EP2816094B1 - Procédé de production d'une essence à basse teneur en soufre et en mercaptans - Google Patents

Procédé de production d'une essence à basse teneur en soufre et en mercaptans Download PDF

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Publication number
EP2816094B1
EP2816094B1 EP14305833.7A EP14305833A EP2816094B1 EP 2816094 B1 EP2816094 B1 EP 2816094B1 EP 14305833 A EP14305833 A EP 14305833A EP 2816094 B1 EP2816094 B1 EP 2816094B1
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Prior art keywords
gasoline
catalyst
weight
cut
range
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EP14305833.7A
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German (de)
English (en)
French (fr)
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EP2816094A1 (fr
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Julien Gornay
Philibert Leflaive
Annick Pucci
Olivier TOUZALIN
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Priority claimed from FR1355749A external-priority patent/FR3007416B1/fr
Priority claimed from FR1453795A external-priority patent/FR3020376B1/fr
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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
    • C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • 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
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/405—Limiting CO, NOx or SOx emissions
    • 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
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2300/80—Additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the present invention relates to a process for producing gasoline with a low sulfur and mercaptan content.
  • the residual sulfur compounds generally present in the desulfurized gasoline can be separated into two distinct families: the unconverted sulfur compounds present in the feed on the one hand, and the sulfur compounds formed in the reactor by so-called recombination side reactions.
  • the majority compounds are the mercaptans resulting from the addition of H 2 S formed in the reactor on the mono-olefins present in the feed.
  • the mercaptans of chemical formula R-SH, where R is an alkyl group are also called recombinant mercaptans and generally represent between 20% and 80% by weight of the residual sulfur in the desulfurized gasolines.
  • An object of the present invention is to provide a process for the treatment of a gasoline containing sulfur, part of which is in the form of mercaptans, which makes it possible to reduce the mercaptan content of said hydrocarbon fraction while minimizing the loss of octane and the consumption of reagents such as hydrogen or extraction solvents.
  • step c) of demercaptization which can also be described as a non-desulfurizing softening step, makes it possible to produce a gasoline having a low mercaptan content specification without requiring a severe and costly hydrodesulfurization finishing step.
  • step a Another advantage of the process according to the invention comes from the fact that it makes it possible to achieve a very low content of mercaptans (eg less than 10 ppm by weight) in the final desulfurized gasoline with operating conditions for the hydrodesulfurization step. (step a) much less severe (for example significant reduction in temperature and / or operating pressure), which has the effect of limiting the loss of octane, of increasing the lifetime of the catalyst of the hydrodesulfurization step and also reduce energy consumption.
  • step a much less severe (for example significant reduction in temperature and / or operating pressure), which has the effect of limiting the loss of octane, of increasing the lifetime of the catalyst of the hydrodesulfurization step and also reduce energy consumption.
  • the group VIII metal is nickel and the group VIB metal is molybdenum.
  • the method according to the invention may include a step in which the effluent from step b) is mixed with a hydrocarbon cut chosen from an LPG cut (liquefied petroleum gas), a gasoline cut resulting from a distillation crude oil, a pyrolysis unit, a coking unit, a hydrocracking unit, an oligomerization unit and a C4 olefinic cut, and the mixture is treated in step c ).
  • a hydrocarbon cut chosen from an LPG cut (liquefied petroleum gas), a gasoline cut resulting from a distillation crude oil, a pyrolysis unit, a coking unit, a hydrocracking unit, an oligomerization unit and a C4 olefinic cut, and the mixture is treated in step c ).
  • the effluent from step c) is fractionated so as to separate an unreacted C4 olefinic cut and said unreacted C4 olefinic cut is recycled to the reactor of step c).
  • the effluent from step b) is mixed with an olefinic cut at C4 in order to promote the reaction for adding mercaptans to olefins in the softening reactor.
  • the effluent from step c) of softening is fractionated so as to separate a cut containing C4 olefins which have not reacted and said olefinic cut into C4 is recycled in the softening reactor.
  • step a) a gasoline distillation step is carried out so as to split said gasoline into at least two light and heavy gasoline cuts and the heavy gasoline cut is treated in steps a), b) and c ).
  • the effluent from step b) is mixed with the light gasoline cut from the distillation so as to produce a mixture and said mixture is treated in step c).
  • step a) a step of distilling the gasoline so as to fractionate said gasoline in at at least two light and heavy petrol cuts, the heavy petrol cut is treated in step a), the light petrol cut is mixed with the effluent from step a) so as to produce a mixture and said mixture is treated in steps b) and c).
  • the mixture with the light gasoline cuts contains up to 50% volume of the light gasoline cut.
  • a gasoline distillation step is carried out so as to split said gasoline into at least three light, intermediate and heavy gasoline cuts respectively and then the gasoline cut is processed intermediate in step a) then step b) and step c).
  • the heavy gasoline fraction resulting from the distillation is advantageously treated in a hydrodesulfurization step in a dedicated unit and then subjected to a step of softening in mercaptans after elimination of the H 2 S.
  • the step softening of the desulfurized heavy petrol cut can be carried out either in a dedicated reactor or in the same softening reactor as that which processes the intermediate petrol cut (the intermediate and heavy cuts are treated as a mixture in a softening reactor) .
  • step a) and before any possible distillation step it is also possible, before step a) and before any possible distillation step, to bring the gasoline into contact with hydrogen and a selective hydrogenation catalyst to selectively hydrogenate the diolefins contained in said gasoline into olefins.
  • This step of selective hydrogenation of diolefins can be carried out in a catalytic distillation column equipped with a section comprising a selective hydrogenation catalyst.
  • steps a) and / or c) can be implemented in reactors which are catalytic columns including at least one catalytic bed, in which both the reaction are carried out catalytic and the separation of gasoline into at least two cuts (or fraction).
  • step a) is carried out in a catalytic column
  • the sections coming from the catalytic column are sent to step b) and c) separately or as a mixture in order to lower the mercaptans content.
  • step a) is carried out in a catalytic column, only the light cut, drawn off at the head of the catalytic column which concentrates the mercaptans, is sent to steps b) and c).
  • the method further comprises a step d) in which the effluent from step c) is sent to a fractionation column and a gasoline cut with a low mercaptan content is separated at the top of the fractionation column and a section of hydrocarbons containing thioether compounds at the bottom of the fractionation column.
