Sulfur in fuels is an undesirable impurity because it is converted to sulfur oxides when these products are burned.
  • Sulfur oxides are undesirable air pollutants that can additionally deactivate most of the catalysts that have been developed for catalytic converters used in cars to catalyze the conversion of harmful exhaust gases. Therefore, it is desirable to reduce the sulfur content of the products entering the gasoline and diesel fuel compositions to the lowest possible levels.
  • Catalytic cracking gasoline is the essential product of the FCC (Fluid Catalytic Cracking FCC) obtained with a yield of the order of 50% and represents about 25 to 30% of the gasoline pool of refineries. 'Western Europe.
  • FCC Fluid Catalytic Cracking FCC
  • the main negative characteristic of these FCC gasolines with respect to commercial fuels is their high sulfur content and thus constitute the main vector of the presence of sulfur in fuels.
  • hydrocarbons produced from catalytic cracking processes are conventionally treated by hydrotreatment.
  • the hydrotreatment process comprises contacting the hydrocarbon feed with hydrogen in the presence of a catalyst to convert the sulfur contained in the impurities to hydrogen sulfide, which can then be separated and converted. in elemental sulfur.
  • Hydroprocessing processes can result in partial destruction of the feed olefins by converting them to saturated hydrocarbons by hydrogenation. This destruction of olefins by hydrogenation is undesirable in the case of cracking gasolines because it results in an expensive consumption of hydrogen and a significant decrease in the octane number of hydrodesulphurized species.
  • the residual sulfur compounds generally present in the desulphurized gasoline can be separated into two distinct families: the non-hydrodesulfurized sulfur compounds present in the feedstock and the sulfur compounds formed in the hydrodesulfurization reactor by so-called recombination side reactions.
  • the major compounds are the mercaptans resulting from the addition of H 2 S formed in the reactor on mono-olefins present in the feedstock. Reduction of the recombinant mercaptan content can be achieved by catalytic hydrodesulphurization but at the expense of saturation of a large portion of the mono-olefins, which then results in a sharp decrease in the octane number of the gasoline. as well as overconsumption of hydrogen.
  • the process of the document EP 902,078 thus treats a distillate from an atmospheric distillation step.
  • This type of distillate contains practically no compounds olefinic hydrocarbons in contrast to the filler treated in the present invention, a section of which contains it contains a large content of olefins, typically greater than 20% by weight relative to the total weight of said cut.
  • the sulfur compounds of majority recombination encountered in the process of the document EP 902,078 are therefore not mercaptans resulting from the addition of the H 2 S formed in the reactor on the mono-olefins present in the feed, but probably the result of the addition of the H 2 S formed on olefins of cracking reactions induced by the high temperature necessary for very deep desulfurization of the feedstock.
  • the heavy naphtha resulting from atmospheric distillation is generally intended to be converted into a catalytic reforming unit and must therefore be desulfurized in a thorough manner (the total sulfur content is typically less than 1 ppm by weight).
  • the specification of permissible sulfur in a gasoline pool is less severe (approximately 10 ppm by weight).
  • the skilled person therefore seeks, in the case of the hydrodesulfurization of a distillate comprising gas oil and fractions whose boiling point is lower than that of gas oil obtained from an atmospheric distillation, to maximize the hydrodesulfurization reaction. while avoiding reactions (including cracking reactions) likely to form olefins.
  • the solution advocated by the patent EP 902,078 consists in carrying out a high hydrodesulphurization at high temperature in a first reactor followed by a softer hydrodesulfurization in a second reactor which makes it possible to eliminate any recombination mercaptans and / or the olefins that would have been produced in the first reactor.
  • This way of operating is unsuited to a feed containing a gasoline from a conversion unit with high olefins content because it may cause significant hydrogenation of said olefins in the first step, thus inducing a loss of octane number unwanted.
  • the document US 2013/0087484 discloses a process for producing p-xylene from a mixture of naphtha and light-cutting oil (LCO, "Light Cycle Oil”) from a catalytic cracking unit.
  • the process comprises a step of hydrodesulfurization of said mixture followed by fractionation of the desulfurized effluent in three sections, namely a light C 2 -C 4 cut, a naphtha cut and a heavy cut.