  • Steps c) and d) are advantageously carried out concomitantly in a catalytic distillation column comprising a catalyst bed from step c).
  • the catalyst of step a) contains at least one group VIB metal and / or at least one group VIII metal on a support having a specific surface of less than 250 m 2 / g, in which the metal content of group VIII expressed as oxide is between 0.5 and 15% by weight and the metal content of group VIB, expressed as oxide, is between 1.5 and 60% by weight relative to the weight of catalyst.
  • the catalyst of step a) comprises cobalt and molybdenum and the density of molybdenum, expressed as being the ratio between said content by weight of MoO 3 and the specific surface of the catalyst, is greater than 7.10 -4 and preferably greater than 12.10 -4 g / m 2 .
  • step c) is carried out in the absence of supply of hydrogen.
  • the invention relates to a process for the treatment of gasolines comprising all types of chemical families and in particular diolefins, mono-olefins, and sulfur-containing compounds.
  • the present invention finds its application particularly in the conversion of conversion essences, and in particular essences from catalytic cracking, catalytic cracking in a fluid bed (FCC), a coking process, a visbreaking process, or a pyrolysis process.
  • FCC fluid bed
  • gasolines from catalytic cracking units (FCC) contain, on average, between 0.5% and 5% by weight of diolefins, between 20% and 50% by weight of mono-olefins, between 10 ppm and 0, 5% sulfur weight
  • the gasoline treated generally has a boiling point of less than 350 ° C, preferably less than 300 ° C and very preferably less than 220 ° C.
  • the fillers for which the process according to the invention applies have a boiling temperature of between 0 ° C and 280 ° C, preferably between 30 ° C and 250 ° C.
  • the fillers can also contain hydrocarbons with 3 or 4 carbon atoms.
  • the hydrodesulfurization step is implemented to reduce the sulfur content of the gasoline to be treated by converting the sulfur compounds to H 2 S which is then eliminated in step b). Its implementation is particularly necessary when the feed to be desulfurized contains more than 100 ppm by weight of sulfur and more generally more than 50 ppm by weight of sulfur.
  • the hydrodesulfurization step consists in bringing the gasoline to be treated into contact with hydrogen, in one or more hydrodesulfurization reactors, containing one or more catalysts suitable for carrying out the hydrodesulfurization.
  • step a) is implemented with the aim of carrying out hydrodesulfurization selectively, that is to say with a hydrogenation rate of the mono-olefins lower than 80%, preferably less than 70% and very preferably less than 60%.
  • the operating pressure of this step is generally between 0.5 MPa and 5 MPa and preferably between 1 MPa and 3 MPa.
  • the temperature is generally between 200 ° C and 400 ° C and preferably between 220 ° C and 380 ° C.
  • the average operating temperature of each reactor is generally at least 5 ° C. higher, preferably at least 10 ° C. and very preferably at least 30 ° C. at the operating temperature of the reactor which precedes it.
  • the amount of catalyst used in each reactor is generally such that the ratio between the flow rate of gasoline to be treated expressed in m 3 per hour at standard conditions, per m 3 of catalyst (also called space speed) is between 0.5 h -1 and 20 h -1 and preferably between 1 h -1 and 15 h -1 .
  • the hydrodesulfurization reactor is operated with a space speed of between 2 h -1 and 8 h -1 .
  • the hydrogen flow rate is generally such that the ratio between the hydrogen flow rate expressed in normal m 3 per hour (Nm 3 / h) and the feed flow rate to be treated expressed in m 3 per hour at standard conditions is between 50 Nm 3 / m 3 and 1000 Nm 3 / m 3 , preferably between 70 Nm 3 / m 3 and 800 Nm 3 / m 3 .
  • the desulfurization rate which depends on the sulfur content of the feed to be treated, is generally greater than 50% and preferably greater than 70% so that the product resulting from stage a) contains less than 100 ppm by weight of sulfur and preferably less than 50 ppm by weight of sulfur.
  • the process comprises a succession of hydrodesulfurization steps, such that the activity of the catalyst of a step n + 1 is between 1% and 90% of the activity of the stage n catalyst, as taught in the document EP 1612255 .
  • Any catalyst known to a person skilled in the art capable of promoting reactions for converting organic sulfur into H 2 S in the presence of hydrogen can be used within the framework of the invention.
  • the hydrodesulfurization catalyst of step a) generally contains at least one metal from group VIB and / or at least one metal from group VIII on a support (groups VIB and VIII according to the CAS classification correspond respectively to the metals groups 6 and groups 8 to 10 of the new IUPAC classification according to CRC Handbook of Chemistry and Physics, CRC press editor, editor-in-chief DR Lide, 81st edition, 2000-2001 ).
  • group VIB metal is preferably molybdenum or tungsten and the group VIII metal is preferably chosen from nickel or cobalt.
  • the catalyst of step a) comprises cobalt and molybdenum.
  • 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 the 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 the catalyst.
  • the catalyst support is usually a porous solid, such as for example an alumina, a silica-alumina, magnesia, silica or titanium oxide, alone or as a mixture.
  • the support consists essentially of transition alumina, that is to say that it comprises at least 51% by weight, preferably at least 60% by weight, very preferably at least 80% by weight , or even at least 90% by weight of transition alumina relative to the total weight of the support. It can optionally consist only of a transition alumina.
  • the hydrodesulfurization catalyst preferably has a specific surface of less than 250 m 2 / g, more preferably less than 230 m 2 / g, and very preferably less than 190 m 2 / g.
  • a catalyst comprising molybdenum alone or in admixture with nickel or cobalt and in which the density of molybdenum, expressed as being the ratio between said content by weight of MoO 3 and the specific surface of the catalyst is greater than 7.10 -4 and preferably greater than 12.10 -4 g / m 2 .
  • a catalyst is chosen comprising cobalt and molybdenum, the density of molybdenum, expressed as being the ratio between said content by weight of MoO 3 and the specific surface area of the catalyst, is greater than 7.10 -4 and preferably greater than 12.10 -4 g / m 2 .
  • the hydrodesulfurization catalyst before sulfiding, has an average pore diameter greater than 20 nm, preferably greater than 25 nm, or even 30 nm and often between 20 and 140 nm, preferably between 20 and 100 nm, and very preferably between 25 and 80 nm.
  • the pore diameter is measured by mercury porosimetry according to standard ASTM D4284-92 with a wetting angle of 140 °.
  • the deposition of metals on the support is obtained for all methods known to those skilled in the art, such as, for example, dry impregnation, by excess of a solution containing the metal precursors. Said solution is chosen so as to be able to dissolve the metal precursors in the desired concentrations.
  • the molybdenum precursor can be molybdenum oxide, ammonium heptamolybdate.
  • cobalt mention may, for example, be made of cobalt nitrate, cobalt hydroxide, cobalt carbonate.
  • the precursors are generally dissolved in a medium allowing their solubilization in the desired concentrations. This can therefore be, depending on the case, carried out in an aqueous medium and / or in an organic medium.
  • the catalyst After introduction of the metal or metals and optionally shaping of the catalyst, the catalyst is in a first activated stage.
  • This activation can correspond either to a calcination (oxidation) then to a reduction, or to a direct reduction, or to a calcination only.
  • the calcination step is generally carried out at temperatures ranging from 100 ° C to 600 ° C and preferably between 200 ° C and 450 ° C, under an air flow.
  • the reduction step is carried out under conditions which make it possible to convert at least part of the oxidized forms of the base metal to metal. Generally, it consists in treating the catalyst under a stream of hydrogen at a temperature preferably at least equal to 300 ° C.
  • the catalyst is preferably used at least in part in its sulfurized form.
  • the introduction of sulfur can occur before or after any activation step, that is to say calcination or reduction.
  • no oxidation step of the catalyst is carried out when the sulfur or a sulfur-containing compound has been introduced onto the catalyst.
  • the sulfur or a sulfur-containing 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 the method according to the invention.
  • the catalyst is preferably sulfurized by passing a charge containing at least one sulfur compound, which once decomposed leads to the fixing of sulfur on the catalyst.
  • This charge can be gaseous or liquid, for example hydrogen containing H 2 S, or a liquid containing at least one sulfur-containing compound.
  • the sulfur-containing compound is added to the catalyst ex situ.
  • a sulfur-containing compound can be introduced onto the catalyst in the optional presence of another compound.
  • the catalyst is then dried, then transferred to the reactor used to carry out the process according to the invention. In this reactor, the catalyst is then treated under hydrogen in order to transform at least part of the main metal into sulphide.
  • a procedure which is particularly suitable for the sulfurization of the catalyst is that described in the documents. FR 2 708 596 and FR 2 708 597 .
  • step a) is carried out in a catalytic distillation column provided with a section comprising a hydrodesulfurization catalyst, in which both the catalytic hydrodesulfurization reaction and the separation are carried out gasoline in at least two cuts (or fractions).
  • the catalytic distillation column comprises two beds of hydrodesulfurization catalyst and the charge is sent to the column between the two catalyst beds.
  • This step is implemented in order to separate the excess hydrogen as well as the H 2 S formed during step a) from the effluent from step a). Any method known to a person skilled in the art can be envisaged.
  • the effluent is cooled to a temperature generally below 80 ° C and preferably below 60 ° C in order to condense the hydrocarbons.
  • the gas and liquid phases are then separated in a separation flask.
  • the liquid fraction which contains the desulfurized gasoline as well as a fraction of the dissolved H 2 S is sent to a stabilization column or debutanizer. This column separates a head section essentially consisting of residual H 2 S and of hydrocarbon compounds having a boiling temperature lower than or equal to that of butane and a bottom section stripped of H 2 S, called stabilized gasoline, containing compounds having a boiling point higher than that of butane.
  • the liquid fraction which contains the desulfurized gasoline as well as a fraction of the dissolved H 2 S is sent to a stripping section, while the gaseous fraction constituted mainly hydrogen and H 2 S is sent to a purification section.
  • the stripping can be carried out by heating the hydrocarbon fraction alone or with an injection of hydrogen or water vapor, in a distillation column in order to extract, at the top, the light compounds which have been entrained by dissolution in the liquid fraction. as well as the residual dissolved H 2 S.
  • the temperature of the stripped gasoline recovered at the bottom of the column is generally between 120 ° C and 250 ° C.
  • Step b) is preferably implemented so that the sulfur in the form of H 2 S remaining in the desulfurized gasoline, before the demercaptization (softening) step c) represents less than 30%, preferably less than 20% and more preferably less than 10% of the total sulfur present in the treated hydrocarbon fraction.
  • This step consists in transforming the sulfur compounds of the mercaptan family into heavier sulfur compounds of the thioether type.
  • These mercaptans are essentially recombinant mercaptans resulting from the reaction of the H 2 S formed in step a) with the olefins of gasoline.
  • the transformation reaction involved in this step c) consists in reacting the mercaptans on the olefins to form heavier sulfur compounds of the thioether type. It should be noted that this step is to be distinguished from a "conventional" hydrodesulfurization step which aims to transform, in the presence of hydrogen, the sulfur-containing compounds into H 2 S.
  • This step also makes it possible to convert the residual H 2 S, which would not have been completely eliminated during step b), into thioether by reaction with the olefins present in the feed.
  • the demercaptization (or softening) reaction is carried out on a catalyst comprising at least one sulfide of a metal chosen from group VIB, group VIII, copper and lead, deposited on a porous support capable of transforming the sulfur compounds of the mercaptan family, by reaction with petroleum olefins to sulfur compounds of the thioether type.
  • the catalyst comprises at least one element from group VIII (groups 8, 9 and 10 of the new periodic classification Handbook of Chemistry and Physics, 76th edition, 1995-1996 ), at least one element from group VIB (group 6 of the new periodic classification) Handbook of Chemistry and Physics, 76th edition, 1995-1996 ) and a support.
  • the element of group VIII is preferably chosen from nickel and cobalt and in particular nickel.
  • the element of group VIB is preferably chosen from molybdenum and tungsten and very preferably molybdenum.
  • the catalyst support of step c) is preferably chosen from alumina, nickel aluminate, silica, silicon carbide, or a mixture of these oxides.
  • Alumina is preferably used, and even more preferably alumina is used. pure.
  • a support is used which has a total pore volume measured by mercury porosimetry of between 0.4 and 1.4 cm 3 / g and preferably between 0.5 and 1.3 cm 3 / g.
  • the specific surface of the support is preferably between 70 m 2 / g and 350 m 2 / g.
  • the support is a cubic gamma alumina or a delta alumina.