  • the intermediate naphtha cut is processed in a catalytic reforming unit to produce aromatic compounds and the heavy cut is hydrocracked to yield a rich aromatic effluent which is recycled to the fractionation column.
  • the second hydrodesulphurization stage is conducted at a temperature at least 10 ° C., preferably at least 20 ° C. lower than that of the first hydrodesulfurization stage.
  • the prior art also includes the document FR 2811328 which teaches a hydrodesulphurization process of a gasoline cut which may be a mixture of gasolines from different conversion processes such as steam cracking, coking or visbreaking processes or even gasolines directly derived from the atmospheric distillation of oil.
  • An object of the invention is to provide a hydrodesulphurization process that can meet the overcapacity problems of the hydrodesulphurisation units of gasolines.
  • the boiling temperatures can fluctuate at plus or minus 5 ° C with respect to the values mentioned.
  • the inventors have surprisingly observed that it is possible to hydrodesulphurize a mixture containing a gasoline cut and a sulfur-rich, low-olefin distillate cut in order to produce a low gasoline cut.
  • sulfur content in particular in mercaptans, without significant loss of the octane number and a sulfur-reduced distillate cut which can then be upgraded to the diesel pool and / or kerosene or as a fuel for maritime use.
  • the treatment in the first hydrodesulfurization step of the hydrocarbon mixture surprisingly leads to limiting the formation of recombinant mercaptans, the reaction products of the addition of H 2 S to the olefins, and thus to obtaining at the end of the process, a gasoline cut having a very low mercaptan content.
  • the second hydrodesulphurization step is carried out under conditions which then favor the hydroconversion of the more refractory sulfur compounds which come essentially from the distillate cut.
  • the method according to the invention responds well to the problem of overcapacity of the hydrodesulfurization units of gasolines insofar as these same units can now be used to desulphurize jointly gasoline cuts and medium or heavy distillate cuts which are bases for the formulation. diesel and / or kerosene fuels or for use as low sulfur marine fuel.
  • the invention therefore relates to a method employing at least two successive hydrodesulphurization stages of a hydrocarbon mixture comprising a first and a second hydrocarbon fraction with an intermediate stage of elimination of hydrogen sulphide (H 2 S) formed in the first hydrodesulphurization step and with a reaction temperature in the second hydrodesulfurization step which is greater than that of the first hydrodesulfurization step.
  • H 2 S hydrogen sulphide
  • the catalyst of step a) is a hydrodesulfurization catalyst which comprises a Group VIII metal selected from nickel and cobalt and a Group VIB metal selected from molybdenum and tungsten.
  • the catalyst of step c) is also a hydrodesulfurization catalyst which comprises a Group VIII metal selected from nickel and cobalt and a Group VIB metal selected from molybdenum and tungsten.
  • the first olefin-containing hydrocarbon fraction is a gasoline cut and most preferably the gasoline cut is from a catalytic cracking unit.
  • the second hydrocarbon fraction of the mixture treated by the process according to the invention is preferably selected from a light oil fraction obtained from a catalytic cracking unit (LCO or "Light Cycle Oil”) according to the English terminology.
  • a light or heavy gas oil cut for example from the direct distillation of petroleum, a vacuum distillate cut, a distillate cut from a thermal cracking unit such as for example a visbreaking agent ("Visbreaking" according to the English terminology).
  • -saxonne or a coker unit for example delayed (“Delayed Coking" according to the English terminology).
  • the feedstock of the process according to the invention is a mixture containing a catlaytic cracking petrol fraction and a light LCO oil fraction.
  • said mixture is the product of a distillation of an effluent from a catalytic cracking unit.
  • LCO low-density polystyrene
  • the light fraction of LCO i.e. compounds having a boiling point of less than 300 ° C, and very preferably less than 265 ° C is used in admixture with the catalytic cracking gasoline.
  • the first fraction or cut of hydrocarbons represents between 30 and 70% by weight of the mixture.
  • the first fraction of the mixture is a heavy fraction of a catalytic cracking gasoline and the second fraction is a light oil fraction LCO.
  • the heavy fraction of the catalytic cracking gasoline is obtained by distillation of a catalytic cracking gasoline fraction in two fractions, a C5- light fraction comprising hydrocarbons having a carbon number of between 2 and 5 atoms and a C6 + heavy fraction comprising hydrocarbons having a number of carbon atoms greater than or equal to 6.
  • said gasoline fraction prior to the step of separating the gasoline fraction of catalytic cracking into two fractions, said gasoline fraction is treated in a step of selective hydrogenation of the diolefins.
  • the first hydrocarbon fraction treated by the process according to the invention is sent via line 1 to a first hydrodesulfurization reactor 2.
  • This first hydrocarbon fraction is further combined (mixed) with a second hydrocarbon fraction.
  • the mixture which can be considered as consisting of two fractions, is then treated in the first hydrodesulfurization reactor 2.
  • the first hydrocarbon cut which constitutes all or part of the first fraction of the mixture is for example an olefinic gasoline cut from a catalytic cracking, steam cracking, coking, visbreaking unit.
  • the gasoline cut is a catalytic cracking gasoline.
  • the petrol fraction has an initial boiling point of between 35 ° C. and 100 ° C. and a final boiling point of 130 ° to 200 ° C., preferably of 150 ° to 170 ° C. and more preferably between 155 and 165 ° C.
  • the olefin content of the first cut (or first fraction making up the mixture) is between 20 and 80% by weight of said cut.
  • the second hydrocarbon cut has an initial boiling point of about 160 ° C and the final boiling temperature of between 260 and 340 ° C and comprises a fraction of at least 10% by weight of hydrocarbons having a temperature boiling point between 220 ° C and its final boiling point.
  • This second cut thus constitutes all or part of the second fraction of the mixture.
  • This second hydrocarbon cut corresponds, for example, to a distillate cut, preferably chosen from a light oil cut obtained from a catalytic cracking unit (LCO or "Light Cycle Oil”), a light or heavy diesel fuel for example from the direct distillation of petroleum, a vacuum distillate cut, a distillate cut from a thermal cracking unit such as for example a visbreaking machine ("Visbreaking" according to the English terminology). ) or a coker unit for example delayed (“Delayed Coking" according to the English terminology).
  • LCO catalytic cracking unit
  • a light or heavy diesel fuel for example from the direct distillation of petroleum
  • a vacuum distillate cut a distillate cut
  • This second cut has an olefin content lower than that of the first cut and a total sulfur content greater than that of the first cut.
  • the second hydrocarbon cut is a light oil derived from a catalytic cracking unit (LCO or "Light Cycle Oil” in English terminology).
  • said second fraction comprises at least 10% by weight of hydrocarbons having a range of boiling temperatures of between 220 ° C. and the final boiling point of the mixture.
  • the first hydrodesulfurization step makes it possible to convert a portion of the sulfur present in the mixture to hydrogen sulphide (H 2 S). It consists in passing the hydrocarbon mixture to be treated in the presence of hydrogen (supplied via line 4) to a hydrodesulfurization catalyst at a temperature of between 200 ° C. and 400 ° C., preferably between 250 ° C. C. and 340 ° C. and at a pressure of between 1 and 10 MPa, preferably between 1.5 and 4 MPa.
  • the liquid space velocity is generally between 1 and 10 h -1 , preferably between 2 and 5 h -1 and the H 2 / H 2 ratio is between 50 Nlitres / liter (l / l) and 500 Nlitres / liter, of preferably between 100 Nlitres / liter and 450 Nlitres / liter, and more preferably between 150 Nlitres / liter and 400 Nlitres / liter.
  • the ratio H 2 / HC is the ratio between the volume flow rate of hydrogen under 1 atmosphere and at 0 ° C and the volume flow rate of hydrocarbons.
  • the effluent resulting from this hydrodesulphurization step taken off line 5 comprises the partially desulfurized hydrocarbon mixture, the residual hydrogen and the H 2 S produced by decomposition of the sulfur compounds.
  • This hydrodesulfurization step is carried out for example in a fixed-bed or moving-bed reactor.