  • a very preferred embodiment of the invention corresponds to the use for step c) of a catalyst containing a content by weight relative to the total weight of nickel oxide catalyst (in NiO form) between 4 and 12%, a content by weight relative to the total weight of molybdenum oxide catalyst (in MoO 3 form) of between 6% and 18%, a nickel / molybdenum molar ratio of between 1 and 2.5, the metals being deposited on a support consisting solely of gamma alumina with a specific surface of between 180 m 2 / g and 270 m 2 / g and the sulfurization rate of the metals constituting the catalyst being greater than 80%.
  • the catalyst for step c) can be prepared using any technique known to those skilled in the art, and in particular by impregnating the metals on the selected support.
  • the latter After introduction of the metals, and possibly shaping of the catalyst, the latter undergoes an activation treatment.
  • This treatment generally aims to transform the molecular precursors of the elements in the oxide phase. In this case it is an oxidizing treatment but a simple drying of the catalyst can also be carried out.
  • an oxidizing treatment also called calcination, it is generally carried out in air or under dilute oxygen, and the treatment temperature is generally between 200 ° C and 550 ° C, preferably between 300 ° C and 500 ° C.
  • the metals deposited on the support are in the form of oxide.
  • the metals are mainly found in the form of MoO 3 and NiO.
  • the sulfurization is preferably carried out in a sulforeductive medium, that is to say in the presence of H 2 S and of hydrogen, in order to transform the metal oxides into sulphides such as for example, MoS 2 and Ni 3 S 2 .
  • Sulfurization is carried out by injecting a flux containing H 2 S and hydrogen onto the catalyst, or else a sulfur-containing compound capable of decomposing into H 2 S in the presence of the catalyst and hydrogen.
  • Polysulfides such as dimethyldisulfide (DMDS) are precursors of H 2 S commonly used to sulfurize catalysts.
  • the temperature is adjusted so that the H 2 S reacts with the metal oxides to form metal sulfides.
  • This sulfurization can be carried out in situ or ex situ (inside or outside the reactor) of the demercaptization reactor, at a temperature between 200 ° C and 600 ° C and more preferably between 300 ° C and 500 ° C.
  • Step c) of softening in mercaptans consists in bringing the desulphurized gasoline and freed of at least part of the H 2 S into contact with the catalyst in sulphide form.
  • the demercaptization reactions according to the invention are characterized by a reaction of the mercaptans on the olefins via a direct addition on the double bond to produce compounds of the thioether type, of formula R1-S-R2 with R1 and R2 being alkyl radicals, whose boiling point is higher than that of the starting mercaptans.
  • This softening step can be carried out in the absence (without addition or addition of hydrogen) or in the presence of hydrogen supplied to the reactor. Preferably, it is carried out in the absence of hydrogen supply. When hydrogen is used, this is injected with the charge so as to maintain a hydrogenating surface state of the catalyst suitable for high conversions to demercaptization.
  • step c) operates with a H 2 / feed ratio of between 0 and 10 Nm 3 of hydrogen per m 3 of feed, very preferably between 0 and 5 Nm 3 of hydrogen per m 3 of feed, and even more preferably between 0 and 2 Nm 3 of hydrogen per m 3 of feed.
  • the entire charge is generally injected at the inlet of the reactor. However, it may be advantageous in certain cases to inject a fraction or all of the charge between two consecutive catalytic beds placed in the reactor.
  • the gasoline to be treated is brought into contact with the catalyst at a temperature between 30 ° C and 250 ° C, and preferably between 60 ° C and 220 ° C, and even more preferably between 90 ° C and 200 ° C, with a liquid space speed (LHSV) of between 0.5 h -1 and 10 h -1 , the unit of the liquid space speed being the liter of feed per liter of catalyst and per hour (l / lh).
  • the pressure is between 0.2 MPa and 5 MPa, preferably between 0.5 and 2 MPa and even more preferably between 0.6 and 1 MPa.
  • the mercaptans which combine with the olefins of the feed to form thioether compounds have a carbon number typically between 5 and 12 and are more generally branched.
  • the mercaptans which may be contained in the feed of step c) are 2-methylhexan-2-thiol, 4-methylheptan-4-thiol, 2-ethyl-hexan-3-thiol or 2,2,4-trimethylpentan-4-thiol.
  • the hydrocarbon fraction treated under the conditions set out above therefore has a reduced mercaptan content (the latter have been converted to thioether compounds).
  • the gasoline produced at the end of step c) contains less than 20 ppm by weight of mercaptans, and preferably less than 10 ppm by weight, and even more preferably less than 5 ppm by weight.
  • the olefins are not or very little hydrogenated, which makes it possible to maintain a good octane number of the effluent at the outlet of the step vs).
  • the rate of hydrogenation of olefins is generally less than 2%.
  • step c) the gasoline treated under the conditions set out above therefore has a reduced content of mercaptans. Indeed the latter were converted into compounds of the thioether type whose molecular point is higher than the starting mercaptans.
  • a fractionation step (step d) of the gasoline softened into mercaptans is carried out into at least one light cut and one heavy cut of hydrocarbons.
  • This fractionation step is carried out under conditions such that the sulfur-containing compounds of the thioether type formed in step c) and optionally the heaviest and most refractory residual mercaptans which have not reacted during step c) concentrate in heavy cutting of hydrocarbons.
  • the fractionation step is carried out in such a way that the light cutting of hydrocarbons with a low sulfur content, in particular mercaptans and sulphide compounds, has a final boiling temperature of between 130 and 160 ° C. .
  • the cutting point ie the final boiling temperature of the light cut of hydrocarbons
  • the light petrol cut has a mercaptan content of less than 10 ppm by weight, preferably less than 5 ppm by weight and more preferably less than 1 ppm by weight and a total sulfur content of less than 50 ppm by weight, preferably less than 20 ppm by weight and more preferably less than 10 ppm by weight.
  • the light cut of hydrocarbons with low sulfur and mercaptan content is advantageously sent to the petrol pool of the refinery.
  • hydrodesulfurization which applies more severe hydrotreatment conditions (higher temperature, higher quantity of hydrogen used) or is alternatively sent to the diesel pool of the refinery.
  • step c) and the fractionation (step d) can be carried out simultaneously by means of a catalytic column equipped with a catalytic bed containing the softening catalyst.