  • the catalyst used during the first hydrodesulfurization step of the hydrodesulfurization process according to the invention comprises an active metal phase deposited on a support, said active phase comprising at least one metal of group VIII of the periodic table of elements ( groups 8, 9 and 10 according to the new notation of the periodic table of elements: Handbook of Chemistry and Physics, 76th edition, 1995-1996 ) and at least one Group VIB metal of the Periodic Table of Elements ( group 6 according to the new notation of the periodic table of elements: Handbook of Chemistry and Physics, 76th edition, 1995-1996 ).
  • the active phase of said catalyst further comprises phosphorus.
  • the catalyst of the first hydrodesulfurization step may also further contain one or more organic compounds.
  • the metal content (ux) of group VIB in said catalyst of the first hydrodesulfurization step is between 4 and 40% by weight of metal oxide (s) (ux) of group VIB, preferably between 8 and 35% by weight of Group VIB metal oxide (s), very preferably between 10 and 30% by weight of Group VIB metal oxide (s) relative to the total weight catalyst.
  • the Group VIB metal is molybdenum or tungsten or a mixture of these two elements, and more preferably the Group VIB metal consists solely of molybdenum or tungsten.
  • the Group VIB metal is very preferably molybdenum.
  • the metal content (ux) of group VIII in said catalyst of the first hydrodesulphurization step is between 1.5 and 9% by weight of metal oxide (s) (ux) of group VIII, from preferred manner between 2 and 8% by weight of metal oxide (s) (ux) group VIII relative to the total weight of the catalyst.
  • the Group VIII metal is a non-noble metal of Group VIII of the Periodic Table of Elements.
  • said group VIII metal is cobalt or nickel or a mixture of these two elements, and more preferably the group VIII metal consists solely of cobalt or nickel.
  • the Group VIII metal is very preferably cobalt.
  • the molar ratio of metal (ux) of group VIII to metal (ux) of group VIB in the catalyst in oxide form is between 0.1 and 0.8, very preferably between 0.2 and 0.6, and still more preferably between 0.3 and 0.5.
  • the phosphorus content of the catalyst of the first hydrodesulfurization step is preferably between 0.1 and 20% by weight of P 2 O 5 , more preferably between 0.2 and 15% by weight. of P 2 O 5 , very preferably between 0.3 and 10% by weight of P 2 O 5 relative to the total weight of the catalyst.
  • the phosphorus to metal molar ratio (ux) of group VIB in the catalyst of the first hydrodesulphurization step is greater than or equal to 0.05, preferably greater than or equal to 0.1, more preferably of between 0.15 and 0.15. and 0.6, even more preferably between 0.15 and 0.5.
  • the catalyst support of the first hydrodesulfurization stage on which the active phase is deposited is advantageously formed of at least one porous solid in oxide form chosen from the group consisting of aluminas, silicas, silica-alumina or oxides of titanium or magnesium used alone or in admixture with alumina or silica-alumina. It is preferably selected from the group consisting of silicas, transition aluminas and silica-alumina. More preferably, said support consists solely of a transition alumina or a mixture of transition aluminas.
  • the specific surface area of the catalyst is generally between 100 and 400 m 2 / g, preferably between 150 and 300 m 2 / g.
  • the catalyst of the first hydrodesulfurization step is advantageously in the form of balls, extrudates, pellets, or irregular and non-spherical agglomerates, the specific shape of which may result from a crushing step.
  • said support is in the form of balls or extrudates.
  • the catalyst of the first hydrodesulfurization step is preferably used at least in part in its sulfurized form.
  • 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 sulphurization step may be carried out in situ, that is to say in the process according to the invention, or ex situ, ie in a unit dedicated to catalyst sulphurations.
  • the process comprises a step where the H 2 S is at least partially removed from the effluent obtained at the end of the first hydrodesulfurization step.
  • This step can be performed using any techniques known to those skilled in the art. It can be carried out directly under the conditions in which the effluent is located at the end of this stage or after the conditions have been changed in order to facilitate the removal of at least a portion of the H 2 S.
  • a gas / liquid separation (where the gas is concentrated in H 2 S and the liquid is depleted in H 2 S), a stripping step the effluent, an amine washing step, a capture of H 2 S by an absorbent mass operating on the gaseous or liquid effluent, a separation of the H 2 S from the gaseous or liquid effluent by a membrane.
  • a gas / liquid separation following which the liquid effluent is sent to a stripping column while the gaseous effluent is sent in an amine wash step.
  • the effluent from the reactor of the first hydrodesulfurization stage is sent via line 5 to a stripping column 6 which makes it possible to separate at the top of the column a gas stream 7 containing hydrogen and H 2 S and bottom an effluent containing a mixture of hydrocarbons 8 partially desulfurized and stripped H 2 S.
  • the effluent comprising the partially desulfurized hydrocarbon mixture is treated in a further hydrodesulfurization (HDS) step to improve the final desulfurization rate.
  • This second step is intended to transform the refractory sulfur compounds present in the mixture and which are essentially provided by the second cut used in the process according to the invention.
  • the effluent is sent via line 8 to a hydrodesulphurization reactor 9 and is brought into contact with a hydrodesulfurization catalyst in the presence of hydrogen brought by line 10.
  • the temperature of the second step of HDS is greater than that of the first step of HDS, preferably greater than at least 5 ° C. and even more preferably at least 10 ° C.
  • the second hydrodesulphurization step uses a catalyst having a selectivity in hydrodesulphurization with respect to the hydrogenation of olefins greater than the catalyst of the first hydrodesulfurization step.
  • the catalyst adapted for this second hydrodesulfurization step comprises at least one Group VIII metal ( groups 8, 9 and 10 according to the new notation of the periodic table of elements: Handbook of Chemistry and Physics, 76th edition, 1995-1996 ) and at least one Group VIB metal ( group 6 according to the new notation of the periodic table of elements: Handbook of Chemistry and Physics, 76th edition, 1995-1996 ) 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 relative to the total weight of catalyst.
  • the metal content of group VIB is generally between 1.5 and 60% by weight, preferably between 3 and 50% by weight relative to the total weight of catalyst.
  • the Group VIII metal is preferably cobalt and the Group VIB metal is generally molybdenum or tungsten.
  • the catalyst of the second hydrodesulfurization step further comprises phosphorus.
  • the phosphorus content of said catalyst is preferably between 0.1 and 20% by weight of P 2 O 5 , more preferably between 0.2 and 15% by weight of P 2 O 5 , very preferably between 0.3. and 10% by weight of P 2 O 5 based on the total weight of the catalyst.
  • the catalyst further comprises one or more organic compounds.
  • 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.
  • 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 200 m 2 / g, more preferably less than 180 m 2 / g, and very preferably less than 150 m 2 / g.
  • the catalyst of the second hydrodesulfurization step is preferably used at least in part in its sulfurized form.
  • Sulfurization consists of passing the 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 sulphurization step may be carried out in situ, that is to say in the process according to the invention, or ex situ, ie in a unit dedicated to catalyst sulphurations.
  • the desulfurized effluent has a total sulfur content generally less than 50 ppm by weight, preferably less than 30 ppm by weight and has a mercaptan content generally less than 10 ppm by weight.
  • the effluent that is withdrawn from the second hydrodesulfurization reactor 9 is sent via line 11 to a separation unit 12.
  • the reactor effluent is first sent to a balloon gas / liquid separation system for separating a gas rich in H 2 S from the liquid effluent.
  • This liquid effluent is then sent to a stabilization column in order to remove the last traces of solubilized H 2 S and to produce a stabilized column bottom product, that is to say the vapor pressure of which has been corrected by elimination of the lightest hydrocarbon compounds.
  • the gas / liquid separation and stabilization steps are conventional steps for those skilled in the art and are not represented in the art. figure 1 .
  • the separation or distillation step consists in separating the stabilized effluent containing the hydrocarbon mixture into at least two hydrocarbon fractions, namely a light hydrocarbon fraction and a heavy hydrocarbon fraction both desulfurized.
  • the cutting point is generally between 160.degree. C. and 220.degree. included.
  • the separation unit used is a distillation column configured to separate at the top of the column a light desulphurized cut 13 equivalent to a gasoline cut and bottom a desulphurized heavy cut 14 equivalent to a distillate cut.