  • the catalytic distillation column has two softening catalyst beds and the charge is sent to the column between the two catalyst beds.
  • step c) of catalytic softening can be implemented directly in series with step b) of separation.
  • step b) of separation is carried out at a temperature compatible with the operating temperature of step c) of catalytic softening
  • the effluent from step b) is sent directly in step c). It can also be envisaged to adjust the temperature between steps b) and c) by means of heat exchange devices.
  • a mixture of the gasoline obtained from step b) is mixed with an LPG cut (liquefied petroleum gas) or another gasoline cut containing sulfur.
  • LPG cut liquefied petroleum gas
  • another gasoline cut containing sulfur such as, for example, petroleum distillation essences, essences resulting from any cracking process such as essences resulting from pyrolysis, coking or hydrocracker processes, or a essence originating from an oligomerization unit and then the mixture is treated in step c).
  • LPG cut liquefied petroleum gas
  • another gasoline cut containing sulfur such as, for example, petroleum distillation essences, essences resulting from any cracking process such as essences resulting from pyrolysis, coking or hydrocracker processes, or a essence originating from an oligomerization unit.
  • step c) softening the essence from step b) mixed with a cut C4 olefinic hydrocarbons to promote the catalytic reaction of addition of mercaptans (recombination) with olefins.
  • a step of distilling the gasoline to be treated is carried out in order to separate two cuts (or fractions), namely a light cut and a heavy cut, and the heavy cut is treated according to the process of the invention.
  • the heavy cut is treated by hydrodesulfurization (step a), then the H 2 S formed present in the heavy hydrodesulfurized cut (step b) is separated, then the light cut (after the distillation) with the heavy cut from step b) and finally the mixture is treated in step c).
  • a light cut is mixed with the heavy hydrodesulfurized cut from step a), the mixture thus obtained is treated in step b) and c) .
  • This third variant has the advantage of not hydrotreating the light cut which is rich in olefins and generally poor in sulfur, which makes it possible to limit the loss of octane by hydrogenation of the olefins.
  • the charge treated in step c) consists of the entire desulfurized heavy cut and a portion of between 0 and 50% volume of the light cut.
  • the light cut has a boiling temperature range of less than 100 ° C. and the heavy cut has a temperature range of more than 65 ° C.
  • a distillation of the gasoline is carried out in two cuts: a first light cut and a first heavy cut of hydrocarbons.
  • the first light cut has a boiling temperature between the initial boiling temperature of the gasoline to be treated and a final boiling temperature between 140 ° C and 160 ° C.
  • the first light cut of hydrocarbons is then treated by hydrodesulfurization (step a), then the H 2 S formed is separated from the hydrodesulfurized effluent (step b), the hydrodesulfurized effluent is softened in mercaptans (step c) and splits the softened effluent into mercaptans (step d) so as to produce a second light gasoline cut (the boiling temperature of which is between the initial boiling temperature of the gasoline to be treated and a lower final boiling temperature or equal to 140 ° C.) with a low content of mercaptans and thioethers and a second heavy cut of hydrocarbons containing thioethers and unconverted mercaptans.
  • the first and second heavy cuts of hydrocarbons can be mixed and treated by hydrodesulfurization in a dedicated unit.
  • a distillation of the gasoline is carried out in three light, intermediate and heavy cuts of hydrocarbons using one or more columns to be distilled.
  • the light cut of hydrocarbons preferably has a boiling temperature between the initial boiling temperature of the gasoline to be treated and a final boiling temperature between 50 ° C and 90 ° C.
  • Such a light cut of hydrocarbons generally contains little sulfur and therefore can be directly valued at the petrol pool of the refinery.
  • the intermediate cut of hydrocarbons which has a range of boiling temperatures generally between 50 ° C and 140 ° C or 160 ° C is treated by hydrodesulfurization (step a), then the H 2 S formed is separated from the hydrodesulfurized effluent (step b), the softened hydrodesulfurized effluent (step c) is softened into mercaptans and the softened effluent is separated into mercaptans (step d) so as to produce a second intermediate gasoline fraction low in mercaptans and thioethers and a second heavy cut of hydrocarbons containing thioethers and unconverted mercaptans.
  • the first and second heavy cuts of hydrocarbons can be mixed and treated by hydrodesulfurization in a dedicated unit.
  • the gasoline to be treated is first subjected to a prior step consisting in a selective hydrogenation of the diolefins present in the feed, as described in the application for EP 1077247 .
  • the selectively hydrogenated gasoline is then distilled in at least two cuts or three cuts of hydrocarbons, a light cut, an intermediate cut and a heavy cut.
  • the steps described above in the case of the third and fourth variants are applicable.
  • the intermediate fraction is treated separately in a hydrodesulfurization stage (stage a), then a stage of separation of H 2 S (stage b) and then in a stage d softening (step c).
  • the effluent from step c) is subjected to a fractionation step d) so as to produce a second intermediate gasoline fraction low in mercaptans and thioethers content and a second heavy fraction of hydrocarbons containing thioethers and non-mercaptans. converted.
  • the second heavy cut of hydrocarbons is mixed with the heavy cut resulting from the distillation upstream of the hydrodesulfurization step and the mixture is treated by hydrodesulfurization in a dedicated unit.
  • step a) is carried out in a catalytic distillation column incorporating a bed of hydrodesulfurization catalyst allowing simultaneously to desulfurize the gasoline and to separate it into two light and heavy cuts of hydrocarbons.
  • the sections produced are then sent in steps b) and c) separately or as a mixture.
  • steps b) and c) only the light gasoline fraction from the catalytic hydrodesulfurization distillation column is treated in steps b) then c).
  • the effluent from step c) can be split into two hydrocarbon fractions in accordance with step d) described above.
  • the heavy cut from the hydrodesulfurization catalytic distillation column can be treated in a second hydrodesulfurization unit, alone or in mixture with the heavy cut from step d) of fractionation of the gasoline cut. light from the catalytic hydrodesulfurization distillation column.
  • step c) In the cases where step c) is carried out on the light cut, in order to improve the conversion rate of the mercaptans (of recombination) into thioether during step c), a mixture of an olefinic cut in C4 is advantageously carried out upstream of step c) with light gasoline so that step c) is advantageously carried out on a mixture containing the light cut of hydrocarbons and an olefinic cut in C4 and not the light cut alone .