  • the petrol cut is sent to the gasoline pool and the desulfurized distillate cut is sent to the diesel pool, kerosene or fuel oil.
  • the sulfur content in the desulphurized light cut (or gasoline cut) is less than 50 ppm by weight, preferably less than 30 ppm by weight and even more preferably less than 10 ppm by weight.
  • the sulfur content in the desulfurized heavy cut (or distillate cut) is less than 50 ppm by weight, optionally less than 30 ppm by weight or even less than 10 ppm by weight.
  • distillate cut is recovered in the bottom, the petrol cut is laterally withdrawn several trays below the top plate while the lighter compounds are removed at the top of the column in the gaseous effluent.
  • the effluent from the stabilization column containing the desulfurized hydrocarbon mixture is separated into three sections.
  • the two cutting points will generally be about 160 ° C and about 220 ° C.
  • the three hydrocarbon cuts have a total sulfur content of less than 50 ppm by weight, preferably less than 30 ppm by weight and even more preferably less than 10 ppm by weight.
  • the inventors have found that the implementation of two successively hydrodesulfurization steps with an intermediate H 2 S removal step on a mixture of a gasoline cut and medium or heavy distillate finally allows to provide a desulphurized gasoline with a low mercaptan content and without noticeable loss of the octane number and without requiring particularly severe hydrodesulphurization conditions which are generally accompanied by a significant hydrogenation of the monohydrogenated hydrocarbon compounds; olefin.
  • the octane loss associated with the hydrogenation of the mono-olefins during the hydrodesulfurization steps is greater the lower the sulfur content, that is to say that when the it seeks to eliminate in depth the sulfur compounds present in the load.
  • a first cut of hydrocarbons of the type essence is sent in a pre-treatment reactor 15 before being mixed with a second hydrocarbon cut.
  • the hydrocarbon feed is preferably a catalytic cracking gasoline cut which generally contains diolefins at a content of between 0.1 and 3% by weight.
  • the pretreatment consists of a step of selective hydrogenation of the diolefins to corresponding mono-olefins, which is carried out in the presence of a catalyst and hydrogen.
  • the catalyst for the selective hydrogenation of diolefins adapted for pretreatment comprises at least one group VIB metal and at least one group VIII metal deposited on a porous support described in the patent application.
  • the selective hydrogenation catalytic reaction is generally conducted in the presence of hydrogen, at a temperature between 80 ° C and 220 ° C, and preferably between 90 ° C and 200 ° C, with a liquid space velocity (LHSV) included between 1 and 10 h -1 , the unit of the liquid space velocity being the liter of charge per liter of catalyst and per hour (I / Ih).
  • LHSV liquid space velocity
  • the operating pressure is between 0.5 MPa and 5 MPa, preferably between 1 and 4 MPa.
  • the gasoline produced contains less than 0.5% by weight of diolefins, and preferably less than 0.25% by weight of diolefins.
  • the first pretreated hydrocarbon fraction is directed via line 16 to a separation column 17 (splitter according to the English terminology) which is designed to fractionate said pretreated feed respectively into a light fraction C5 - and a heavy fraction C6 +.
  • the light fraction is advantageously sent to the gasoline pool via line 18, while the heavy C6 + fraction entering in line 1 is hydrodesulphurized by the process described above, that is to say in a mixture with a middle distillate cut or heavy, low olefins.
  • a hydrodesulfurization ⁇ catalyst is obtained by impregnation "without excess solution" of a transition alumina in the form of specific surface beads of 130 m 2 / g and a pore volume of 0.9 ml / g, by a 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 the ⁇ catalyst is 3% by weight of CoO and 10% by weight of MoO 3 .
  • ⁇ catalyst 50 ml of the ⁇ catalyst 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% by weight of sulfur in the form of dimethyldisulphide in n-heptane.
  • the treated feed C is a catalytic cracking gasoline whose initial boiling point is 61 ° C and the end point is 162 ° C. Its sulfur content is 765 ppm by weight and its bromine number (IBr) is 75.9 g / 100 g which corresponds to approximately 42% by weight of olefins.
  • This charge C is treated with the catalyst ⁇ , under a pressure of 2 MPa, a volume ratio hydrogen on charge to be treated (H 2 / HC) of 300 NI / I and a VVH of 4 h -1 .
  • H 2 / HC volume ratio hydrogen on charge to be treated
  • VVH volume ratio hydrogen on charge to be treated
  • the effluent is cooled and the H 2 S-rich hydrogen is separated from the liquid gasoline, and the gasoline is subjected to a stripping treatment by injecting a stream of hydrogen in order to eliminate the residual traces of H 2 S dissolved in the desulfurized gasoline.
  • Table 1 shows the influence of the temperature involved on the desulfurization rates and the RON index of the desulfurized effluents.
  • Table 1 Analysis of the desulfurized gasoline Temperature in the hydrodesulfurization reactor, 285 ° C. Temperature in the hydrodesulfurization reactor, 295 ° C. Mercaptans, ppm weight 16 7 Total sulfur, ppm 25 12 Desulfurization rate,% 96.7 98.4 RON loss 6.9 8.4
  • a hydrodesulfurization ⁇ catalyst in the form of extrudates with a specific surface area of 180 m 2 / g, the content (weight of oxide (s) relative to the total weight of the catalyst) of cobalt, molybdenum and phosphorus are respectively 4.4% by weight of CoO and 21.3% by weight of MoO 3 and 6.0% by weight of P 2 O 5 are placed in a fixed-bed tubular hydrodesulfurization reactor.
  • the catalyst is first sulphurized by treatment for 4 hours under a pressure of 2 MPa at 350 ° C., in contact with a feedstock consisting of 2% by weight of sulfur in the form of dimethyldisulphide in n-heptane.
  • the treated feedstock D has an initial boiling point of 160 ° C and an end point of 269 ° C. Its sulfur content is 5116 ppm by weight and its bromine number (IBr) is 19.5 g / 100 g which corresponds to approximately 10% by weight of olefins.
  • the fraction of the feed D with a boiling point between 220 ° C. and 269 ° C. is 26.3% by weight.
  • the charge D is treated with the catalyst ⁇ , at a temperature of 300 ° C., under a pressure of 2 MPa, with a volume ratio hydrogen on charge to be treated (H 2 / HC) of 300 NI / I and a VVH of 4 h -1 .
  • H 2 / HC volume ratio hydrogen on charge to be treated
  • the effluent is cooled, H 2 S-rich hydrogen is separated from the liquid effluent, and the effluent is subjected to a stripping treatment by injecting a stream of hydrogen in order to eliminate the residual traces of dissolved H 2 S before being analyzed.
  • Table 2 shows the desulfurization rate and the sulfur and mercaptan content of the desulphurized effluent.
  • Table 2 Analysis Mercaptans, ppm weight 12 Total sulfur, ppm 34 Desulfurization rate,% 99.3
  • a charge E tested in Example 3 is a mixture containing 50% by weight of the charge C and 50% by weight of the charge D.
  • the initial boiling point of the mixture is 61 ° C. and the end point 269 ° C. vs.
  • Its sulfur content is 2512 ppm by weight and its bromine number (IBr) is 53.4 g / 100 g which corresponds approximately to 29.2% by weight of olefins.
  • This charge E is first treated on the catalyst ⁇ , at a temperature of 330 ° C., under a pressure of 2 MPa, with a volume ratio hydrogen on charge to be treated (H 2 / HC) of 300 NI / I and a VVH 4 h -1 .
  • H 2 / HC volume ratio hydrogen on charge to be treated
  • the effluent is cooled, H 2 S-rich hydrogen is separated from the liquid effluent, and the effluent is subjected to a stripping treatment by injecting a stream of hydrogen in order to eliminate the residual traces of dissolved H 2 S.
  • the effluent is then separated into two sections: a first cut (gasoline cut) with a boiling point of 160 ° C and a second cut with an initial point of 160 ° C.
  • Table 3 Analysis 1st cutting 61 ° C-160 ° C 2 nd cut 160 ° C-269 ° C Mercaptans, ppm weight 6 8 Total sulfur, ppm 6 49 Desulfurization rate,% 99.2 99 RON loss 9.8 Not applicable
  • the feedstock E used in example 3 is treated in a first hydrodesulphurization step on the ⁇ catalyst, at a temperature of 260.degree. C., under a pressure of 2 MPa, with a volume ratio of hydrogen on feedstock to be treated (H 2 / HC) of 300 NI / I and a VVH of 4 h -1 .