  • the effluent softened in mercaptans is sent to a separation column which separates an olefinic cut C4 and a light cut softened in mercaptans.
  • the olefinic cut C4 withdrawn from the separation column is advantageously recycled in the reactor of step c).
  • step c) is carried out on an intermediate or heavy cut, in order to improve the rate of conversion of the mercaptans (of recombination) into thioether during step c), all or part of the light gasoline is advantageously added to the intermediate or heavy cut upstream of step c) so that step c) is advantageously carried out on a mixture containing olefins provided by the light cut of hydrocarbons.
  • the gasoline to be treated is sent by line 1 and hydrogen by line 3 in a hydrodesulfurization unit 2.
  • the gasoline treated is generally a gasoline cracking, preferably a catalytic cracking essence.
  • Gasoline is characterized by a boiling temperature typically ranging between 30 ° C and 220 ° C.
  • the hydrodesulfurization unit 2 is for example a reactor containing a hydrodesulfurization catalyst (HDS) in a fixed bed or in a fluidized bed, preferably a reactor in a fixed bed is used. The reactor is operated under operating conditions and in the presence of an HDS catalyst, as described above to decompose the sulfur compounds and form hydrogen sulfide (H 2 S).
  • HDS hydrodesulfurization catalyst
  • an effluent (gasoline) containing H 2 S is removed from said hydrodesulfurization reactor 2 via line 4.
  • the effluent is then subjected to a step of removing H 2 S (step b) which consists, in the embodiment of the figure 1 ,
  • step b To treat the effluent in a stabilization column 5 in order to separate the head of the column via line 6 a stream containing C4 hydrocarbons - the majority of H 2 S and unreacted hydrogen and bottom of the column a so-called stabilized gasoline.
  • the stabilized petrol is sent via line 7 to a softening reactor 8 (step c) in order to reduce the mercaptan content of the stabilized petrol.
  • the mercaptans contained in this stabilized gasoline are mainly recombinant mercaptans resulting from the reaction of H 2 S on olefins.
  • the softening reactor implements a catalyst making it possible to carry out the reaction for adding mercaptans to olefins via direct addition to the double bond to produce compounds of the thioether type, of formula R1-S -R2 with R1 and R2 being alkyl radicals, of molecular weight is higher than that of the starting mercaptan.
  • the catalytic reaction for converting mercaptans can optionally be carried out in the presence of hydrogen supplied by line 9.
  • the gasoline stabilized and softened in mercaptans drawn off by line 10 of the reactor 8 is advantageously sent to a separation column 11 which is designed and operated to separate at the head (via line 12) a light stabilized gasoline whose temperature range boiling is preferably between 30 ° C and 160 ° C or between 30 ° C and 140 ° C and which has mercaptan contents and in total sulfur respectively less than 10 ppm by weight and 50 ppm by weight.
  • a heavy petrol is recovered via line 13 which contains the thioether type compounds formed in the softening reactor 8.
  • the light petrol is sent to the petrol pool while the heavy petrol is either hydrodesulfurized in a dedicated hydrotreating unit, or sent to the diesel or distillate pool of the refinery.
  • the figure 2 represents a second embodiment based on that of the figure 1 and which is differentiated by the fact that the stabilized gasoline is treated in the mercaptans softening reactor 8 in the presence of an olefinic hydrocarbon cut, preferably a C4 olefinic cut, provided by line 14.
  • an olefinic hydrocarbon cut preferably a C4 olefinic cut, provided by line 14.
  • the purpose the addition of this olefinic cut is to promote the addition reaction of mercaptans on olefins by providing reactive olefins in the reaction medium.
  • the effluent from the softening reactor is sent to a separation column 15 in order to recover the fraction of the olefinic cut which has not reacted in the softening reactor 8.
  • the separation column 15 used is equivalent to a debutanizer which separates at the head of column 15 a cut C4 which is recycled in the softening reactor 8 via line 16.
  • the bottom cut 17 recovered from column 15 is fractional in column 11 as described under figure 1 in order to provide a light gasoline cut low in sulfur and mercaptans content via line 12 and a heavy gasoline cut containing the thioether compounds formed in the softening reactor 8.
  • the figure 3 illustrates a third embodiment of the method according to the invention.
  • the gasoline charge to be treated which typically comprises hydrocarbons boiling between 30 ° C. and 220 ° C.
  • the gasoline charge to be treated which typically comprises hydrocarbons boiling between 30 ° C. and 220 ° C.
  • a distillation column 20 configured to split the gasoline charge into three sections.
  • a head section comprising the compounds lighter than butane and including the latter is drawn off by line 21.
  • An intermediate section comprising the hydrocarbons having 6 to 7 or 6 to 8 carbon atoms is recovered by line 22.
  • a bottom section consisting of hydrocarbons having a number of carbon atoms greater than 7 or 8 carbon atoms is drawn off by line 23.
  • the petrol charge before being fractionated is advantageously pretreated in a selective hydrogenation reactor 19 of the diolefins to olefins.
  • This catalytic reaction is preferably carried out under the conditions and in the presence of a catalyst as described in the documents. EP 1445299 or EP 1800 750 .
  • the bottom section is treated in a hydrodesulfurization reactor 24 in the presence of hydrogen (supplied by line 25) and a hydrodesulfurization catalyst as described above.
  • the desulphurized effluent is withdrawn from reactor 24 by line 26 and sent to a separation unit 27 of H 2 S, such as for example a stripping column, from which a gas fraction is separated by line 28 essentially containing H 2 S and hydrogen and a low sulfur bottom section through line 29.
  • the intermediate petrol cut is treated by the method according to the invention.
  • the intermediate gasoline cut is sent via line 22 to a hydrodesulfurization reactor 2 to be desulfurized there in the presence of hydrogen supplied by line 3.
  • the effluent from reactor 2 is freed of the H 2 S formed during from the HDS stage in a separation unit 5.
  • the intermediate gasoline depleted in H 2 S is sent via line 7 with optionally hydrogen brought by line 9 into a mercaptan softening reactor 8.
  • the section intermediate gasoline softened in mercaptans is sent via line 10 to a fractionation column 11 operated to separate an intermediate gasoline cut with low mercaptans and sulfur content and an intermediate bottom cut. re in which the thioether compounds produced during the softening stage are concentrated.