  • H 2 / HC volume ratio of hydrogen on feedstock to be treated
  • the effluent from the first hydrodesulphurization step is cooled, H 2 S-rich hydrogen is separated from the liquid effluent, and the effluent is subjected to stripping treatment by injection of a stream of hydrogen to remove residual traces of dissolved H 2 S.
  • the stripped effluent constitutes the feed F treated in the second hydrodesulfurization step.
  • the charge F is then treated in a second hydrodesulphurization step on the ⁇ catalyst, at a temperature of 280 ° C., under a pressure of 2 MPa, with a volume ratio of hydrogen on charge to be treated (H 2 / HC) of 300. I / I and a VHV of 4 h -1 .
  • H 2 S-rich hydrogen is separated from the liquid effluent, and the effluent is subjected to stripping treatment by injection of a stream of hydrogen to remove residual traces of dissolved H 2 S.
  • the effluent of the second hydrodesulfurization step is then separated into two sections: a first section (gasoline section) with a boiling point of 160 ° C and a second section with an initial point of 160 ° C.
  • Table 4 References 1st cutting 61 ° C-160 ° C 2 nd cut 160 ° C-269 ° C Mercaptans, ppm weight 7 11 Total sulfur, ppm 9 42 Desulfurization rate,% 98.8 99.2 RON loss 5.9 Not applicable
  • Example 4 shows that it is possible from a mixture of hydrocarbons comprising at least a first hydrocarbon fraction having a boiling point between 61 ° and 160 ° C. and whose olefin content is 42% by weight and a second cut of hydrocarbons having a boiling point between 160 ° and 269 ° C, the fraction having a boiling point greater than 220 ° C is 26.3%, to obtain two desulfurized cuts with a sulfur content of less than 10 ppm sulfur by weight, respectively, for the desulphurized section with a boiling point of between 61 ° C and 160 ° C and less than 50 ppm by weight of sulfur for the desulfurized section having a temperature of boiling range between 160 ° and 269 ° C while limiting the loss of RON index linked in particular to the hydrogenation of a portion of the olefins present in the mixture.

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FR3056599B1 (fr) * 2016-09-26 2018-09-28 IFP Energies Nouvelles Procede de traitement d'une essence par separation en trois coupes.
FR3099172B1 (fr) * 2019-07-23 2021-07-16 Ifp Energies Now Procede de traitement d'une essence par separation en trois coupes
FR3099174B1 (fr) * 2019-07-23 2021-11-12 Ifp Energies Now Procédé de production d'une essence a basse teneur en soufre et en mercaptans
FR3142487A1 (fr) * 2022-11-30 2024-05-31 IFP Energies Nouvelles Procédé d’hydrodésulfuration de finition des essences mettant en œuvre un catalyseur à base de métaux du groupe VIB et VIII et du phosphore sur support alumine à faible surface spécifique

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FR2837831A1 (fr) 2002-03-29 2003-10-03 Inst Francais Du Petrole Procede de production d'hydrocarbures a faible teneur en soufre et en mercaptans
EP2161076A1 (de) 2008-09-04 2010-03-10 Ifp Selektives Hydrierungsverfahren zum Einsatz eines Sulfidkatalysators mit spezifischer Zusammensetzung
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FR2988732A1 (fr) 2012-03-29 2013-10-04 IFP Energies Nouvelles Procede d'hydrogenation selective d'une essence
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FR2837831A1 (fr) 2002-03-29 2003-10-03 Inst Francais Du Petrole Procede de production d'hydrocarbures a faible teneur en soufre et en mercaptans
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US20130087484A1 (en) 2011-10-07 2013-04-11 Uop Llc Integrated catalytic cracking gasoline and light cycle oil hydroprocessing to maximize p-xylene production
FR2988732A1 (fr) 2012-03-29 2013-10-04 IFP Energies Nouvelles Procede d'hydrogenation selective d'une essence
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