  • the intermediate gasoline cut with low mercaptans and sulfur content is evacuated by line 12 to the petrol pool of the refinery while the intermediate bottom cut evacuated by line 13 is either desulphurized in a hydrotreating unit (for example a diesel hydrodesulfurization unit), or sent directly to the refinery's diesel pool.
  • a hydrotreating unit for example a diesel hydrodesulfurization unit
  • the intermediate bottom cut 13 can be desulphurized in the hydrodesulphurization reactor 24 in admixture with the bottom cut 23 resulting from the first fractionation step carried out in column 20.
  • the figure 4 discloses a fourth embodiment of the process according to the invention using catalytic distillation columns.
  • the petrol charge for example a cut of hydrocarbons boiling between 30 ° C and 220 ° C or between 30 ° C and 160 ° C, or even between 30 ° C and 140 ° C, is sent by line 1 in a first column catalytic distillation 40 comprising a reaction section 41 containing a catalyst for the selective hydrogenation of diolefins.
  • the hydrogen necessary for the conduct of the hydrogenation reaction is supplied via line 2.
  • the use of the catalytic column 40 makes it possible to carry out not only the catalytic reaction of selective hydrogenation but also the fractionation into a section of light hydrocarbons at the top of the column and a cut of heavy hydrocarbons at the bottom of the column 40.
  • the cut of light hydrocarbons in mixture with unreacted hydrogen is drawn off by line 42 and the cut of heavy hydrocarbons is drawn off by line 43.
  • the light cut is for example a C4 cut - and the heavy hydrocarbon cut is a boiling cut in the range (C5 - 220 ° C) or (C5 - 160 ° C) or (C5 - 140 ° VS).
  • the cut of heavy hydrocarbons is then treated according to the process of the invention which consists of a hydrodesulfurization step carried out, in this embodiment, in a catalytic distillation column 45 comprising two beds of hydrodesulfurization catalysts. preferably the cut of heavy hydrocarbons is injected with hydrogen (via line 44) between the two beds of hydrodesulfurization catalysts 46.
  • the catalytic distillation column 45 also makes it possible to split the cut of heavy hydrocarbons into one intermediate head cup boiling in the range (C5 - 140 ° C) or (C5 - 160 ° C) and a bottom cup whose boiling temperature is higher than 140 ° C or 160 ° C respectively.
  • the latter in order to reduce the mercaptan content of the intermediate cut, the latter is evacuated via line 47 and subjected to a step of removing H 2 S by means of the stabilization column 5 in order to separate at the top of the column via line 6 a stream containing the majority of the H 2 S and at the bottom of the column via line 7 the stabilized intermediate section.
  • the latter is treated in a softening reactor 8.
  • the intermediate cut softened in mercaptans from reactor 8 is then via line 10 fractionated in column 11 so as to recover at the top (via line 12) a low-content gasoline sulfur, mercaptans and thioethers boiling in the range (C5 - 140 ° C) or (C5 - 160 ° C).
  • the bottom section which contains the sulphides generally comprising at least 10 carbon atoms and more, products of the reaction for adding mercaptans to olefins, is drawn off by line 13 from the bottom of column 11.
  • the intermediate cut is treated in the softening reactor 8 in admixture with the cut of light hydrocarbons, via line 49, coming from the head of the catalytic distillation column 40.
  • the intermediate cut softened in mercaptans from the reactor 8 can optionally undergo a stabilization step carried out in a stabilization column 31 from which a cut C4 is extracted - and a stabilized intermediate cut softened in mercaptans, respectively at the head and at bottom of said column 31.
  • the stabilized intermediate section softened in mercaptans is then sent by line 33 to the fractionation column 11.
  • the mercaptan softening step and the fractionation can be carried out simultaneously by means of a catalytic column equipped with a catalytic bed containing the softening catalyst.
  • a hydrodesulfurization catalyst A is obtained by impregnating “without excess solution” with a transition alumina in the form of beads with a specific surface of 130 m 2 / g and a pore volume of 0.9 ml / g, with a aqueous solution containing molybdenum and cobalt in the form of ammonium heptamolybdate and cobalt nitrate respectively.
  • the catalyst is then dried and calcined in air at 500 ° C.
  • the cobalt and molybdenum content of this sample is 3% by weight of CoO and 10% by weight of MoO 3 .
  • catalyst A 50 ml of catalyst A are placed in a tubular hydrodesulfurization reactor with a fixed bed.
  • the catalyst is first sulfurized by treatment for 4 hours under a pressure of 3.4 MPa at 350 ° C, in contact with a charge consisting of 2% by weight of sulfur in the form of dimethyldisulfide in n-heptane.
  • the treated charge C1 is a catalytic cracking gasoline whose initial boiling point is 55 ° C, the end point is 242 ° C, whose MON is 79.8 and the RON is 89.5. Its sulfur content is 359 ppm by weight.
  • This charge is treated on catalyst A, under a pressure of 2 MPa, with a hydrogen volume ratio on charge to be treated (H 2 / HC) of 360 l / l and a space velocity (VVH) of 4 h -1 .
  • H 2 / HC hydrogen volume ratio on charge to be treated
  • VVH space velocity
  • Table 1 shows the influence of the temperature on the desulfurization rates, and on the octane number by catalyst A at a hydrodesulfurization temperature of 240 ° C (A1) or 270 ° C (A2).
  • Table 1 Hydrodesulfurized gasoline A1 A2 HDS temperature (° C) 240 270 H 2 S, ppm weight 0.5 0.5 Mercaptans, ppm weight (as S) 24 11 Total sulfur, ppm weight 86 19 Total olefins,% by weight 24.6 20.4 Desulfurization rate,% 76.2 94.6 Delta MON 1.1 2.3 Delta RON 1.5 3.9
  • the hydrodesulfurization of the feed C1 with the catalyst A makes it possible to reduce the total sulfur content but also the mercaptans content. It should be noted that it is necessary to treat the charge at a temperature of at least 270 ° C to reach approximately 11 ppm by weight of mercaptans. This increase in the temperature of the hydrodesulfurization reaction also has the effect of promoting the hydrogenation reaction of the olefins which results in a decrease in the total olefin content in the hydrodesulfurized gasoline.
  • Catalyst B is obtained by impregnating a nickel aluminate with a specific surface of 135 m 2 / g and a pore volume of 0.45 ml / g, with an aqueous solution containing molybdenum and nickel. The catalyst is then dried and calcined in air at 500 ° C. The nickel and molybdenum content of this sample is 7.9% by weight of NiO and 13% by weight of MoO 3 .
  • the gasoline A1 as obtained and described in Example 1 is treated in the absence of hydrogen on the demercaptization catalyst B, at a pressure of 1 MPa, a VVH of 3 h -1 and a temperature of 100 ° C. After treatment, the gasoline B1 obtained is cooled.
  • Table 2 presents the main characteristics of the B1 gasoline obtained. Table 2 References of the treated species B1 H 2 S, ppm weight 0 Mercaptans, ppm weight (as S) 8 Total sulfur, ppm weight 86 Total olefins,% by weight 24.6 Demercapture rate,% 67 Hydrogenation rate of olefins,% 0
  • step c The implementation of the demercaptization step (step c) thus makes it possible to convert the mercaptans of essence A1 without hydrogen and without hydrogenating the olefins.
  • a catalyst D is obtained by impregnating an alumina with a specific surface of 239 m 2 / g and a pore volume 0.6 ml / g, with an aqueous solution containing molybdenum and nickel. The catalyst is then dried and calcined in air at 500 ° C. The nickel and molybdenum content of this sample is 9.5% by weight of NiO and 13% by weight of MoO 3 .
  • the essence A1 as obtained and described in example 1 is mixed with a charge C2 to obtain a charge C3.
  • the charge C2 is a light cracked gasoline having undergone a selective hydrogenation of the diolefins, whose initial boiling point is 22 ° C and the end point is 71 ° C, whose MON is 82.5 and RON is 96.9. Its sulfur content is 20 ppm by weight, its mercaptan content less than 3 ppm by weight and its olefin content by 56.7% by weight.
  • the charge C3 is obtained by mixing 80% by weight of gasoline A1 with 20% by weight of charge C2.
  • the mixture obtained is a gasoline with an initial boiling point of 22 ° C and a final point of 242 ° C. Its sulfur content is 73 ppm, its mercaptan content is 19 ppm by weight and its olefin content is 31% by weight.
  • Charge C3 is treated in the presence of hydrogen on the demercaptization catalyst D, under a pressure of 1 MPa, a VVH of 3 h -1 , with a hydrogen by charge ratio of charge to be treated (H 2 / HC) of 2 l / l and a temperature of 100 ° C.
  • the gasoline mixture is cooled so as to recover a gas phase rich in hydrogen and H 2 S and a fraction of liquid gasoline.
  • the liquid fraction is subjected to a stripping treatment by injection of a stream of hydrogen in order to remove any traces of H 2 S dissolved in the gasoline.
  • Table 3 presents the main characteristics of D1 gasoline obtained after stripping. References of hydrodesulfurized gasoline D1 Temperature, ° C 100 Mercaptans, ppm weight 4 Total sulfur, ppm weight 73 Total olefins,% by weight 31 Demercapture rate,% 79 Hydrogenation rate of olefins,% 0
  • the process makes it possible to reduce the content of mercaptans in gasoline A1 by converting them selectively into thioethers, without hydrogenation of the olefins and therefore without loss of octane.

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  • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
EP14305833.7A 2013-06-19 2014-06-02 Procédé de production d'une essence à basse teneur en soufre et en mercaptans Active EP2816094B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1355749A FR3007416B1 (fr) 2013-06-19 2013-06-19 Procede de production d'une essence a basse teneur en soufre et en mercaptans
FR1453795A FR3020376B1 (fr) 2014-04-28 2014-04-28 Procede de production d'une essence a basse temperature en soufre et en marcaptans.

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EP2816094B1 true EP2816094B1 (fr) 2020-04-29

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EP (1) EP2816094B1 (zh)
KR (1) KR102322556B1 (zh)
CN (1) CN104232156B (zh)
BR (1) BR102014014718B1 (zh)
RU (1) RU2665701C2 (zh)

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Publication number Priority date Publication date Assignee Title
FR3035117B1 (fr) * 2015-04-15 2019-04-19 IFP Energies Nouvelles Procede d'adoucissement en composes du type sulfure d'une essence olefinique
FR3049955B1 (fr) * 2016-04-08 2018-04-06 IFP Energies Nouvelles Procede de traitement d'une essence
FR3056599B1 (fr) * 2016-09-26 2018-09-28 IFP Energies Nouvelles Procede de traitement d'une essence par separation en trois coupes.
FR3057578B1 (fr) * 2016-10-19 2018-11-16 IFP Energies Nouvelles Procede d'hydrodesulfuration d'une essence olefinique.
FR3075072B1 (fr) 2017-12-14 2021-11-26 Ifp Energies Now Catalyseur d'hydrodesulfuration selective des essences de fcc
FR3099173B1 (fr) * 2019-07-23 2021-07-09 Ifp Energies Now Procédé de production d'une essence a basse teneur en soufre et en mercaptans
FR3099175B1 (fr) 2019-07-23 2021-07-16 Ifp Energies Now Procédé de production d'une essence a basse teneur en soufre et en mercaptans
FR3108333B1 (fr) * 2020-03-20 2022-03-11 Ifp Energies Now Procédé de production d'une essence a basse teneur en soufre et en mercaptans

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FR2708597B1 (fr) 1993-07-30 1995-09-29 Inst Francais Du Petrole Procédé d'isomérisation d'oléfines sur des catalyseurs métalliques imprégnés de composés organiques soufrés avant chargement dans le réacteur.
FR2708596B1 (fr) 1993-07-30 1995-09-29 Inst Francais Du Petrole Procédé d'isomérisation d'oléfines externes en oléfines internes conjointement à l'hydrogénation des dioléfines.
FR2797639B1 (fr) 1999-08-19 2001-09-21 Inst Francais Du Petrole Procede de production d'essences a faible teneur en soufre
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Publication number Publication date
CN104232156A (zh) 2014-12-24
RU2014124384A (ru) 2015-12-27
US20140374315A1 (en) 2014-12-25
US9957448B2 (en) 2018-05-01
BR102014014718A2 (pt) 2015-06-02
EP2816094A1 (fr) 2014-12-24
KR20140147737A (ko) 2014-12-30
RU2665701C2 (ru) 2018-09-04
CN104232156B (zh) 2018-12-07
KR102322556B1 (ko) 2021-11-04
BR102014014718B1 (pt) 2021-02-09

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